Engineering Materials

Engineering Materials
Pietro Pedeferri
Corrosion
Science and
Engineering
Edited by Luciano Lazzari and
MariaPia Pedeferri
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Pietro Pedeferri
Corrosion Science
and Engineering
Edited by Luciano Lazzari and MariaPia Pedeferri
In Cooperation with Marco Ormellese, Andrea Brenna,

Silvia Beretta, Fabio Bolzoni, Maria Vittoria Diamanti
123
Pietro Pedeferri (Deceased)
Politecnico di Milano
Milan, Italy
ISSN 1612-1317 ISSN 1868-1212 (electronic)

ISBN 978-3-319-97624-2 ISBN 978-3-319-97625-9 (eBook)
https://doi.org/10.1007/978-3-319-97625-9
Library of Congress Control Number: 2018950812
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Preface
This Pedeferri’s Corrosion Science and Engineering textbook is the English edition
of Pietro Pedeferri’s Corrosione e Protezione dei Materiali, Polipress, Milano
(2007), with many integrations made by his collaborators of the PoliLaPP, the
Laboratory of Corrosion of Materials that Pedeferri founded. The main goal while
translating and integrating the original Italian book, so far very appreciated in Italy
with about 2000 copies printed, is to give a modern and updated handbook on
corrosion and corrosion prevention for a twofold use: as a teaching textbook and a
modern, technical support for industrial applications. This textbook stands as an
ideal learning resource for students of corrosion courses in chemical, mechanical,
energy and materials engineering at graduate and advanced undergraduate levels, as
well as a valuable reference for engineers.
This English edition, integrated and updated, contains 30 chapters, dealing with
corrosion theory (9 chapters), forms of corrosion (7), corrosion control and pre-
vention methods (3), applications in different environments as waters, air, soil,
concrete (4), and industrial applications as petrochemical plants, refinery and high
temperature (2) as well as corrosion of implants in the human body. Four chapters
are dedicated to design, corrosion monitoring, laboratory tests and the statistical
processing of corrosion data. Chapters dedicated to the on-field applications pro-
pose an overview of the most used metals and relevant case histories. Emphasis has
been devoted to cathodic protection and corrosion of reinforced concrete to give
merit to the pioneering works carried out by Pietro Pedeferri. Each chapter is
enriched by pictures of corrosion case studies analysed by PoliLaPP; most of the
samples are actually available at the “Corrosion Museum”, where Pietro Pedeferri
and his school have collected the most significant corrosion case studies.
The book offers the reader and the user many case histories and an important
number of questions and exercises to help check the acquired knowledge. Questions
and exercises included in each chapter represent the experience gathered by
Pedeferri and his school over the last 50 years as a fruit of teaching, research,
consultancy on material selection, failure analysis and corrosion engineering.
Answers and solutions of exercises for readers will be available on PoliLaPP
website (http://polilapp.chem.polimi.it).
v
vi Preface
Finally, a warm thank to all collaborators Andrea Brenna Silvia Beretta, Fabio
Bolzoni, Maria Vittoria Diamanti for their hard, precious and tenacious work in
contributing to the translation, integration and revision of the chapters and the effort
spent on collecting more than 300 exercises. Special mention to Marco Ormellese
for the unparalleled contribution. Thanks to Roberto Chiesa for reviewing the
chapter related to corrosion in the human body, Giorgio Re for the suggestions on
chapters dedicated to environmental-assisted cracking, Eleonora Faccioli for the
drawing of figures and tables and Davide Prando for the collection of the original
pictures.
Milan, Italy Luciano Lazzari

June 2018 MariaPia Pedeferri
Contents
1 General Principles of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Corrosion as Metallurgy in Reverse . . . . . . . . . . . . . . . . . . . . 2
1.2 The Economic Impact of Corrosion . . . . . . . . . . . . . . . . . . . . 3
1.3 Corrosion Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.1 Uniform or Generalized Corrosion . . . . . . . . . . . . . . 5
1.3.2 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.3 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . 7
1.4 Corrosion Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4.1 Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.5 Corrosion Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2 Electrochemical Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1 Electrochemical Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2 Historical Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1 Evans’s Experiences . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3 Local Cell Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3.1 Mixed Potential Theory . . . . . . . . . . . . . . . . . . . . . . 24
2.4 Corrosion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.1 Anodic Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.2 Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.4.3 Other Cathodic Processes . . . . . . . . . . . . . . . . . . . . 27
2.4.4 Complementary Processes . . . . . . . . . . . . . . . . . . . . 27
2.5 Stoichiometry (Faraday Law) . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5.1 Corrosion Current Density . . . . . . . . . . . . . . . . . . . . 28
2.6 Change of the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
vii
viii Contents
3 Thermodynamics of Aqueous Corrosion . . . . . . . . . . . . . . . . . . . . . 37

3.1 Driving Voltage and Free Energy . . . . . . . . . . . . . . . . . . . . . . 38
3.2 Corrosion and Immunity Condition . . . . . . . . . . . . . . . . . . . . 39
3.3 Standard Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.4 Potential of an Electrochemical Reaction . . . . . . . . . . . . . . . . 43
3.5 Potential of Metal Dissolution Reaction . . . . . . . . . . . . . . . . . 44
3.5.1 Corrosion and Immunity Conditions . . . . . . . . . . . . 45
3.6 Potential of Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . 45
3.6.1 Potential of Hydrogen Evolution Reaction . . . . . . . . 46
3.6.2 Potential of Oxygen Reduction Reaction . . . . . . . . . 47
3.6.3 Applications of Thermodynamic Criteria . . . . . . . . . 48
3.7 Insoluble Products and Complexing Species . . . . . . . . . . . . . . 50
3.8 Reference Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.9 Electrochemical Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.9.1 Concentration Cells . . . . . . . . . . . . . . . . . . . . . . . . . 53
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4 Pourbaix Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.1 Oxygen Reduction and Hydrogen Evolution . . . . . . . . . . . . . . 58
4.2 Metal Immunity, Corrosion and Passivation . . . . . . . . . . . . . . 58
4.2.1 Equilibrium Between Immunity and Corrosion . . . . . 59
4.2.2 Equilibrium Between Immunity and Passivation . . . . 61
4.2.3 Equilibrium Between Corrosion and Passivation . . . . 62
4.3 Amphoteric Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.3.1 Electrochemical Dissolution in Alkaline Solution . . . 63
4.3.2 Chemical Dissolution in Alkaline Solution . . . . . . . . 64
4.4 Pourbaix Diagrams of Some Metals at 25 °C . . . . . . . . . . . . . 64
4.5 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5 Kinetics of Aqueous Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.1 Driving Force and Corrosion Rate . . . . . . . . . . . . . . . . . . . . . 74
5.2 Dissipations in Corrosion Systems . . . . . . . . . . . . . . . . . . . . . 75
5.3 Activation Overvoltage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.3.1 Exchange Current Density and Tafel Law . . . . . . . . 76
5.3.2 Potential-Current Density Diagrams (or
Characteristic Curves) . . . . . . . . . . . . . . . . . . . . . . . 79
5.3.3 Oxidation or Reduction of a Metal . . . . . . . . . . . . . . 81
5.3.4 Hydrogen Evolution (Activation Overvoltage) . . . . . 82
5.3.5 Oxygen Reduction (Activation Overvoltage) . . . . . . . 85
5.4 Concentration Overvoltage . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.4.1 Oxygen Reduction: Limiting Current . . . . . . . . . . . . 87
Contents ix
5.4.2 Total Oxygen Overvoltage . . . . . . . . . . . . . . . . . . . 89

5.5 Other Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.6 Passivation and Passivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.6.1 Film Formation Mechanisms . . . . . . . . . . . . . . . . . . 92
5.6.2 Oxide Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.6.3 Active-Passive Metals . . . . . . . . . . . . . . . . . . . . . . . 95
5.6.4 Passivity-Related Parameters . . . . . . . . . . . . . . . . . . 97
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
6 Evans Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 103
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 104
6.2 Evans Diagrams of Active Metals . . . . . . . . . . . . ....... . . 104
6.3 Corrosion Conditions in the Presence of an Ohmic Drop . . . . . 108
6.4 Multiple Cathodic Processes . . . . . . . . . . . . . . . . ....... . . 110
6.5 Imposed Polarization . . . . . . . . . . . . . . . . . . . . . . ....... . . 111
6.6 Experimental Polarization Curves . . . . . . . . . . . . . ....... . . 112
6.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . ....... . . 115
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 118
7 Corrosion Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7.1 Metal Affecting Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7.1.1 Modification of Metal Surface Composition . . . . . . . 120
7.1.2 Nobility by Alloying . . . . . . . . . . . . . . . . . . . . . . . . 121
7.1.3 Overvoltage of Cathodic Processes . . . . . . . . . . . . . 122
7.1.4 Cathodic Alloying . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.1.5 Reduction of Anodic Areas . . . . . . . . . . . . . . . . . . . 124
7.1.6 Passivation Induced by Alloying . . . . . . . . . . . . . . . 124
7.2 Environment Affecting Factors . . . . . . . . . . . . . . . . . . . . . . . . 124
7.2.1 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7.2.2 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7.2.3 Differential Aeration . . . . . . . . . . . . . . . . . . . . . . . . 126
7.2.4 Salt Formation/Precipitation . . . . . . . . . . . . . . . . . . . 128
7.2.5 Cation Displacement . . . . . . . . . . . . . . . . . . . . . . . . 129
7.2.6 Microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
7.3 Metal/Environment Affecting Factors . . . . . . . . . . . . . . . . . . . 133
7.3.1 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
7.3.2 Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
7.3.3 Corrosion Products and Deposits . . . . . . . . . . . . . . . 135
7.3.4 Flow Regime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
7.3.5 Active–Passive Related Parameters . . . . . . . . . . . . . 135
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
x Contents
8 Uniform Corrosion in Acidic and Aerated Solutions . . . . . . . . . . . . 145

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
8.2 Acidic Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
8.2.1 Strong Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.2.2 Carbonic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.2.3 Hydrogen Sulphide . . . . . . . . . . . . . . . . . . . . . . . . . 154
8.2.4 Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
8.2.5 Corrosion of Passive Metals . . . . . . . . . . . . . . . . . . 155
8.3 Aerated Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
8.3.1 Oxygen Limiting Diffusion Current . . . . . . . . . . . . . 157
8.3.2 Presence of Chlorine . . . . . . . . . . . . . . . . . . . . . . . . 158
8.3.3 Dimensionless Number Approach . . . . . . . . . . . . . . 159
8.3.4 Corrosion of Noble Metals . . . . . . . . . . . . . . . . . . . 160
8.3.5 Corrosion of Non-noble Metals . . . . . . . . . . . . . . . . 160
8.3.6 Corrosion of Passive Metals . . . . . . . . . . . . . . . . . . 162
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
9 Macrocell Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
9.1 Electrical Field in Uniform Corrosion . . . . . . . . . . . . . . . . . . . 170
9.2 Electrical Field in a Macrocell . . . . . . . . . . . . . . . . . . . . . . . . 170
9.2.1 Pure Ohmic Systems . . . . . . . . . . . . . . . . . . . . . . . . 171
9.2.2 Two-Electrode Macrocell . . . . . . . . . . . . . . . . . . . . 172
9.3 Current Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
9.3.1 Primary Current Distribution . . . . . . . . . . . . . . . . . . 173
9.3.2 Secondary Current Distribution . . . . . . . . . . . . . . . . 173
9.4 Throwing Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
9.5 Typical Geometries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9.5.1 Inside a Pipe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9.5.2 Outside a Pipeline . . . . . . . . . . . . . . . . . . . . . . . . . . 178
9.5.3 On a Plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
9.6 Maximum Surface Area Ratio . . . . . . . . . . . . . . . . . . . . . . . . 180
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
10 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
10.1 Effects on Metal Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 184
10.2 Galvanic Effects on Less Noble Metal . . . . . . . . . . . . . . . . . . 188
10.3 Galvanic Effects on More Noble Metal . . . . . . . . . . . . . . . . . . 189
10.4 Galvanic Coupling Representation by Evans Diagrams . . . . . . 192
10.5 Four Main Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
10.5.1 Practical Nobility . . . . . . . . . . . . . . . . . . . . . . . . . . 195
10.5.2 Cathodic Overvoltage on More Noble Metal . . . . . . 197
10.5.3 Surface Area Ratio and Maximum
Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Contents xi
10.5.4 Electrolyte Resistivity . . . . . . . . . . . . . . . . . . . . . . . 198

10.5.5 Geometry of the Domain . . . . . . . . . . . . . . . . . . . . . 199
10.6 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
11 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
11.1 Pitting Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
11.2 Pitting Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
11.2.1 Pit Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
11.2.2 Propagation of Stable Pits . . . . . . . . . . . . . . . . . . . . 215
11.2.3 Corrosion Rate of Stable Pits . . . . . . . . . . . . . . . . . . 216
11.3 Pitting on Stainless Steels in Chloride-Containing
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
11.3.1 PREN Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
11.3.2 Free Corrosion Potential . . . . . . . . . . . . . . . . . . . . . 218
11.3.3 Pitting Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
11.3.4 Repassivation Potential . . . . . . . . . . . . . . . . . . . . . . 218
11.3.5 Pedeferri’s Diagram . . . . . . . . . . . . . . . . . . . . . . . . 220
11.3.6 Pitting Induction Time . . . . . . . . . . . . . . . . . . . . . . 220
11.4 Pitting Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
11.4.1 Critical Pitting Temperature and Critical
Pitting Chloride Concentration . . . . . . . . . . . . . . . . . 223
11.5 Pitting on Carbon Steel in Chloride-Contaminated
Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
11.6 Pitting on Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 224
11.7 Pitting as Markovian Process or Prevention of Pitting . . . . . . . 225
11.8 Prevention of Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . 227
11.9 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
12 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
12.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
12.2 Crevice Critical Gap Size (CCGS) . . . . . . . . . . . . . . . . . . . . . 232
12.3 Mechanism of Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . 233
12.3.1 First Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.3.2 Second Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.3.3 Third Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
12.4 Metal Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
12.5 Environmental Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
12.6 Prevention of Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . 237
12.7 Crevice-Like Corrosion of Active Metals . . . . . . . . . . . . . . . . 238
xii Contents
12.7.1 Corrosion Under Insulation . . . . . . . . . . . . . . . . . . . 238

12.7.2 Automotive Related Corrosion . . . . . . . . . . . . . . . . . 238
12.7.3 Riveted Structures . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.7.4 Stored Plates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.8 Filiform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
13 Stress Corrosion Cracking and Corrosion-Fatigue . . . . . . . . . . . . . 243
13.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
13.2 SCC Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
13.3 Morphology and Conditions of Occurrence . . . . . . . . . . . . . . . 247
13.3.1 Crack Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
13.3.2 Crack Propagation . . . . . . . . . . . . . . . . . . . . . . . . . 249
13.4 Mechanical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
13.4.1 Stress Intensity Factor, KI, and Fracture
Toughness, KIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
13.4.2 Crack Growth and KISCC . . . . . . . . . . . . . . . . . . . . . 251
13.4.3 Crack Growth Rate and KI . . . . . . . . . . . . . . . . . . . 252
13.4.4 Crack Growth and Strain Rate . . . . . . . . . . . . . . . . . 253
13.4.5 Test Methods—SSRT . . . . . . . . . . . . . . . . . . . . . . . 253
13.5 Environment-Related Parameters . . . . . . . . . . . . . . . . . . . . . . 255
13.6 Metallurgical Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
13.6.1 Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
13.6.2 Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . 259
13.6.3 Sensitization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
13.7 SCC Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
13.7.1 Reduction of Stress and Defect Size . . . . . . . . . . . . 261
13.7.2 Control of Environment, Metallurgy
and Polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
13.8 Corrosion-Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
13.8.1 Mechanical Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . 262
13.8.2 Influencing Factors . . . . . . . . . . . . . . . . . . . . . . . . . 264
13.8.3 Corrosion-Fatigue and Fracture Mechanics . . . . . . . . 265
13.8.4 True Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . . . 265
13.8.5 Stress Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . . 267
13.8.6 Prevention of Corrosion-Fatigue . . . . . . . . . . . . . . . 268
13.9 Some Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Contents xiii
14 Hydrogen-Induced Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

14.1 Hydrogen Induced Damage . . . . . . . . . . . . . . . . . . . . . . . . . . 276
14.1.1 Adsorption, Dissolution and Trapping . . . . . . . . . . . 276
14.1.2 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
14.1.3 Atomic Hydrogen Produced by a Cathodic
Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
14.1.4 Decomposition and Solubility of Hydrogen
at High Temperature . . . . . . . . . . . . . . . . . . . . . . . . 283
14.2 HT-HID or Hydrogen Attack . . . . . . . . . . . . . . . . . . . . . . . . . 283
14.3 LT-HID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
14.3.1 Delayed Fracture . . . . . . . . . . . . . . . . . . . . . . . . . . 286
14.3.2 HIC and Blistering . . . . . . . . . . . . . . . . . . . . . . . . . 287
14.3.3 HE Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
14.3.4 Failure Mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
14.3.5 HE by Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
14.3.6 Sulphide Stress Cracking (SSC) . . . . . . . . . . . . . . . . 292
14.4 Prevention of LT-HID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
14.4.1 Prevention of HIC and Blistering . . . . . . . . . . . . . . . 293
14.4.2 Materials for Sour Service . . . . . . . . . . . . . . . . . . . . 293
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
15 Intergranular and Selective Corrosion . . . . . . . . . . . . . . . . . . . . . . 297
15.1 Impurities and Segregations . . . . . . . . . . . . . . . . . . . . . . . . . . 298
15.2 Sensitization of Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . 298
15.3 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
15.4 Prevention of Intergranular Corrosion . . . . . . . . . . . . . . . . . . . 301
15.5 Weld Decay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
15.5.1 Knife-Line Attack . . . . . . . . . . . . . . . . . . . . . . . . . . 303
15.6 Intergranular Corrosion of Nickel Alloys . . . . . . . . . . . . . . . . 303
15.7 Intergranular Corrosion Without Sensitization . . . . . . . . . . . . . 304
15.8 Exfoliation of Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . 306
15.9 Intergranular Corrosion Tests . . . . . . . . . . . . . . . . . . . . . . . . . 307
15.10 Selective Corrosion of an Alloying Element . . . . . . . . . . . . . . 307
15.10.1 Dezincification of Brass . . . . . . . . . . . . . . . . . . . . . 308
15.10.2 Cast Iron Graphitization . . . . . . . . . . . . . . . . . . . . . 309
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
16 Erosion-Corrosion and Fretting . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
16.1 Erosion-Corrosion Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
16.1.1 Corrosion by Turbulence . . . . . . . . . . . . . . . . . . . . . 315
xiv Contents
16.1.2 Cavitation Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 317

16.1.3 Metal Affecting Properties . . . . . . . . . . . . . . . . . . . . 319
16.1.4 Environment Affecting Properties . . . . . . . . . . . . . . 320
16.1.5 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
16.2 Fretting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
16.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
16.2.2 Main Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
16.2.3 Fretting Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . 322
16.2.4 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
16.2.5 Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
17 Corrosion Prevention by Coatings . . . . . . . . . . . . . . . . . . . . . . . . . 327
17.1 Metallic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.1 Coating Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.2 Cathodic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.3 Anodic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
17.1.4 Multilayer Coatings . . . . . . . . . . . . . . . . . . . . . . . . 330
17.1.5 Methods for Obtaining Metallic Coatings . . . . . . . . . 333
17.1.6 Zinc Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
17.1.7 Tin Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
17.1.8 Nickel Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
17.1.9 Chromium Coatings . . . . . . . . . . . . . . . . . . . . . . . . 338
17.1.10 Copper Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
17.1.11 Precious Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2 Conversion Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2.1 Phosphate Coatings . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2.2 Chromate Filming . . . . . . . . . . . . . . . . . . . . . . . . . . 340
17.2.3 Anodic Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 341
17.3 Other Inorganic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
17.3.1 Hot Enamels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
17.3.2 Thick Cementitious Coatings . . . . . . . . . . . . . . . . . . 344
17.3.3 Thick Corrosion Resistant Coatings . . . . . . . . . . . . . 344
17.4 Paintings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
17.4.1 Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
17.4.2 Corrosion Under Paintings . . . . . . . . . . . . . . . . . . . 349
17.4.3 Protective Action of Paints . . . . . . . . . . . . . . . . . . . 350
17.4.4 Paint Film Properties . . . . . . . . . . . . . . . . . . . . . . . . 353
17.4.5 Painting Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
17.4.6 Pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
17.4.7 Paint Application . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Contents xv
17.4.8 Painting Maintenance . . . . . . . . . . . . . . . . . . . . . . . 358

17.4.9 Threats at the Workplace . . . . . . . . . . . . . . . . . . . . . 358
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
18 Environmental Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
18.1 pH Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
18.2 Oxygen Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
18.3 Corrosion Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
18.3.1 Classification of Inhibitors . . . . . . . . . . . . . . . . . . . . 368
18.3.2 Cathodic Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . 369
18.3.3 Anodic Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . 369
18.3.4 Mixed Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
18.3.5 Inhibitor Adsorption Mechanism . . . . . . . . . . . . . . . 373
18.3.6 Adsorption Isotherm . . . . . . . . . . . . . . . . . . . . . . . . 374
18.3.7 Inhibitor Effectiveness . . . . . . . . . . . . . . . . . . . . . . . 375
18.4 Biocides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
19 Cathodic and Anodic Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
19.1 Cathodic Protection (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
19.1.1 Protection Potential . . . . . . . . . . . . . . . . . . . . . . . . . 384
19.1.2 Thermodynamic Effect . . . . . . . . . . . . . . . . . . . . . . 385
19.1.3 Kinetic Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
19.1.4 Protection Criteria and Overprotection . . . . . . . . . . . 386
19.1.5 Protection Current Density . . . . . . . . . . . . . . . . . . . 387
19.1.6 Anodic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 388
19.1.7 Coatings and Scales . . . . . . . . . . . . . . . . . . . . . . . . 389
19.1.8 Current Distribution . . . . . . . . . . . . . . . . . . . . . . . . 390
19.2 CP Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
19.2.1 Galvanic Anodes Cathodic Protection Systems
(GACP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
19.2.2 Impressed Current Cathodic Protection Systems
(ICCP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
19.2.3 CP Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
19.3 Anodic Protection (AP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
19.3.1 Electrode Reactions . . . . . . . . . . . . . . . . . . . . . . . . 408
19.3.2 AP Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
19.3.3 AP Versus Active-Passive Metals . . . . . . . . . . . . . . 409
19.3.4 Throwing Power of AP . . . . . . . . . . . . . . . . . . . . . . 411
19.3.5 Potentiostatic Feeding . . . . . . . . . . . . . . . . . . . . . . . 412
19.3.6 CP-AP Comparison . . . . . . . . . . . . . . . . . . . . . . . . . 413
xvi Contents

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
20 Corrosion in Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
20.1 Types of Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
20.2 Factors Influencing Corrosion Likelihood . . . . . . . . . . . . . . . . 425
20.2.1 Oxygen Content . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
20.2.2 Water Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
20.2.3 Scaling Tendency . . . . . . . . . . . . . . . . . . . . . . . . . . 426
20.2.4 Water Resistivity . . . . . . . . . . . . . . . . . . . . . . . . . . 429
20.2.5 Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
20.2.6 Other Cathodic Reactant . . . . . . . . . . . . . . . . . . . . . 429
20.3 Uniform Corrosion Rate Evaluation . . . . . . . . . . . . . . . . . . . . 430
20.4 Metals for Freshwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
20.4.1 Steel and Cast Iron . . . . . . . . . . . . . . . . . . . . . . . . . 432
20.4.2 Galvanized Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
20.4.3 Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
20.4.4 Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
20.5 Brackish Water and Seawater . . . . . . . . . . . . . . . . . . . . . . . . . 438
20.5.1 Corrosion Zones in Seawater . . . . . . . . . . . . . . . . . . 439
20.5.2 Materials for Seawater . . . . . . . . . . . . . . . . . . . . . . 440
20.6 Applicable Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
21 Corrosion in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
21.1 Soil Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
21.2 Corrosion in Aerated Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
21.2.3 Corrosion Index . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
21.2.4 Differential Aeration Corrosion . . . . . . . . . . . . . . . . 451
21.2.5 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 452
21.2.6 Effect of Soil Resistivity . . . . . . . . . . . . . . . . . . . . . 457
21.3 Microbial Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
21.4 Corrosion by Stray Currents . . . . . . . . . . . . . . . . . . . . . . . . . 461
21.4.1 Electrochemical Reactions on the Interfered
Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
21.4.2 Interference Current . . . . . . . . . . . . . . . . . . . . . . . . 464
21.4.3 Interference assessment . . . . . . . . . . . . . . . . . . . . . . 466
21.4.4 Criteria for Interference Acceptance . . . . . . . . . . . . . 467
21.4.5 Prevention and Control of Stray Current
Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
Contents xvii
21.4.6 Alternating Current Interference . . . . . . . . . . . . . . . . 471

21.4.7 Typical Cases of Improbable Interference . . . . . . . . . 474
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
22 Atmospheric Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
22.1 Liquid Film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2 Factors Affecting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2.1 Relative Humidity . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2.2 Time of Wetness . . . . . . . . . . . . . . . . . . . . . . . . . . 481
22.2.3 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
22.2.4 Atmosphere Composition . . . . . . . . . . . . . . . . . . . . 483
22.2.5 Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
22.3 Classification of Environments . . . . . . . . . . . . . . . . . . . . . . . . 485
22.3.1 Microenvironments . . . . . . . . . . . . . . . . . . . . . . . . . 486
22.3.2 Classification of Atmospheric Corrosiveness . . . . . . . 487
22.3.3 Indoor Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . 488
22.4 Corrosion Behaviour of Most Used Metals . . . . . . . . . . . . . . . 490
22.4.1 Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
22.4.2 Weathering Steels (Cor-Ten) . . . . . . . . . . . . . . . . . . 494
22.4.3 Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
22.4.4 Copper and Copper-Alloys . . . . . . . . . . . . . . . . . . . 501
22.4.5 Aluminium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
22.4.6 Other Metallic Materials . . . . . . . . . . . . . . . . . . . . . 502
22.5 Corrosion and Protection of Metallic Cultural Heritage . . . . . . 505
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
23 Corrosion in Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
23.1 Initiation, Propagation and Morphology of Corrosion . . . . . . . 510
23.2 Corrosion by Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
23.2.1 Carbonation Depth . . . . . . . . . . . . . . . . . . . . . . . . . 513
23.2.2 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
23.3 Chloride-Induced Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 516
23.3.1 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
23.3.2 Structures at a Risk . . . . . . . . . . . . . . . . . . . . . . . . . 519
23.4 Hydrogen Embrittlement . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
23.5 Corrosion by Stray Currents . . . . . . . . . . . . . . . . . . . . . . . . . 525
23.6 Prevention of Reinforcement Corrosion . . . . . . . . . . . . . . . . . 525
23.6.1 Quality of Concrete . . . . . . . . . . . . . . . . . . . . . . . . 526
23.6.2 Cover Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
23.6.3 Common Mistakes . . . . . . . . . . . . . . . . . . . . . . . . . 528
xviii Contents
23.7 Additional Protections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529

23.7.1 Concrete Surface Treatments . . . . . . . . . . . . . . . . . . 531
23.7.2 Corrosion Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . 532
23.7.3 Stainless Steel Reinforcements . . . . . . . . . . . . . . . . . 532
23.7.4 Galvanized Steel Reinforcements . . . . . . . . . . . . . . . 534
23.7.5 Cathodic Prevention (CPrev) . . . . . . . . . . . . . . . . . . 535
23.7.6 Comparison of Additional Protections . . . . . . . . . . . 535
23.7.7 Evaluation of service life by performance based
methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
23.8 Diagnosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
23.8.1 Concrete Cover Thickness Measurements
and Rebar Identification . . . . . . . . . . . . . . . . . . . . . 538
23.8.2 Analysis of Concrete . . . . . . . . . . . . . . . . . . . . . . . . 538
23.8.3 Electrochemical Techniques . . . . . . . . . . . . . . . . . . . 539
23.9 Repair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
23.9.1 Traditional Repair . . . . . . . . . . . . . . . . . . . . . . . . . . 541
23.9.2 Electrochemical Repair Techniques . . . . . . . . . . . . . 543
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
24 Corrosion in Petrochemical Plant . . . . . . . . . . . . . . . . . . . . . . . . . . 549
24.1 Petrochemical Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
24.2 The Corroding Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
24.3 Water Wetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
24.4 Corrosion Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
24.5 CO2-Related Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
24.5.1 Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . 556
24.5.2 Corrosion Rate Evaluation . . . . . . . . . . . . . . . . . . . . 557
24.5.3 Metals for Sweet Condition . . . . . . . . . . . . . . . . . . . 558
24.6 H2S-Related Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
24.6.1 Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . 562
24.6.2 Generalized Corrosion . . . . . . . . . . . . . . . . . . . . . . . 563
24.6.3 Hydrogen Induced Cracking (HIC) . . . . . . . . . . . . . 563
24.6.4 Sulphide Stress Cracking (SSC) . . . . . . . . . . . . . . . . 564
24.6.5 Metals for Sour Service Condition . . . . . . . . . . . . . . 565
24.7 Downstream Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
24.7.1 Corrosion by S/H2S Atmosphere . . . . . . . . . . . . . . . 566
24.7.2 Corrosion by Sulphur . . . . . . . . . . . . . . . . . . . . . . . 567
24.7.3 Corrosion by H2/H2S . . . . . . . . . . . . . . . . . . . . . . . 568
24.7.4 Corrosion by Naphthenic Acid . . . . . . . . . . . . . . . . 568
24.7.5 Hydrogen Attack . . . . . . . . . . . . . . . . . . . . . . . . . . 569
24.7.6 Organic Acid Corrosion . . . . . . . . . . . . . . . . . . . . . 569
24.7.7 Polythionic Acid Stress Corrosion Cracking . . . . . . . 570
Contents xix
24.7.8 High Temperature Sulphidation . . . . . . . . . . . . . . . . 570

24.8 International Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
25 Corrosion in the Human Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
25.1 Characteristics of Metals for Orthopaedic Purpose . . . . . . . . . . 576
25.1.1 Mechanical Resistance . . . . . . . . . . . . . . . . . . . . . . 576
25.1.2 Fatigue Resistance . . . . . . . . . . . . . . . . . . . . . . . . . 576
25.1.3 Resistance to Generalized Corrosion . . . . . . . . . . . . 577
25.1.4 Resistance to Crevice Corrosion . . . . . . . . . . . . . . . 577
25.1.5 Resistance to Fretting Corrosion . . . . . . . . . . . . . . . 577
25.1.6 Corrosion for Galvanic Coupling . . . . . . . . . . . . . . . 578
25.1.7 Biocompatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
25.2 Classes of Metals Employed in Orthopaedics . . . . . . . . . . . . . 579
25.2.1 Austenitic Stainless Steels . . . . . . . . . . . . . . . . . . . . 579
25.2.2 Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
25.2.3 Titanium and Titanium Alloys . . . . . . . . . . . . . . . . . 581
25.3 Surface Finishing Treatments . . . . . . . . . . . . . . . . . . . . . . . . . 581
25.3.1 Barrel Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
25.3.2 Electropolishing . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
25.3.3 Passivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
25.3.4 Titanium Anodising . . . . . . . . . . . . . . . . . . . . . . . . 582
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
26 High Temperature Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
26.1 Corrosive Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
26.2 Thermodynamics and Kinetics . . . . . . . . . . . . . . . . . . . . . . . . 590
26.3 Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
26.3.1 Non Protective Oxides . . . . . . . . . . . . . . . . . . . . . . 592
26.3.2 Protective Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 593
26.4 Wagner Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
26.4.1 Oxide Conductivity and Lattice Defects . . . . . . . . . . 595
26.5 Morphology of Oxide Films . . . . . . . . . . . . . . . . . . . . . . . . . 597
26.6 Oxidation of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
26.7 Oxidation of Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
26.7.1 Oxidation of Only One of Two Metals
in Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
26.7.2 Oxidation of Both Metals in Alloy . . . . . . . . . . . . . 603
26.8 Other Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.1 Sulphidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.2 Carburization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.3 Halogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
xx Contents
26.9 Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606

26.9.1 Oxygen and Air . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.2 Steam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.3 Sulphur Compounds . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.4 Combustion Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
26.9.5 Nitridation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
26.10 Materials for Use at High Temperatures . . . . . . . . . . . . . . . . . 608
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
27 Prevention of Corrosion in Design . . . . . . . . . . . . . . . . . . . . . . . . . 611
27.1 Design Life and Reliability . . . . . . . . . . . . . . . . . . . . . . . . . . 612
27.1.1 How to Choose Reliability and Related
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
27.2 Prevention in Design Phase . . . . . . . . . . . . . . . . . . . . . . . . . . 613
27.2.1 Evaluation of Aggressiveness . . . . . . . . . . . . . . . . . 613
27.2.2 Reduction of Aggressiveness . . . . . . . . . . . . . . . . . . 613
27.2.3 Local Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . 614
27.2.4 Homogeneity Is Preferred . . . . . . . . . . . . . . . . . . . . 614
27.2.5 Change of Aggressiveness in Space
and with Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
27.3 Metal Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
27.3.1 Basic Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
27.3.2 Technological Criteria . . . . . . . . . . . . . . . . . . . . . . . 616
27.4 Some General Features of Used Metals . . . . . . . . . . . . . . . . . 616
27.4.1 Carbon and Low Alloy Steels . . . . . . . . . . . . . . . . . 616
27.4.2 Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
27.4.3 Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
27.4.4 Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 621
27.4.5 Copper Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
27.4.6 Titanium and Its Alloys . . . . . . . . . . . . . . . . . . . . . 622
27.5 General Philosophy for Metal Selection in Industry . . . . . . . . . 622
27.5.1 Alkaline Solutions . . . . . . . . . . . . . . . . . . . . . . . . . 623
27.5.2 Chloride-Free Acidic Solutions . . . . . . . . . . . . . . . . 624
27.5.3 Chloride-Containing Environments . . . . . . . . . . . . . 625
27.6 Prevention by Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
27.7 Prevention in Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
27.8 Prevention in Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
27.9 Commissioning and Start-up . . . . . . . . . . . . . . . . . . . . . . . . . 628
27.10 Prevention During Operation . . . . . . . . . . . . . . . . . . . . . . . . . 631
27.11 Planned Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
Contents xxi
28 Monitoring and Inspections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635

28.1 Corrosion Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
28.1.1 Selection of Monitoring Locations . . . . . . . . . . . . . . 637
28.2 Common Monitoring Methods . . . . . . . . . . . . . . . . . . . . . . . . 637
28.2.1 Corrosion Coupon . . . . . . . . . . . . . . . . . . . . . . . . . 637
28.2.2 Corrosion Spool . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
28.2.3 Electrical Resistance Probe . . . . . . . . . . . . . . . . . . . 639
28.2.4 Linear Polarisation Resistance . . . . . . . . . . . . . . . . . 639
28.2.5 Galvanic Probe . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
28.2.6 Potential Measurement . . . . . . . . . . . . . . . . . . . . . . 641
28.2.7 Bio-probe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
28.2.8 Hydrogen Probe . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
28.3 Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
28.3.1 Electrochemical Noise . . . . . . . . . . . . . . . . . . . . . . . 646
28.3.2 EIS (Electrochemical Impedance Spectroscopy) . . . . 646
28.3.3 Acoustic Emission . . . . . . . . . . . . . . . . . . . . . . . . . 646
28.4 Plant Inspection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
28.4.1 Liquid Penetrant . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.2 Magnetic Particles . . . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.3 Radiographic Testing . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.4 Ultrasonic Testing . . . . . . . . . . . . . . . . . . . . . . . . . 648
28.4.5 Eddy Current Method . . . . . . . . . . . . . . . . . . . . . . . 649
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
29 Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
29.1 Test Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
29.2 Accelerated Tests and Statistics . . . . . . . . . . . . . . . . . . . . . . . 653
29.3 Exposure Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
29.3.1 Mass Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
29.3.2 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 655
29.3.3 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 656
29.3.4 Galvanic Coupling . . . . . . . . . . . . . . . . . . . . . . . . . 659
29.3.5 Integranular Corrosion . . . . . . . . . . . . . . . . . . . . . . 660
29.3.7 Erosion, Cavitation and Fretting . . . . . . . . . . . . . . . 664
29.3.8 Artificial Atmosphere—Cabinet Test . . . . . . . . . . . . 664
29.4 Electrochemical Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
29.4.2 Pitting Potential and Repassivation Potential . . . . . . 672
29.4.3 Galvanic Coupling . . . . . . . . . . . . . . . . . . . . . . . . . 672
29.4.4 Intergranular Corrosion . . . . . . . . . . . . . . . . . . . . . . 673
xxii Contents

29.4.6 Other Electrochemical Techniques . . . . . . . . . . . . . . 674
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
30 Statistical Analysis of Corrosion Data . . . . . . . . . . . . . . . . . . . . . . . 679
30.1 Fundamentals of Statistics . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
30.1.1 Mean and Variability of Data Distribution . . . . . . . . 680
30.1.2 Statistical Distributions of Scatter Data . . . . . . . . . . 681
30.1.3 Reliability and Hazard Functions . . . . . . . . . . . . . . . 682
30.2 Probability Distributions Observed in Corrosion . . . . . . . . . . . 682
30.2.1 Normal (Gaussian) Distribution . . . . . . . . . . . . . . . . 683
30.2.2 Lognormal Distribution . . . . . . . . . . . . . . . . . . . . . . 685
30.2.3 Poisson and Exponential Distributions . . . . . . . . . . . 685
30.2.4 Generalized Extreme Value Statistics . . . . . . . . . . . . 687
30.2.5 Gumbel Extreme Value Statistics . . . . . . . . . . . . . . . 688
30.2.6 Weibull Extreme Value Statistics . . . . . . . . . . . . . . . 691
30.3 Sample Size and Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . . 694
30.3.1 Sample Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
30.3.2 Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
30.4 International Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
About the Author
… ‘I see that water, nay, I see

that fire and air and earth, and all their mixtures
become corrupt, and but a little while
endure; and yet created things were these!
Dante, The Divine Comedy, Paradise VII
Born “valtellinese”, adopted “milanese”, with heart

and spirit in Nestrelli
Pietro Pedeferri
Pietro Pedeferri was a Full Professor in Corrosion and

Protection of Materials at the School of Engineering at
Politecnico di Milano, Italy.
He graduated in chemical engineering (cum laude) at
Politecnico di Milano as Montecatini gold medal holder
and won the De Nora Award with a thesis on electro-
chemistry under the supervision of Professor Roberto
Piontelli. His career started and continued at Politecnico
di Milano, as an Assistant Professor first and then Full
Professor in electrochemistry and later in corrosion and
protection of materials. In 1968, he was appointed as
lecturer of the first ever course on corrosion and pro-
Pietro Pedeferri (1938–2008) tection at an Italian university. He was a Visiting
Professor at the University of Cambridge, UK, and the
University of Connecticut, USA. From 1993 to 1999,
he was Head of the Department of Applied Physical
Chemistry at the Politecnico di Milano.
His first academic activity was electrochemistry
research; then, in the 1963, he moved on to the corro-
sion field focusing on industrial and engineering
aspects. His topics of study in electrochemistry were
overvoltage in sulphamic solutions, anodic effects in Al
production cells, anodic oxidation of Ti and so-called
xxiii
xxiv About the Author
valve metals and relevant chromatic effects. His

research in corrosion started with cold-worked stainless
steels and continued with implanted metals in simulated
physiological solutions, corrosion of bronze artefacts
and cathodic protection. Since 1985, he dealt with
corrosion of steel reinforcements in concrete, indicating
factors and conditions for initiation and propagation. In
1991, he invented and proposed a new technique called
cathodic prevention for concrete structures destined to
be chloride contaminated, nowadays included in oper-
ative international standards. From the study of the
corrosion behaviour of stainless steel reinforcements,
he proposed a potential-to-chloride diagram for inter-
pretation: this diagram is now called the Pedeferri
Diagram.
Meanwhile, he continued his studies on Ti colour-
ing, winning an award in 1988 in Paris, within the
international event Science pour l’art, and displaying
his work in the Fondazione Corrente Gallery in Milan,
Italy. He revisited the publications of Alessandro Volta
and Leopoldo Nobili and then rewrote several chapters
of the history of electrochemistry. Some of the
Pedeferri’s findings on Volta priorities in corrosion are
reported in this book.
He published 388 papers and 34 books, and took out
8 patents.
Symbols and Abbreviations
aMz þ Activity (or concentration) of ions of metal M in a solution (mol/L)

a Coefficient (adimensional)
b Tafel slope (module) (V/decade)
ba Tafel slope of the anodic curve (module) (V/decade)
bc Tafel slope of the cathodic curve (module) (V/decade)
bFe Tafel slope of iron dissolution reaction (V/decade)
bH 2 Tafel slope of hydrogen evolution reaction (V/decade)
bO 2 Tafel slope of oxygen reduction reaction (V/decade)
C Concentration (mol/L)
Crate Corrosion rate (mm/y)
Crate,m Mass loss rate (mdd)
CCGS Critical crevice gap size (µm)
CCT Critical crevice temperature (°C)
CIPP Close interval potential profile
CP Cathodic protection
CPrev Cathodic prevention
CPCC Critical pitting chloride concentration
CPT Critical pitting temperature (°C)
CSE Saturated copper sulphate electrode (+0.32 V SHE)
d Distance (m)
deq Diameter of the coating equivalent defect (m)
D Diffusion coefficient (m2/s)
DL Design life
d Diffusion layer thickness (m)
e− Electron
E Electrode potential (V)
EXY Potential difference between electrode X and Y (V)
E0 Standard potential (V)
Ea Anodic potential (V)
Ec Cathodic potential (V)
xxv
xxvi Symbols and Abbreviations
Ecorr Free corrosion potential (V)

Eeq Equilibrium potential given by Nernst equation (V)
EIR-free Potential free of the ohmic drop in CP applications (V)
Eoff Off-potential in CP applications (V)
Eon On-potential in CP applications (V)
Ep Passivation potential (V)
Epit Pitting potential or passivity breakdown potential (V)
Epp Primary passivation potential (V)
Eprot Protection potential (V)
Erp Repassivation potential (V)
Etr Transpassive potential (V)
EMF Electromotive force (V)
DE Driving voltage or potential difference (V)
e Efficiency (unitary fraction)
F Faraday constant (96,485 C)
FEM Finite element method
/ Diameter (m)
G Gibbs free energy (J/mol)
GACP Galvanic anode cathodic protection
c Mass density (g/cm3)
DG Standard Gibbs free energy variation (J/mol)
H Activation energy (J/mol)
HE Hydrogen embrittlement
HIC Hydrogen-induced cracking
HID Hydrogen-induced damage
g Overvoltage (with respect to the equilibrium potential) (V)
ga Anodic overvoltage (V)
gact; O2 Activation overvoltage of oxygen reduction (V)
gc Cathodic overvoltage (V)
gconc; O2 Concentration overvoltage of oxygen reduction (V)
gH2 Activation overvoltage of hydrogen evolution reaction (V)
gM Activation overvoltage of metal dissolution reaction (V)
gO2 Overvoltage of oxygen reduction (V)
i Current density (mA/m2)
ia Anodic current density (mA/m2)
ic Cathodic current density (mA/m2)
icorr Corrosion current density (mA/m2)
icp Critical passivation current density (mA/m2)
iGC Current density in galvanic coupling (mA/m2)
iL Oxygen limiting current density (mA/m2)
i0 Exchange current density (mA/m2)
i0; H2 Exchange current density of hydrogen evolution (mA/m2)
i0,M Exchange current density of metal M (mA/m2)
Symbols and Abbreviations xxvii
i0; O2 Exchange current density of oxygen (mA/m2)

ip Passivity current density (mA/m2)
iprot Protection current density (mA/m2)
I Current (A)
Ia Anodic current (A)
Ic Cathodic current (A)
Ie External current (A)
Iel Current in the electrolyte (A)
Iinterf Interference current (A)
Iprot Protection current (A)
ICCP Impressed current cathodic protection
k Constant (generic)
j Conductivity of an electrolyte (S/m)
Ks Complex stability constant
L Length (m)
Lmax Throwing power (m)
LSI Langelier saturation index
m Mass (g)
M Generic metal, less noble metal in a coupling
Mz+ Oxidised metal species
MIC Microbiologically influenced corrosion
MOB Manganese oxidising bacteria
MMO Mixed metal oxides (of noble metals Ir, Rh, Ru)
MW Atomic or molecular weight (g/mol)
N More noble metal in a coupling
Na Anode number
p Porosity of a scale (unitary fraction)
pCO2 Partial pressure of CO2 (bar)
pH 2 S Partial pressure of H2S (bar)
P Pressure of a gas (bar)
PREN Pitting resistance equivalent number
Q Flux of electrical charges (C)
R Generic ohmic resistance (X)
R Gas constant (1.987 cal/mol K = 8.314 J/mol K)
R0 Coating insulation resistance (X m2)
Ra Anode resistance (X)
Rc Cathode resistance (X)
Rcable Resistance of feeding cables (X)
Rtot Total resistance (X)
RH Relative humidity
RSI Ryznar saturation index
q Resistivity (X m)
qel Electrolyte resistivity (X m)
qmet Metal resistivity (X m)
xxviii Symbols and Abbreviations
s Thickness (m)
S Surface (m2)
Sa Anodic surface (m2)
Sc Cathodic surface (m2)
SM Surface of the less noble metal in a coupling (m2)
SN Surface of the more noble metal in a coupling (m2)
SHE Standard hydrogen electrode
SCC Stress corrosion cracking
SCE Saturated calomel electrode (+0.24 V SHE)
SOHIC Stress-oriented hydrogen-induced cracking
SRB Sulphate-reducing bacteria
SSC Silver/silver chloride reference electrode (+0.25 V SHE)
SSC Sulphide stress cracking
r Conductivity (S/m)
t Time (s)
T Temperature (°C; K)
T/R Transformer/rectifier
TDS Total dissolved solids or salinity (g/L or mg/L)
v Velocity (m/s)
V Voltage or feeding voltage (V)
DV Voltage drop or ohmic drop (V)
n Coating efficiency (unitary fraction)
w Anode consumption (kg/A y)
w Polarisation or potential shift from the free corrosion potential (V)
w* Thermodynamic and kinetic contribution of electrode reactions (V)
z Valence, number of electrons in an electrodic reaction (adimensional)
ZN Zinc/sea water reference electrode (−0.8 V SHE)
Units
A Ampere
cal Calorie
C Coulomb
°C Degree centigrade
h Hour
J Joule
K Degree Kelvin
L Litre
m Metre
M Molar
mol Mole
X Ohm
s Second
Symbols and Abbreviations xxix
S Siemens
V Volt
W Watt
Chapter 1
General Principles of Corrosion
You are dust and to dust you shall return.

Genesis, 3.19
Abstract This introductory chapter presents the general aspects of corrosion: its
origins, the main forms it can take, the general mechanism and corrosion rate
involved, and the impact it has on society, with particular reference to the economic
aspects. All technical information here briefly mentioned will be addressed in more
details in specific chapters.
Fig. 1.1 Case study at the PoliLaPP Corrosion Museum of Politecnico di Milano
© Springer Nature Switzerland AG 2018 1

P. Pedeferri, Corrosion Science and Engineering, Engineering Materials,
https://doi.org/10.1007/978-3-319-97625-9_1
2 1 General Principles of Corrosion
1.1 Corrosion as Metallurgy in Reverse
Materials exposed to aggressive environments may undergo chemical and physical

degradation (Fig. 1.1). This degradation is called “corrosion” when the material
concerned is a metal. The term corrosion derives from Medieval Latin [corrosionis,
from the verb corrodere], Middle English [corosioun] and Old French [corrosion].
Corrosion is often defined as “destruction or degradation of a material caused
by a reaction to its environment” and also “the spontaneous tendency of a metallic
component to return to its original state as found in nature” [quoted from Fontana].
For this reason, corrosion is also called metallurgy in reverse, because the corrosion
process returns metals to their more thermodynamically stable natural state as
oxides or sulphides or other compounds, from which metallurgy transforms to
metal by supplying energy. Figure 1.2 shows the whole corrosion related life cycle
of iron.
Definitions of Corrosion
The breaking down or destruction of a material, especially a metal, through
chemical reactions. The most common form of corrosion is rusting which
occurs when iron combines with oxygen and water [The American Heritage®
Science Dictionary].
Corrosion is the deterioration of a material due to interaction with its
environment. It is the process by which metallic atoms leave the metal or
form compounds in the presence of water and gases. Metal atoms are
removed from a structural element until it fails or oxides build up inside a
pipe until it is plugged [DOE Fundamentals Handbook Material Science,
Volume 1 of 2].
Corrosion can be defined as the deterioration of material by reaction to its
environment. Corrosion occurs because of the natural tendency of most
Fig. 1.2 The corrosion process as metallurgy in reverse (adapted from M. Fontana)
1.1 Corrosion as Metallurgy in Reverse 3
metals to return to their natural state; e.g., in the presence of moist air iron
will revert to its natural state—iron oxide. Metals can be corroded by the
direct reaction of metal to a chemical; e.g. zinc will react with dilute sulfuric
acid and magnesium will react with alcohols [NASA, Corrosion Control And
Treatment Manual-TM-584C Rev-C.].
Physicochemical interaction between a metal and its environment which
results in changes in the properties of the metal and which may often lead to
impairment of the function of the metal, the environment or the technical
system of which these form a part [ISO 8044].
EFC Definition of Corrosion

In simple terms, corrosion processes may be considered metal’s reactions to
species in the environment to form chemical compounds. Note that in the
definition of corrosion given by the ISO 8044-1986 international standard the
term ‘corrosion’ applies to the process, not to the result, the latter being ‘cor-
rosion damage’, deterioration or effect. Implicit in the concept of corrosion as a
process is the corrosion reaction rate; implicit in the damage caused is the extent
and nature of the damage in relation to the function of the systems concerned.
A broader, but widely accepted alternative definition, from the
International Union of Pure and Applied Chemistry (IUPAC), encompasses
the degradation of non-metals as well as metallic materials, as follows:
“Corrosion is an irreversible interfacial reaction of a material (metal,
ceramic, polymer) with its environment which results in consumption of the
material or in dissolution into the material of a component of the environ-
ment. Often, but not necessarily, corrosion results in effects which are
detrimental to the usage of the material considered. Exclusively physical or
mechanical processes such as melting or evaporation, abrasion or
mechanical fracture are not included in the term corrosion” [EFC Working
Party 7: Corrosion Education].
1.2 The Economic Impact of Corrosion
Corrosion involves industry, infrastructure and cultural heritage concurrently. No

sector is left out: energy, transport, chemistry, food and beverages, oil and gas,
pharmaceutics, machinery, civil engineering. Corrosion hits metallic and reinforced
concrete structures, pipelines transporting hydrocarbons and water, aerial, terrestrial
and naval transport infrastructure, bridges, piers, offshore structures, chemical
plants and nuclear reactors, power plants, electronic devices, body implants, cul-
tural heritage, artefacts and many more.
The entity of corrosion damage is impressive. It is well summarized by a sign

displayed at an NACE conference in capital letters:
While You Are Reading This Message, 10 Tons of Iron Is Corroding Around
the World
Estimates by the UK and Japanese Ministries of Industry, the National Bureau of
Standards on behalf of the US Congress and the US National Institute of Science
and Technology have confirmed that the so-called cost of corrosion accounts for
around 3–4% of the GNP of industrialized countries. A recent study by NACE
(IMPACT 2016) estimates the global cost of corrosion to be US$2.5 trillion,
roughly 3.4% of the global Gross Domestic Product (GDP) of a generic country.
The cost of corrosion is given by the sum of direct (for example, the costs of
damaged components and associated substitution costs,1 prevention method costs—
e.g. protective coatings, cathodic protection, corrosion allowance or redundant
solutions, corrosion resistant materials2) and indirect costs (for example, production
loss costs, pollution related costs, loss of image and so on) which also encompass
unquantifiable costs such as the loss of human life when catastrophic failures
occur.3 Indirect costs are often difficult to assess and can exceed direct costs.
Corrosion cannot be halted but only reduced to a much greater extent than is
normally achieved. In 1971, Hoar suggested, based on various sources, that the costs
of corrosion could be reduced by 15–35% simply by applying basic knowledge of
corrosion principles, adopting the most familiar techniques such as cathodic pro-
tection, corrosion inhibitor injection or selecting a resistant material and improving
design. The NACE IMPACT report (2016) confirmed that implementing corrosion
prevention best practices could result in global savings of between 15 and 35% of the
cost of damage or US$375–875 billion. In a later chapter, the cost of corrosion will
be assessed in the context of economic appraisal in material selection.
It must be emphasized that corrosion does not always mean damage but simply
an industrial cost, which also has human, social and cultural aspects. Corrosion
prevention (i.e., associated corrosion costs) greatly contributes to making industrial
processes possible, reducing energy and raw material consumption, making energy
conservation, making plants safer and more reliable, preserving cultural heritage
and much more.
There is also ‘constructive’ metal corrosion such as, for example, chemical
attack used to highlight its microstructure or to make it rough or glossy, build up a
protective or attractive layer, carve its surface, perform selective removal of
material, produce specific corrosion components or hydrogen and more. Some
1
It has been estimated that about 40% of steel produced is made to replace corroded steel.
2
Cost is calculated as that in excess of the carbon steel solution cost, taken as reference.
3
Eminent historians (Mommsen among them) have suggested that the decline and fall of the
Roman Empire was caused by the corrosion of the lead employed for food and beverage pots
which poisoned people.
1.2 The Economic Impact of Corrosion 5
applications lead to artistic or creative corrosion, as was common in the Middle

Ages, to decorate weapons, armour and other objects by chemical etching and
produce acqueforti from steel and copper plates etched with nitric acid. Anodic
oxidation of titanium allowed an artist—one of the many Pedeferri’s facets—to
recreate boreal dawns or magical soap bubbles on its surface. All of these are
corrosion processes, which open a window into the world of art.
1.3 Corrosion Forms
Corrosion damage presents two main morphologies with regard to the environ-
mentally exposed surface: on the whole surface, so-called generalized corrosion,
only on a small portion of it, so-called localized corrosion. Moreover, in specific
conditions and in the presence of a tensile load, attacks can cause cracks perpen-
dicular to the tensile stress to form, so-called stress corrosion cracking. In general,
corrosion processes bring all the constituents of the material into solution even if in
some cases only one constituent is dissolved (selective corrosion) or only the grain
border is attacked producing intergranular corrosion. Figure 1.3 shows the mor-
phology of the various forms of corrosion schematically.
1.3.1 Uniform or Generalized Corrosion
This is a form of corrosion which affects the whole surface of the metallic material
in contact with the corrosive environment. If the attack is spread evenly, it is
referred to as uniform corrosion, otherwise corrosion is unevenly generalized.
Material thinning, called also thickness loss, is generated at a typically predictable
rate provided that the environmental conditions are known. For example, the cor-
rosion of carbon steel exposed to the atmosphere takes place at a rate varying from a
few tens to a few hundred lm/year depending on humidity, temperature, the
presence of chlorides and other pollutants. When zinc coatings are used in the same
environment, the corrosion rate drops to a value about 10–30 times lower.
Is Corrosion Really a Cost?

The ‘corrosion is a cost’ approach is misleading. Corrosion has an economic
impact in the sense that it implies a net cost that someone has to pay.
However, the corrosion cost is inevitable like the corrosion process as ther-
modynamics states. The logical consequence of this is that corrosion costs
should be considered the best option cost, once design targets are achieved,
for instance, transporting fluids in total safety for people and the environment.
If this new approach is accepted, it means that the cost of using a corrosion
resistant material or using a corrosion prevention method should not be listed
as a direct cost because it is most likely necessary in order to ensure reliability

and safety level targets as should be specified at the design stage. In other
words, the minimum inevitable cost is not the mild steel cost, as is assumed in
an economic appraisal, but rather that which fits the quality requirements
specified in the design documents.
Finally, corrosion prevention costs are not pure costs which could theo-
retically be saved but rather necessary costs (to be reduced as far as possible,
of course) to minimize or even eliminate the risk of material failure.
Fig. 1.3 Figure showing typical corrosion forms occurring on metals

1.3 Corrosion Forms 7
1.3.2 Localized Corrosion
Localized corrosion takes place on specific sections of an exposed surface because

of two general conditions: a non-homogeneous condition for the material or the
environment and a specific localized attack due to the presence of aggressive
species.
Non-homogeneous conditions lead to galvanic corrosion (also called bimetallic
corrosion) when different materials are in contact (i.e., a material coupling in which
a noble material is present, as in the case of aluminium and copper) or to differential
aeration corrosion caused by non-homogeneous oxygen availability on a metal
surface or under deposit corrosion when oxygen diffusion is impeded by a deposit
(scales or even former corrosion products) or by so-called interstitial corrosion
(crevice corrosion) when a gap is present on the material (a typical example is
under a gasket in flanged joints) or stray current corrosion when an electrical field
is present in the environment (typically in soil).
Localized attacks can occur because of environmental flows or micro motions
between two metals: the former leads to erosion-corrosion (due to the turbulence of
the aggressive solution) or impingement corrosion (when a liquid hits the material)
or cavitation corrosion as in case of pump impellers, the latter to fretting corrosion.
Localized attacks also take place in homogeneous environments when aggres-
sive species locally destroy the passive film present on a metal surface as in the case
of stainless steels and many other passive alloys. The morphology of an attack
depends on diameter-to-depth ratio and varies from large cavities (craters) to small
pinholes, called pitting, often showing penetration rates up to more than 1 mm/year.
1.3.3 Stress Corrosion Cracking
For specific material-to-environment couplings and under an enduring tensile load,

corrosion attack can take the form of cracks penetrating materials in a direction
which is perpendicular to its tensile stress.
This is called stress corrosion cracking (SCC) or corrosion fatigue depending
on whether tensile stress is constant or varies cyclically. It is particularly dangerous
because it can jeopardize the reliability of a plant where it occurs.
If crack growth is due to the action of atomic hydrogen, produced on a metal
surface for various reasons and then diffusing in the metal, cracking is called
hydrogen embrittlement (HE). Furthermore, atomic hydrogen in metal, in addition
to cracks, can cause other types of damage such as blister or bulge formation or
small internal cracks (blistering and stepwise cracking).
1.4 Corrosion Rates
Regardless of the morphology of an attack, corrosion leads to a loss in mass. In this

event, corrosion rates can be expressed as mass loss per time per unit area as is
often used in laboratories. In engineering, penetration rate (or thickness loss rate) is
preferred. For some forms of corrosion, such as SCC or corrosion-fatigue giving
rise to crack formation, mass loss and reductions in thickness are of no practical use
since time to failure or crack propagation rate (crack growth) is more useful.
1.4.1 Uniform Corrosion
Uniform corrosion, i.e., when corrosion attacks are uniformly distributed over the
surface of a material, can be measured by the mass loss rate per unit area, Crate,m,
exposed to the aggressive environment and calculated by the equation:
Dm
Crate;m ¼ ð1:1Þ
St
where Dm is mass loss in time, t, and S is exposed surface area.

The most frequently used units of measurement of mass loss rate are mg/
dm2day (mdd) and mg/m2hour (mmh). These units are of interest when the amount
of dissolved metal is of concern, for example in pollution related matters, as in the
case of the contamination of tin in tomato cans. It is most frequently used in
laboratory testing.
In industrial applications, thinning rates (thickness loss rate or penetration rate)
are preferred to mass loss as a corrosion measurement and given as, Crate in the
equation:
Dm Crate;m
Crate ¼ ¼ ð1:2Þ
cSt c
where c is mass metal density. The most frequently used units of measurement of
thickness loss rates are mm/y and mpy (mils per year) (1 mpy = 0.025 mm/year or
25.4 lm/year).
The relationship between the mass loss rate, Crate,m, and the penetration rate,
Crate, for most industry-used metals such as iron, copper and zinc, which have a
mass density in the range of 7–8 Mg/m3 (tons per cubic meter) is:
1 mdd ffi 5 lm=year 1 mmh ffi 1 lm=year ð1:3Þ
Table 1.1 shows an industry accepted corrosion rate classification for metallic
materials first proposed by Fontana’s classic Corrosion Engineering textbook. The
values reported are valid for the oil and gas and chemical industries (although they
1.4 Corrosion Rates 9
Table 1.1 Classification of industry accepted corrosion rates (adapted from Fontana 1986)
Corrosion behaviour Corrosion rate
mpy (mils/year) lm/year nm/h pm/s mm/year
Excellent <1 <25 <2 <1 <0.02
Very good 1–5 25–100 2–10 1–5 0.02–0.01
Good 5–20 100–500 10–50 5–20 0.1–0.5
Average 20–50 500–1000 50–150 20–50 0.5–1
Poor 50–200 1000–5000 150–500 50–200 1–5
Inacceptable >200 >5000 >500 >200 >5
Units as nm/h and pm/s are reported for comparison purposes only
seem quite high) but not for other industrial sectors such as energy, nuclear, food
and beverage, pharmaceutical, biomedical and construction. For example, the
corrosion of steel reinforcements in concrete structures is considered negligible
when it is below 1.5–2 lm/year or, according to European standards, nickel release
rates from objects in contact with human skin must be less than 2 lg/cm2 week
which is equivalent to 0.12 lm/year (nickel density 8.9 Mg/m3).
When corrosion is localized a distinction has to be made between mass loss rate,
which represents an average value related to the entire exposed surface, and the
maximum penetration rate which is the value of concern. The equivalence con-
sidered above for uniform corrosion attacks is obviously not applicable.
1.5 Corrosion Mechanisms
Metal corrosion follows two different mechanisms: high temperature corrosion

which is typical of metals exposed to hot gas, for instance in boilers and turbines,
and aqueous corrosion which takes place on metals exposed to waters, soil,
chloride contaminated or carbonated concrete and many process fluids, in a word to
an electrolyte. However, there are environments, such as melted salts or melted
metals and non-aqueous solutions, whose corrosion attacks do not correspond to
one alone of the above mechanisms but show features of both.
The two distinct types of corrosion imply two different mechanisms. The former
is an electrochemical process which is the result of two simultaneous and com-
plementary reactions, one anodic and one cathodic, in which electrons play a key
role. Wet corrosion follows thermodynamic laws and electrochemistry kinetics.
The second mechanism relates to chemical reactions, which obey the thermo-
dynamic laws and chemistry kinetics of heterogeneous reactions. Since hot corro-
sion involves the formation of protective layers (typically oxides) the kinetics of the
corrosion process are generally more complicated and depend on a range of factors
such as adhesion, consistence, porosity, type of conduction (ionic or electronic) and
film conductivity.
1.6 Questions and Exercises
1:1 A zinc plate with a surface area of 1 m2 is exposed to an aggressive solution

then suffers a uniform mass loss of 2 g/day. Calculate the corrosion rate
expressed in: mdd (mg/dm2day), mmh (mg/m2h) and in µm/year (Zn
density = 7.14 Mg/m3).
1:2 A carbon steel alloy suffers a uniform mass loss of 1 mdd. How much is it the
corrosion rate in µm/y (Fe density = 7.85 Mg/m3)?
1:3 A home heating system is made of carbon steel (MWFe = 55.85 g/mol).
Total volume is 1 m3. After the circuit is filled with water, calculate mass
loss and thickness loss assuming that the oxygen content in water is 8 mg/L
(MWO = 16 g/mol) and the total exposed internal surface area is 3.6 m2. The
corrosion reaction is: Fe + ½ O2 + H2O ! Fe(OH)2.
1:4 Define the mathematical equation to determine the thickness loss of the
piping system in a home heating plant as a function of pipe diameter and
oxygen content.
1:5 The corrosion rate of a tin plate is 2.6 mdd (Sn ! Sn2+ + 2e−). Which is the
corresponding corrosion current density (mA/m2) and penetration rate (µm/
y)? (MWSn = 118.7 g/mol, Sn density = 7.3 Mg/m3).
1:6 Calculate the maximum allowed corrosion rate of the tin layer of a tomato
containing can (can size 7.6 cm in diameter and 10 cm high) if max tin
concentration after 2 years should not exceed 50 mg/kg (the European
Standard reports 200 mg/kg as the maximum permitted value—CE 1881/
2006—19.12.06). Tin density is 7.28 Mg/m3. Tomato sauce density is
1.11 kg/dm3.
1:7 Calculate the expiration time of a tin layer of a tomato containing can (can
size 7.6 cm in diameter and 10 cm high) if max tin concentration should not
exceed 100 mg/kg. Tin average corrosion rate in declared working condition
is 0.05 µm/year.
1:8 The maximum allowable corrosion rate of a carbon steel rebar in concrete is
2 lm/year. Assuming a bar diameter of 10 mm, estimate the cross section
reduction after 20 years.
1:9 According to European standards, nickel release rates from objects in contact
with human skin must be less than 2 lg/cm2 week. How much is it the
corrosion rate in lm/year? (Ni density = 8.9 Mg/m3).
1.6 Questions and Exercises 11
1:10 Why is corrosion considered “metallurgy in reverse”?

1:11 Which are the main differences between uniform and localized corrosion?
Great Steps Forward in the Study of Corrosion Phenomena

Right up to the beginning of the 1950s, corrosion experts, «corrosionists»
were a sort of old fashioned local medical officer who worked in the field and
in all fields «visiting» corroded plants, perforated pipelines, shut-down
boilers, burst reactors and «sick» structures and then making their diagnoses,
perhaps followed by an appropriate remedy on the basis of their limited
knowledge of processes of deterioration and prevention, common sense and
professional experience. The «corrosionist’s» business was said to be an art
not a science. Indeed, even at that time knowledge was not behind the times
and not even solely empirical. U. R. Evans, who pointed out the electro-
chemical mechanism of corrosion phenomenon in the 1920s, published
important books (in 1926, 1937 and 1948, others were to appear later) cov-
ering the phenomena of passivation, corrosion by differential aeration, by
galvanic coupling and by stray currents and provided a great deal of infor-
mation on other forms of attack, on techniques of prevention and on the
corrosion related properties of various materials. In 1948, H. H. Uhlig edited
a manual on corrosion with the intention of collating data that was scattered
through the already plentiful scientific and technical literature. In 1951, E.
Rabald published his «Corrosion Guide» describing the behaviour of thou-
sands of metal/environment couples of interest to industry. Already before the
Second World War, Vernon made clear the effect of the principal factors of
atmospheric corrosion such as relative humidity or pollutants. In the case of
buried structures, the knowledge of the day went back to experiments that the
National Bureau of Standards had initiated in 1910, exactly like those of
today (in particular, Romanoff had already published results obtained by
exposing no fewer than thirty-seven thousand samples in 97 different types of
soil and on timeframes that varied from a few to 17 years!) to these condi-
tions. As far as stainless steel in particular is concerned, intergranular cor-
rosion, and the method used to block it, had been known since the 1930s to
the extent that stabilised steels with a low carbon content were already
available for use in welded structures. Similarly well-known were the con-
ditions that could foster pitting or stress corrosion, the influence of the main
environmental factors (chlorides, pH, temperature), those related to compo-
sition (e.g. the effect of molybdenum) and to the structure of the steel. In
short, a great deal of knowledge, above all empirical, already existed. Not
everyone who dealt with corrosion, however, was aware of it.
Those Fabulous Sixties. The end of the fifties saw the conditions that
enabled «corrosionists» to make a great leap forward develop. These, five in
number, were as follows. The first three concern what may be termed the
«software» of corrosion, that is: (1) the availability of electrochemical
models, originally introduced by Evans and then gradually developed and
adapted to explain the different forms of corrosion and control; (2, 3) po-
tential/pH diagrams, conceived and developed by Pourbaix, permitting the
evaluation of driving forces for different corrosion processes and specifying
the ranges of pH and potential in which conditions of immunity, passivity or
activity are established; finally, (4, 5) potential/current curves permitting the
identification and definition of the conditions for the functioning of corrosive
systems. The last two conditions, on the other hand, concern the «hardware»,
the availability of new equipment facilitating electrochemical measurements
and the study of surfaces.
This included the potentiostat, an instrument that simplified, and increased
the accuracy of, the tracing of potential/current curves for the most diverse
metals and in the most diverse environmental conditions, and new instru-
ments for the study of surfaces (optical and electronic microscopes, X-ray)
made possible by post-war development in this sector. Starting from these
five assets, research in the sixties developed extensively and clarified many
aspects of corrosion phenomena that had up to then been unknown. The
obvious consequence was the development of methods of corrosion pre-
vention and control: starting with corrosion-resistant materials (from stainless
steel to super-alloys to plastics) and continuing through inhibitors, treatment
and surface coatings to the control of the environment and cathodic protec-
tion. All this contributed to the formation of a body of knowledge that was
based on electrochemistry but had links to metallurgy and crossed the border
into applied chemistry, electrics and mechanics rising in rank to become a
genuine scientific discipline which could include corrosion phenomena and
methods for controlling them and took the name «Corrosion Science».
The Beatles Years. Over the five years from 1963 to 1968, an impressive
series of texts were published on the foundations of this discipline. These
were the years of the Beatles. In 1963, the Liverpool four had just recorded
their first single, Love me Do, and were working on She Loves You and I Want
to Hold Your Hand when U. R. Evans published—«An Introduction to
Metallic Corrosion», L. L. Sheir—«Corrosion»; H. H. Uhlig—«Corrosion
and Corrosion Control», F. L. La Que and H. R. Copson—«Corrosion
Resistance of Metals and Alloys». By 1964–65, the Beatles were a success
and drew crowds with A Hard Day’s Night, Yesterday, We Can Work it Out
and, on the corrosion front, J. Benard sent «L’oxydation des Métaux» and K.
Hauffe «Oxidation of Metals» for printing. We’re now in 1966–67. The
Liverpool four were singing Yellow Submarine, Penny Lane, Strawberry
Fields for Ever when M. Pourbaix, N. Thomashov, J. M. West, J. C. Scully
and H. Kaeshe, respectively, published their «Atlas of Electrochemical

Equilibria in Aqueous Solutions», «Theory of the Corrosion and Protection
of Metals», «Electro-deposition and Corrosion Processes», «The
Fundamentals of Corrosion» and «Die Korrosion der Metallen». Finally, in
1967–68, the time of All You Need is Love, Lady Madonna, and Hey Jude,
«Corrosion Engineering» by M. G. Fontana and N. D. Green and
«Corrosione e Protezione dei Metalli» by G. Bianchi and F. Mazza were
appearing in the bookshops. As 1969 neared, the golden age of the Beatles
was coming to an end: they had yet to write Something and Come Together
and little else and then they split up. And on the corrosion front also, the era
of assembly-line publication was over. Those books went everywhere, even if
not quite like the Beatles’ records, and enabled the «corrosionists» of the new
generation to base their professional training on solid theoretical foundations.
These books are still today the most widely read texts on corrosion, true
«evergreens» just like many of the songs of the «fabulous four».
No Longer «A Devoted Subject of Empiricism». In the course of those

years, things changed to such an extent that Professor Roberto Piontelli who
was still defining the world of corrosion as «a devoted subject of empiricism»
in 1961 referred to «corrosionists» in these terms in 1968:
«Corrosionists must concern themselves above all with correlating the
properties of composition, structure, and surface condition of metals with
their behaviour; with establishing the boundaries of compatibility, foreseeing
the onset of corrosion phenomena, their probable type (nature and distri-
bution), the course they follow in time, with diagnosing the causes of the
phenomena that have occurred, with suggesting expedients that can prevent
or limit them. Within an ambit of industrial activity in which, in addition to
other risks, pace imposes an exceptional economic burden on any shut-down,
they must prevent the catastrophic forms in which corrosion phenomena may
occur. They must therefore, know how to arrange things so that any possible
deterioration of their materials will be negligible, or gradual, so as to permit
an adequately precise estimate of their working lives in safe working con-
ditions. To face up to this extremely exacting burden of tasks and duties, they
seek assistance from thermodynamics, in order to know the conditions for the
possible onset of such dreaded phenomena in advance, investigating struc-
ture (internal or surface) no longer simply by using metallography or X-rays
but exploiting all the most modern resources (electronic microprobes,
Mossbauer Effect, neutron diffraction, slow electrons). They mobilise the
most complex equipment for kinetic electrochemical investigation and anal-
ysis. With the help of all these means, they patiently create their atlas of
«pathological anatomy» of metals exposed to the most diverse corrosive
environments, build up a ‘corpus’ of diagnostics, develop an increasingly

efficient anti-corrosion pharmacology». (Incidentally, perhaps Piontelli let
things get a little out of hand in mentioning the Mossbauser Effect or neutron
diffraction, which very few «corrosionists» know the applications of.)
Anticorrosion Engineering. At the end of the sixties it was recognised that,

in an industrialised country, corrosion generates extremely serious losses—in
terms of wasted resources, reduced service life of consumer goods, cost of
preventative measures—and it was evident that certain kinds of technical
progress—those which condition the future of mankind itself, involving
petroleum, the nuclear industry, water, the conquest of the depths of the ocean
—are blocked and precisely by these very problems of corrosion. This gave
rise to a number of initiatives to channel the knowledge gained by the newly
born science of corrosion into the fight against corrosion, first of all by
spreading this new knowledge among technicians. In this context corrosion
engineering, or as some prefer to term it, anti-corrosion engineering, was
born. The new discipline shifted attention from the metal that corroded, to the
system, i.e. to the structure, the equipment, the plant, the manufactured
article, in which the phenomenon took place, and from the mechanism and
the generic laws that govern the phenomenon, to the means and procedures
necessary for the system to be able to function in conditions of deterioration
that are acceptable. The change modified the approach to corrosion and
introduced the concepts of reliability and service life and drew the attention of
corrosion engineers to the design and construction of the structure and on the
programmes for the inspection, monitoring and maintenance to which it must
be subject.
The Seventies Also Dawn. The propulsive thrust imparted by the turning
point of the sixties, though weakened, continued into the following decade,
on both scientific and corrosion engineering fronts. In 1972, Pourbaix defined
the conditions of perfect and imperfect passivity, opening the way to the
cathodic protection of materials with an active-passive type of behaviour, like
stainless steel. Parkins demonstrated the importance of conditions of slow
deformation, the «slow strain rate», in causing the growth of cracks due to a
combination of stress and corrosion. Meanwhile, fear that failures in off-shore
platform protection and consequent collapses due to corrosion-fatigue in the
early years of North Sea oil-wells could be repeated resulted in the devel-
opment of research in the sector which led to enormous progress in the field
of cathodic protection and huge increases in knowledge of fatigue phenomena
in sea water. Moreover, the need to exploit deeper oil wells richer in carbon
dioxide and hydrogen sulphide required the development of petrochemical
industry specific materials. At the end of the seventies another sector opened
up: ever more frequently occurring damage in reinforced concrete structures
that, up to that time, had been considered everlasting, or almost, brought
corrosion engineers into the world of building construction. Much progress
was made possible by the development of surface analysis techniques some
of which had just recently become available. These included photo-electronic
spectroscopy (XPS or ESCA) and AUGER electronic spectroscopy
(AES) which are sensitive to all the elements that involve corrosion, with the
exception of hydrogen, and hence of great utility in the study of surface films.
Meanwhile, and to an even greater extent in the two decades which fol-
lowed, trade and professional associations, cultural societies, public author-
ities and, above all, standards institutes began, more and more frequently, to
issue guidelines, recommendations and standards concerning corrosion cov-
ering a wide range of applications. I remember in particular the ASTM,
NACE, ISO and CEN standards. It was precisely on the basis of the infor-
mation contained in these directives, and the know-how within the various
companies concerned with plant design and running, that the guide-lines that
all companies use in the choice of material were developed and, at the same
time, expert systems and intelligent data banks were set up. Soon the
importance of this «structured» knowledge was recognized since it contained
both the theoretical laws derived from science and from corrosion engi-
neering and the rules deriving from experience. It is a fine reward for the
corrosion engineers of the writer’s generation who for years thought that there
could be no more room for empirical knowledge in this sector.
Pietro Pedeferri, Pianeta inossidabili/XLIII, 2002
Bibliography
Bardal E (2004) Corrosion and protection. Springer-Verlag London Limited, UK

Bianchi G, Mazza F (1989) Corrosione e protezione dei metalli, 3rd edn. Masson Italia Editori,
Milano (in Italian)
Evans UR (1948) An introduction to metallic corrosion. Edward Arnold, London, UK
Fontana M (1986) Corrosion engineering, 3rd edn. McGraw-Hill, New York
Hoar TP (1971) Report of the committee on corrosion and protection, Department of Trade and
Industry, H.M.S.O., London, UK
Jacobson G (2016) IMPACT report international measure of prevention, application and
economics of corrosion technologies study. NACE International, Houston
NBS publication 511-1-2-3 (1978) Economic effects of metallic corrosion in the United States,
Report to Congress by the National Bureau of Standards, Washington D.C
Piontelli R (1961) Elementi di teoria della corrosione a umido dei materiali metallici. Longanesi,
Milano (in Italian)
Pourbaix M (1973) Lectures on electrochemical corrosion. Plenum Press, New York
Roberge PR (1999) Handbook of corrosion engineering. McGraw-Hill, London
Shreir LL, Jarman RA, Burstein GT (1994) Corrosion. Butterworth-Heinemann, London

Speller FN (1926) Corrosion. Causes and prevention. McGraw-Hill, London
Tomashov N (1966) Theory of corrosion and protection of metals: the science of corrosion.
McMillan, New York
Winston Revie R (2000) Uhlig’s corrosion handbook, 2nd edn. Wiley, London
Chapter 2
Electrochemical Mechanism
Possibly it is really the strangeness of corrosion reactions

which causes the orthodox physical chemist to regard the
whole subject of corrosion with suspicion.
U. R. Evans
Abstract Wet corrosion is based on an electrochemical mechanism in which two

reactions sum up to give the overall corrosion process; a cathodic reaction that
consumes electrons and an anodic one, where electrons are released by the metal
oxidation. In this chapter, the electrochemical mechanism is examined in details,
and the most important anodic and cathodic processes are described. From these
basic principles stoichiometric considerations will be drawn, leading to the corre-
lation between corrosion rate and current density by the use of Faraday law.
Fig. 2.1 Evans drop test at the PoliLaPP Corrosion Museum of Politecnico di Milano

https://doi.org/10.1007/978-3-319-97625-9_2
18 2 Electrochemical Mechanism
2.1 Electrochemical Processes
The corrosion of a metal, M, can be expressed by the following general reaction:
M þ aggressive environment ! corrosion products ð2:1Þ
If the environment is an electrolyte (aqueous or wet corrosion) the corrosion

reaction is the sum of two electrochemical reactions, as highlighted experimentally
in Fig. 2.1:
• an anodic process which consists of the oxidation of the metal
• a cathodic process which is a reduction reaction, typically oxygen reduction or
hydrogen ion reduction.
In the case of iron, the anodic reaction is:
2Fe ! 2Fe2 þ þ 4e ð2:2Þ
where electrons are made available; these electrons are taken by the cathodic
reaction, for instance by oxygen, with production of alkalinity:
O2 þ 2H2 O þ 4e ! 4OH ð2:3Þ
or by hydrogen ions in the case of an acidic solution, with consumption of acidity

(i.e., production of alkalinity):
4H þ þ 4e ! 4H2 O þ 2H2 ð2:4Þ
In addition to the above reactions, a corrosion process implies two further pro-
cesses, namely: (1) an electron flow within the metal from the anodic area, where
electrons are released, to the cathodic zone, where electrons are consumed; the
electron flow direction is opposite to the conventional current direction (since
electron charge is negative). (2) a current flow (circulation) within the electrolyte by
ion transportation, from the anode to the cathode zone; positive ions move in the
same direction of the current and negative ions in the opposite one. In short, a
corrosion process consists of four processes in series, as depicted in Fig. 2.2.
These four processes occur at the same rate. In fact, (a) the number of electrons
released by the anodic reaction, i.e., the anodic current, Ia, exchanged on the metal
surface, (b) the number of electrons consumed by the cathodic reaction, i.e., the
cathodic current, Ic, (c) the current flowing within the metal from the cathode to the
anodic zone, Im, and (d) finally the current circulating within the electrolyte, Iel,
must be the same:
Ia ¼ Ic ¼ Im ¼ Iel ¼ Icorr ð2:5Þ

2.1 Electrochemical Processes 19
Ia Anodic process Im
e-
Cations
Current Current
Ia = Iel = Ic = Im = Icorr
transport in transport in
Anions
the electrolyte the metal
Iel Cathodic process Ic
Anodic process
Iron Oxidation products + Electrons (in metallic phase)
Cathodic process
Oxygen + Water + Electrons (in metallic phase) Alkalinity
Ionic current in the electrolyte

Cations move as current direction, anions in opposite direction
Electronic current in the metal

Electrons move from anode, where they are released, to cathode
(i.e., in opposite direction of conventional current)
Fig. 2.2 Electrochemical mechanism of a corrosion process
This common current flow, Icorr, measures, in electrochemical units, the corrosion
process rate.
Electrochemical Mechanism of Corrosion

An electrochemical reaction implies the participation of chemical species
(neutral molecules or ions) and electrons. They are oxidation reactions, called
anodic reactions, which make available free electrons in the metal, and re-
duction reactions, called cathodic reactions, which take those electrons.
As far as anode and cathode terms are concerned, an anode is an electrode
hosting an oxidation and the electric current leaves the anode toward the
electrolyte; a cathode is an electrode hosting a reduction and the electric
current enters the cathode from the electrolyte.
In a galvanic or bi-electrode system, the positive pole is the one at higher

(more noble) potential which is connected to: (1) an anode, when current
flows due to an external source (a DC current feeder); (2) a cathode, when the
system is a voltaic pile as in the corrosion process.
2.2 Historical Notes
It is generally quoted that the Swiss scientist August De La Rive, around 1830, first
advanced the hypothesis that corrosion is produced by an electrochemical mecha-
nism, even though important observations on the matter were made previously by
the Florentine Lorenzo Fabbroni in 1792 and the Italian Alessandro Volta shortly
after his invention of the battery in 1800. Also, the English Humphrey Davy in
1824 showed that it was possible to protect the copper sheets which at that time
covered the hulls of wooden ships, through a connection with blocks of iron or zinc.
It might be of some surprise to note that despite this promising start—shortly
followed by the brief and successful incursion into the matter of Shömbein and
Faraday, who dealt with the passivity of metals in the late 1830s—the interest in
corrosion faded for the whole XIX century.
At that time, electrochemists addressed their attention to problems aroused by
Volta’s invention, the solution of which was also important for building a solid
scientific basis for the corrosion phenomena; namely, the laws between chemical
effects and electrical charge (Faraday 1835), the conductivity of the solutions
(Arrhenius 1880) and electrochemistry related energy (Nernst and Ostwald 1890).
2.2.1 Evans’s Experiences
Starting in 1923, Evans developed a series of ingenious and simple laboratory

experiences, that have become historical, to prove the corrosion theory. He used
mild steel strips, an aerated neutral solution containing potassium chloride, KCl
(3%) and two indicators: potassium ferricyanide, which turns blue when iron ions,
Fe2+, released by the corrosion reaction are complexed by ferricyanide ions, and
phenolphthalein, which turns pink for pH greater than 9. In order to measure the
circulating current, Evans used an ammeter. The two most well-known experiences
are illustrated below.
Evans’s first experience. As shown in Fig. 2.3, a droplet of the above solution is
laid on a mild steel strip. Soon, small blue dots and pink spots form
randomly (Fig. 2.3a). The blue areas indicate the presence of Fe2+ ions, identifying
the points at which the oxidation of iron occurs; while the pink zones identify where
pH increased, that is, where oxygen is reduced.
2.2 Historical Notes 21
(a) Micro-anodic
(b)
Micro-cathodic areas Anodic Cathodic
areas area area
Corrosion
products
Fig. 2.3 Evans experience (or Evans drop test): a initial condition; b steady condition
The distribution of the coloured areas changes over time and, within a few hours
or a few days, the centre of the droplet becomes blue, while its border becomes
pink (Fig. 2.1). Meanwhile, as the Fe2+ ions diffuse towards the oxygen-rich border,
they are oxidized to Fe3+ ions, which precipitate as Fe(OH)3 in an intermediate
region between the centre and the edge of the droplet (Fig. 2.3b). At the end of the
experiment, the metal surface in correspondence of the droplet border is not cor-
roded, while in the centre a corrosion crater is formed.
This experience proves that even in neutral aerated solution the corrosion attack
of the iron is produced through an electrochemical mechanism implying two
electrochemical processes: the oxidation of iron (anodic process) and oxygen re-
duction (cathodic process). The two processes take place on separated areas of the
metal surface, which act as anodic and cathodic zones, respectively. Since the
oxidation (anodic) process releases electrons, while the reduction (cathodic) process
consumes them, it can be concluded that within the metal a current circulates from
cathode to anode and within the electrolyte in the opposite direction as shown in
Fig. 2.4.
This experience of Evans’s also shows that the electrochemical mechanism is
“self-organizing:” at the beginning, corrosion seems to be randomly distributed
over the entire surface of the steel strip; then, once a steady state condition is
reached, corrosion localizes and proceeds at the centre of the droplet where the
oxygen diffusion slows down. The organizing criterion is governed by the
Fig. 2.4 Current flow in O2 O2

Evans drop test
O2 I I O2
OH- OH-
Fe2+
Fe(OH)3 e- e- Fe
(a) Iron (b)

strip
I
Preferential zone Cathodic
of oxygen reduction area
Insulating A
joint
Preferential zone
of corrosion
Anodic
area
Fig. 2.5 Evans second experience
non-uniform distribution of oxygen inside the droplet, which eventually determines

the morphology of the attack. Instead, one could expect a casual morphology
determined by the initial attack, which is intrinsically random because of the
presence of a continuous, oxygen-containing film.
Evans’s second experience. In a second experiment, Evans highlighted the current
flow between the cathodic and anodic zones established on the metal surface.
Figure 2.5 illustrates the set up that consists of a strip of iron (or zinc) immersed in
a cylinder containing the solution above described. Evans noted that corrosion
attack occurred preferentially on the bottom, which is far from the solution free
surface (Fig. 2.5a), where the cathodic process of oxygen reduction took place. As
in the case of the droplet, the attack tends to localize in areas where the oxygen
initially present is consumed and not replaced. Then, Evans proceeded by cutting
the strip along the separation line between the corroded areas (at the bottom) and
those not corroded (at the top). He then connected the two pieces by means of an
insulating joint, then restoring the electrical continuity through an external metallic
circuit. An ammeter was inserted in the circuit for measuring the current, as shown
in Fig. 2.5b. The ammeter showed a current flow from the cathodic upper region
toward the corroding lower anodic zone: the electrochemical nature of the process
was then brilliantly demonstrated.
Corrosion Mechanism
August De La Rive proposed an electrochemical mechanism based on the
observation that impure zinc in acidic solutions corroded faster than pure
zinc, which he attributed to an electrical effect between matrix and impurities.
Towards the end of the century, corrosion experienced a new awakening
as soon as it was considered a normal chemical reaction between metals and
2.2 Historical Notes 23
acids; even rust was believed to be the result of a reaction with the carbonic
acid present in the atmosphere. Curiously, no one recognized the enormous
importance of the role played by oxygen, even the Swedish Palmaer who
rediscovered the electrochemical mechanism at the beginning of the
Twentieth century. He reconsidered De La Rive’s observation about the
influence of impurities on the corrosion of zinc in acidic solutions, and
pointed out how this was related to the action of micro cells made of
impurities and the surrounding metal matrix. This suggested to the scientist
the wrong theory—endorsed by the scientific community at the time—that a
perfectly pure metal, assuming it would be manufactured, cannot corrode
because of the lack of impurities, i.e., the lack of the tiny local electrodes to
set up the corrosion microcell.
Only twenty years later, U. R. Evans and his School at the University of
Cambridge showed that metals corrode even in the absence of impurities, in
environments of any pH, often because of the presence of dissolved oxygen
in the solution; he also contributed to give experimental and quantitative
support to the electrochemical theory of corrosion.
2.3 Local Cell Theory
Evans’s experience is based on a separation of anodic and cathodic regions (at

micro scale the former, and at macro scale the latter). Indeed, this separation is
confirmed by direct visual check with a microscope. This evidence suggested the
so-called local cell theory, which can be summarized by the two following
statements:
• The mechanism of corrosion processes is electrochemical
• Different zones of the metal surface could assume a behaviour either anodic or
cathodic
According to this theory, corrosion consists of electrodes in short circuit like the
short-circuited battery shown in Fig. 2.6. M and N are the regions exhibiting the
anodic and cathodic behaviour, respectively, IMN is current of the local cell flowing
from cathode to anode within the metal, and e is the electrolyte (aggressive
environment).
However, in most corrosion case studies, local cells cannot be found even at
micro scale, although laboratory experiments proved that affecting parameters and
their relationships are the same. This evidence suggested the presence of hetero-
geneities or impurities or metallurgical defects at a “submicroscale” acting as
anodic and cathodic zones. On this basis, the local cell theory was considered valid
also for those case studies.
Fig. 2.6 Electrochemical cell IMN

model of a corrosion process
(M anodic surface, N cathodic
surface; short-circuited)
2.3.1 Mixed Potential Theory
Truthfully, some doubts still remained. There are homogeneous systems, such as
the amalgams, in which the local cell at “sub-microscale” cannot exist; in this case
study, the local cell theory seems to fail. To eliminate this contradiction, in 1938
Wagner and Traud proposed that on homogeneous materials exposed to homoge-
neous environments both anodic and cathodic reactions could take place simulta-
neously and alternatively on the same place. This theory is called mixed potential or
Wagner and Traud theory, which states as follows:
• The corrosion process follows an electrochemical mechanism (even in the
absence of any kind of heterogeneity), and proceeds through electrochemical
anodic and cathodic reactions over the entire metal surface
• The rate of each anodic or cathodic process depends on potential only,
regardless any other processes
• Anodic and cathodic processes are complementary. In other words, the sum of
all anodic process rates equals the sum of all cathodic process rates. This is the
principle of conservation of charge: the number of electrons released at the
anode is the same of those used at the cathode.
Wagner and Traud came to the formulation of their theory after studying, in acidic
solutions, the rate of hydrogen evolution on mercury and homogeneous amalgams.
The two scientists noted that if pure mercury was maintained at the potential to
which amalgam of zinc freely corrodes, the rate of hydrogen evolution was the
same. This proved that hydrogen evolution is determined by the potential regardless
if the process is spontaneous (as it was for the amalgam) or imposed (as it was for
the pure mercury).
After this initial assertion, Wagner and Traud extended their theory to hetero-
geneous conditions either for the metal surface or the environment, assuming that a
zone could be predominantly anodic or cathodic and not merely anodic or cathodic,
as in the local cell theory. In this light, the local cell theory can be regarded as a
special case of the more general mixed potential theory.
2.4 Corrosion Reactions 25
2.4 Corrosion Reactions
The corrosion process involves various aspects, which deal with anodic and
cathodic reactions, electrophoretic migration of ionic species within the electrolyte,
secondary chemical reactions between metal and anodic or cathodic products, as
illustrated hereafter.
2.4.1 Anodic Process
A generic anodic process of a metal is an oxidation reaction, which can produce a

metallic ion, releasing electrons:
M ¼ Mz þ þ ze ð2:6Þ
where z− is the number of electrons, M is a generic metal and Mz+ is a metal ion
which passes into solution. Or, in specific ranges of pH or in the presence of
particular species, metal ions are separated as insoluble compounds (oxides,
hydroxides, salts), as for example:
M þ zH2 O ¼ MðOHÞz þ zH þ þ ze ð2:7Þ
where M(OH)z is an insoluble product, in this reaction example a hydroxide.

Examples of anodic reactions, with metal dissolution and formation of metal
ions, complexes or precipitates, are:
Ag ! Ag þ þ e
Fe ! Fe2 þ þ 2e
Al ! Al3 þ þ 3e
Al þ 2H2 O ! AlO2 þ 4H þ þ 3e
Mg þ 2OH ! MgðOHÞ2 þ 2e
Ag þ Cl ! AgCl þ e
Fe þ CO3 2 ! FeCO3 þ 2e
In anodic processes the species electron is produced by the reaction; therefore, it

appears in the second member of the reaction.
Corrosion Science and Corrosion Engineering

Starting from the third decade of last century, research in the corrosion field
headed to electrochemistry, and in half a century, scientist like Evans first and
then Vernon, Pourbaix, Piontelli, Uhlig, Hoar, Tomashov, Stern and others
created a body of knowledge framed by electrochemistry, with links to
metallurgy, applied chemistry, electronics, and mechanics. In the ’70s of the
XX century this knowledge rose to the rank of a scientific discipline that took
the name of Corrosion Science, which enables to rationalize corrosion phe-
nomena and their control methods.
In those years, it was realized that corrosion produces very high losses,
especially in industrialized countries. This appeared as a clutch for techno-
logical developments in strategic industry related activities for the future of
humanity, such as oil and gas, nuclear, deep water and many others.
Consequently, within the fight against corrosion, a series of actions developed
to steer the knowledge of the newborn corrosion science, primarily by
teaching and training. In this context, corrosion scientists/engineers—such as
Fontana, Green, Bianchi, Parkins, Staehle and many others—gave rise to
Corrosion Engineering.
This new discipline shifted the focus from the corroding metal itself, to the
system in which corrosion occurs (i.e., structures, equipment, plants, com-
ponents) and to the laws that govern the phenomenon, its mechanism and
control methods with the aim to make corrosion acceptable from an industry
viewpoint.
This change altered the approach to corrosion introducing the concepts of
risk, reliability, service life. It also brought to the attention of corrosion
engineers not only the choice of materials, but also design, construction,
inspection, monitoring and maintenance programs to guarantee the design
life. In the early 1990s, Giuseppe Bianchi (1919–1996) indicated “corrosion
informatics” as the new branch of corrosion.
2.4.2 Cathodic Processes
The cathodic process takes the released electrons from the metal to reduce the
chemical species present in the environment. The generic reaction is:
OXy þ þ ze ¼ RDw þ ð2:8Þ
where z = y − w, OXy+ is oxidized species and RDw+ is reduced species.

Cathodic reactions of practical interest for corrosion are limited in number. In the
case of corrosion in an acidic solution, the cathodic process is the reduction of
hydrogen ions to produce either atomic or molecular hydrogen, according to the
reactions:
H þ þ e ¼ H or 2H þ þ 2e ¼ H2 ð2:9Þ
In neutral or alkaline environments and in natural environments (atmosphere, soil

and waters), the most important cathodic reaction is the oxygen reduction reaction:
2.4 Corrosion Reactions 27
O2 þ 2H2 O þ 4e ¼ 4OH ð2:10Þ
In acidic solution, the corresponding reaction is:
O2 þ 4H þ þ 4e ¼ 2H2 O ð2:100 Þ
The reactant oxygen that appears in the above reactions is the molecular oxygen
dissolved in water, the concentration of which varies from 0 to 12 milligrams per
kilogram of water (ppm).
In addition, water can give a cathodic reaction in a specific potential range, as
follows:
2H2 O þ 2e ! 2OH þ H2 ð2:1000 Þ
Another relevant cathodic reaction is the reduction of chlorine to chloride:
Cl2 þ 2e ! 2Cl ð2:10000 Þ
2.4.3 Other Cathodic Processes
There are other possible cathodic processes that occur in peculiar conditions:
1. reduction of metal ions to a lower valence:
Fe3 þ þ e ! Fe2 þ
Cu2 þ þ e ! Cu þ
Hg2 þ þ e ! Hg þ
2. reduction of anions:
2ClO þ 2H þ þ 2e ! 2Cl þ H2 O

NO2 þ 2H þ þ e ! NO þ H2 O
Cr2 O7 2 þ 14H þ þ 6e ! 2Cr3 þ þ 7H2 O
2.4.4 Complementary Processes
Since the circulation of current and subsequent chemical modifications do not alter
the electrical state of the system, anodic and cathodic reactions must be comple-
mentary from the viewpoint of the electrical charge balance, and must be
simultaneous from the viewpoint of the reaction rate. This implies that the stoi-
chiometric coefficients of the electron, usually denoted by z, must be identical: this
is called equivalence of the chemical reaction (see examples in box).
2.5 Stoichiometry (Faraday Law)
The stoichiometry of electrochemical reactions is governed by the Faraday law,

which reads as follows. The mass, DmðgÞ, of the chemical species and the charge,
Q (Coulomb), exchanged in the electrode process are linked through the electro-
chemical equivalent, according to the relation:
echem MW
Dm ¼ eech Q ¼ Q¼ It ð2:11Þ
F zF
where eech is the electrochemical equivalent, echem is the chemical equivalent, F is

Faraday’s constant (96,485 C or 26.8 A h), I is current (A), t is time (s) and MW is
atomic or molecular mass (g/mol). Electrochemical equivalent, eech, and chemical
equivalent, echem, represent the mass relative to a charge of 1 C or to 1 F,
respectively.
2.5.1 Corrosion Current Density
The corrosion rate can be obtained through Eq. 2.11 as follow:
C rate;m Dm eech Q 1
C rate ¼ ¼ ¼ ¼ eech ia ð2:12Þ
c cSt cSt c
where ia is the anodic current density, also called corrosion current density.
In electrochemical units, the corrosion rate is measured in mA/m2, or in
lA=cm2 ð1 lA=cm2 ¼ 10 mA=m2 Þ. The constant eech =c in Eq. 2.12 depends on
metal as reported in Table 2.1. As rule of thumb, penetration rate, Crate, expressed
in lm=year corresponds approximately, in electrochemical units, to mA/m2, for
many metals such as iron, copper, nickel, aluminium.
2.6 Change of the Environment
The environment composition varies as corrosion proceeds. First, there may be

significant variations in pH. In particular, in cathodic zones, alkalinity increases due
to both oxygen reduction and hydrogen evolution; whereas, in anodic regions,
2.6 Change of the Environment 29
Table 2.1 Equivalence of the corrosion rate (mm/year) for an anodic current density of 1 mA/m2
Metal Valence Density (g/cm3) Equivalent Corrosion rate
mass (g/eq) ðlm=yearÞ
Iron Fe2+ 7.87 27.92 1.17
Nickel Ni2+ 8.90 29.36 1.09
Copper Cu2+ 8.96 31.77 1.17
Aluminium Al3+ 2.70 8.99 1.09
Lead Pb2+ 11.34 103.59 2.84
Zinc Zn2+ 7.13 2.68 1.50
Tin Sn2+ 7.30 59.34 2.67
Titanium Ti2+ 4.51 23.95 1.75
Zirconium Zr4+ 6.50 22.80 1.91
AISI 304 Fe2+, Cr3+, Ni2+ 7.90 25.12 1.04
2+ 3+ 2+ 3+
AISI 316 Fe , Cr , Ni , Mo 8.00 24.62 1.04
acidity increases due to the hydrolysis of corrosion products. Other changes in

composition also take place. For example, metal ions accumulate in the anodic
regions when, in suitable conditions, current is mainly transported by anions; or in
the cathodic regions, the dissolved oxygen content decreases.
Examples of Complementary Processes

1. The corrosion of iron in an acidic solution takes place as a result of two
reactions:
Fe ! Fe2 þ þ 2e
2H þ þ 2e ! H2
Therefore, the global reaction is:
Fe þ 2H þ ! Fe2 þ þ H2
The equivalence of this reaction is then 2. Recalling that the atomic mass
of iron is 55.8, and 2 g/mol for hydrogen, the oxidation of 55.8 g of iron
results in the development of 2 g of hydrogen gas.
2. The corrosion of iron in an aerated solution takes place as a result of the
following two reactions:
2Fe ! 2Fe2 þ þ 4e

O2 þ 2H2 O þ 4e ! 4OH
Therefore, the global reaction is:

2Fe þ 2H2 O þ O2 ! 2Fe2 þ þ 4OH
In this case, the equivalence of the reaction is 4. The oxidation of 111.6 g

(= 55.8 g 2) of Fe to Fe2+, requires the reduction of 32 g of O2 (since
32 g/mol is the molecular mass of oxygen), and the consumption of 36 g
of water, being 18 g/mol the molecular mass of the water.
3. If the corrosion of iron takes place according to the following two reac-
tions:
2Fe ! 2Fe3 þ þ 6e
3=2O2 þ 3H2 O þ 6e ! 6OH
the global reaction is:
2Fe þ 3H2 O þ 3=2 O2 ! 2Fe3 þ þ 6OH
and the equivalence of the reaction is 6. The oxidation of 111.6 g

(= 55.8 g 2) of Fe to Fe3+, requires the reduction of 48 g of O2
(1.5 32 g), and the consumption of 54 g of water (= 3 18 g).
How to Calculate Chemical (MW/z) and Electrochemical (MW/zF)

Equivalent
MW is the molar mass and z the valence to form an ion Mz+. For example, in
the case of the reaction Fe = Fe2+ + 2e−, the mass of iron which is oxidized
by a charge of 1 F or 1 C is equal to respectively 55.8 g / 2 = 27.6 g and
55.8 g / (2 96,485) = 1.036 10−5 g.
MW is the molar mass of a species partially oxidized or reduced by a
valence change of z. For example, in the case of the reaction
Fe2+ = Fe3+ + e−, the mass of ferrous ion which oxidizes by a charge of 1 F
or 1 C is, respectively, 55.8 g and (55.8 g / 96,485) = 2.072 10−5 g.
(MW/F)(z/Z) or MW(z/Z), where MW is the molecular mass of a generic
neutral species participant to the electrode process with stoichiometric coef-
ficient z, and Z is the stoichiometric coefficient of the electron. For example,
in the case of the reaction O2 + H2O + 4e− ! 4OH−, the mass of oxygen
consumed by a charge of 1 F or 1 C is, respectively, 32 g / 4 = 8 g and 32 / 4
F, that is 8 / 96,485 = 8.29 10−5 g.
In the case of alloys, the electrochemical equivalent is approximately the
weighted average of that of each element of the alloy composition. For
example, the electrochemical equivalent of a stainless steel of composition
19% Cr, 9.25% Ni and 71.75% Fe (all other elements with content less than
1% are neglected), is 25.12, bearing in mind that the valence of the three
2.6 Change of the Environment 31
elements is 3, 2 and 2, and their molecular weight is 52, 59 and 56,

respectively.
The specific enunciation of the Faraday law is not necessary if in the
formulation of the electrochemical reaction the electron is considered as any
other chemical species. Then, the symbol e− represents, from the stoi-
chiometry viewpoint, a mole of electrons, i.e., a number of electrons equal to
Avogadro’s number (6.022 1023), and then with charge 1 F, or 96,485 C or
26.8 A h (obtained by multiplying the elementary charge of the electron,
equal to 1.602 10−19 C, to Avogadro’s number). Since the ‘chemical
species’ electron is monovalent, one mole of electrons also corresponds to
one gram-equivalent of electrons; precisely engaging, in an electrochemical
reaction, a gram-equivalent of substance.
Therefore, for example:
• A mole of hydrogen (2 g), according to the reaction 2H+ + 2e− = H2,
needs two moles of electrons, i.e., 2F and then 2 96,485 C, or 2 26.8
A h to oxidize one mole of iron (55.8 g) to ferrous ions; according to the
reaction Fe = Fe3+ + 3e−, 3 mol of electrons are required, i.e., 3F and
then 3 96,485 C, or 3 26.8 A h to oxidize one mole of iron (55.8 g)
to ferric ions
• To reduce one mole of oxygen (32 g), according to the reaction
O2 + 2H2O + 4e− = 4OH−, 4 mol of electrons are needed that is, 4F and
then 4 96,485 C, or 4 26.8 A h.
It is worthwhile recalling that an anodic current of 1 A brings into solution a
metal mass of echem/96.485 = 0.00001036 echem (g/s), or echem/
26.8 = 0.000373 echem (g/h), and also 326 echem (g/year). For example, 1 m2
iron plate which corrodes according to the anodic reaction Fe = Fe2+ + 2e−,
for a total current of 1 A, the amount of iron which goes into solution in a year
is equal to Crate,m = 326 echem (g/year) = 326 (55.8/2) = 9.1 kg/year. Since
the density of iron, c, is 7.85 Mg/m3, the penetration rate, Crate, is equal to
DW=ðScÞ ¼ 9:1 kg/(1 m2 7.85 Mg/m3) = 1.17 mm/year. In conclusion, an
anodic current of 1 A/m2 produces a corrosion attack of about 1 mm/year.
Then, a current density of 1 mA/m2 causes an attack of about 1 lm=y.
The magnitude of the variation of composition strongly depends on electrode

reactions and on electrophoretic transport, diffusion and convection within the
solution. The latter become particularly important in those cases—which will be
studied more in detail later—in which particular geometries (created by the pres-
ence of cracks, dead spaces, corrosion products or deposits) lead to a split of the
electrolyte composition between anode and cathode, with the formation of occluded
cells, where aggressive species can concentrate.
Furthermore, reduced or oxidized species formed by cathodic and anodic pro-
cesses can react with the separation of basic salts, oxides, hydroxides often able to
produce layers on the metal surface which play a key role in determining the
corrosion behaviour of the metal in that environment.
2:1 In a corrosion cell, which is the positive and the negative electrode? Which
reactions occur at the positive and negative electrode? Give an electrical
explanation.
2:2 In natural environments, such as seawater, fresh water, soil and condensed
water (dew) in the atmosphere, which is the dominating cathodic reaction in
the corrosion of mild steel? Write the reaction equation. Can rust formation
affect the corrosion rate?
2:3 Which property of the corrosion medium (the aqueous solution) is the most
important prerequisite for electrochemical corrosion?
2:4 What can be said about the relationship between the anodic current, Ia, and
the cathodic current, Ic, in a corrosion process? And what about current
densities, respectively?
2:5 Estimate carbon steel corrosion rate corresponding to 1 mA/m2 anodic cur-
rent density.
2:6 A steel plate has corroded on both sides in seawater. After 10 years, a
thickness reduction of 3 mm is measured. Calculate the average corrosion
current density. Take into consideration that the dissolution reaction is
mainly Fe = Fe2+ + 2e−, and that the density and the atomic mass of iron are
7.8 Mg/m3 and 56 g/mol, respectively.
2:7 Suppose and reproduce Evans’s first experience on a copper plate with a
seawater drop. Write the corrosion reaction and indicate inside the seawater
drop where presumably the corrosion product forms, namely the copper
oxy-chloride (approximately Cu(OH)Cl).
2:8 Evans’s second experience does not work when using copper. Try to indicate
possible causes.
2:9 Write the cathodic reaction occurring by copper ion displacement and
determine the value of constant eech =c of Eq. 2.12. [Hint: refer to Sect. 7.2.5]
2:10 Write the corrosion reaction of silver exposed in a solution containing H2S.
By means of Faraday Law, calculate the corrosion rate ðlm=yÞ, if corrosion
current is 0.01 A, and if the silver sample has a surface area of 0.1 m2.
2:11 How much oxygen is necessary to completely corrode a square carbon steel
plate (10 cm in side, 10 mm thick).
2:12 The corrosion current density on a galvanized steel plate (steel coated with
zinc coating) is 1.25 10−7 A/cm2. Zinc coating thickness is 0.02 mm.
After how many years the coating will be completely corroded?
(MWZn = 65.3 g/mol, cZn ¼ 7:14 Mg=m3 ).
Alessandro Volta Priorities

Pietro has reviewed and read almost completely the writings and letters of
Alessandro Volta, highlighting some interesting discoveries obtained by the
scientist. This book includes four of them, related to the first law of Faraday
(hereafter), the Ohm’s law (Chap. 5), the definition of the potential ranking
and driving force (Chap. 10) and the principle of cathodic protection
(Chap. 19).
Alessandro Volta and the First Faraday Law

From the letter that Volta sent to Van Marum (June 1802 1), it is clear how
Alessandro Volta knew not only to identify the physical elements related to
the pile but also to specify the quantitative relationship that links them
together. In this letter, Volta anticipates many of the chemical effects pro-
duced by the current circulation, that Faraday will obtain thirty years later.
Volta asks Van Marum to carried out a series of tests, as he is not able to
perform because he did not have powerful generators. In the letter he wrote
“An important thing is to try to obtain the hydrogen gas evolution, and the
oxidation of the two metal wires immersed in water […] produced by the
continuous functioning of the pile, to obtain the effect, I say, with many
charges [of capacitor banks] reiterated by shooting from the current of a
good pile. Things can be easily arranged in such a way that such charges and
alternate discharges occur with the interval of half a second or less. But I
would like it even more if you succeed in another way that I have already
proposed to you: with the direct electric current using your big generator.
This copious current, perhaps like that of a good pile (you believe it even
more abundant, but I doubt it a lot), forced by a convenient arrangement to
move from one wire through the water to another in free communication with
the wet soil or, even better, with the bearings of the machine in action, it
should make almost the same amount of hydrogen gas appearing around a
wire and oxygen gas or metal oxide around the other, as with the pile. Yes,
the same quantity and in the same way and with the same appearances, if
really your great and prodigious generator is able to provide and to allow to
flow through endless conductors as much electric fluid in every moment or in
a given time, as the pile supplies. It will therefore be the success of the
experiment that decides which of the two devices is able to supply more. For
other generators that are not as big and excellent as your, it is already
proven that they provide much less current than even a small pile”
1
The letter is part of Volta’s correspondence with the Dutch physics Van Marum, who
had a powerful scrubbing electric machine in Rotterdam. Unfortunately, Van Marum, unlike what
he did with previous letters, did not make it public. The letter was only disclosed in 1905 when
J. Bosscha published the correspondence Volta-Van Marum.
Volta makes some fundamental statements. He hypothesises the identity,

as regards the chemical effects produced, of the electric fluid regardless of
whether it is generated by a battery, a capacitors bank or a scrubbing
machine. Anticipate the first Faraday law of electrochemical stoichiometry.
He proposes to compare the quantity of electric fluid produced by two dif-
ferent generators on the basis of the extent of the chemical effects resulting
from the current circulation. Moreover, he states that a similar evaluation has
already been made (evidently by him and in the manner just indicated) to
compare the amount of electric fluid supplied by the pile and by generators
less powerful than that of Van Marum.
The text shows how Volta in 1802 and Faraday in 1832–33 follow the
same scientific path. Both start from the problem of verifying the identity of
the electric fluid produced by different generators,2 then arriving at the law
that links the mass formed or transformed at the electrodes to the circulated
charge, finally they both propose to apply the law to the measurement of the
exchanged charge.3
We can now compare the law indicated by Volta in the case of hydrogen
evolution, oxygen or oxide formation and the general law enunciated thirty
years later by Faraday.
Volta in 1802 wrote: “The same quantity of hydrogen is produced at the
cathode and the oxygen or oxide are formed at the anode […]—the same
quantity, in the same way, with the same appearances—if really the electric
scrubbing machine is able to provide and to allow circulating […] as much
electric fluid in every moment or in a given time as it provides and passes the
pile.”
Faraday, thirty years later, wrote: “Electricity, whatever may be its source,
is identical in its nature. […] For a constant quantity of electricity the
amount of electro-chemical action is also constant.”
2
Faraday checked the chemical effects not only produced by the electricity obtained from the pile,
from the friction machine or from the batteries of condensers—which called “voltaic electricity” or
“common electricity”—but also the effect of the “animal electricity”, of the “thermoelectric”
(Seebek effect) and of the “magneto-electric” one (by induction).
3
Pietro Pedeferri wondered a lot of time why Faraday proposed in 1833 to call Volta-electrometer
and then in 1838 Voltameter, the instrument he developed to determine the charge circulated
through the measurement of the chemical effects produced, since Volta was at that time was accused
(as, moreover, happens today: read for example what the former president of the Senate Pera wrote
on Volta in his book “The Ambiguous Frog”, Princeton University Press) to have always disin-
terested in the correlation between the circulated charge and the chemical effects, indeed the
chemical effects “tout court”. In light of the priority just mentioned, it is clear that Faraday could not
find a more suitable name, even if he could not know it. In fact, the English scientist could not know
the content of the letter that Volta had written to Van Marum that will be disclosed only in 1905.
“And I do not even think—Pietro Pedeferri said—that when, in 1812 in Milan, Faraday, still very
young and unknown, took part with Davy at the meeting with the almost seventy, very famous and
acclaimed Volta, the inventor of the pile may have talked about this with him.
Bibliography 35
Bibliography
Evans UR (1948) An introduction to metallic corrosion. Edward Arnold, London

Milano (in Italian)
Tomashov N (1966) Theory of corrosion and protection of metals: the science of corrosion.
McMillan, New York
Chapter 3
Thermodynamics of Aqueous Corrosion
There is nothing more practical than a good theory.

W. Nernst
Abstract This chapter addresses the thermodynamic aspects of corrosion, starting

from the concept of free energy: indeed, corrosion can take place only if the free
energy variation associated with the reaction is negative, i.e., the reaction is ther-
modynamically favoured. This translates in terms of variation of potential, outlined
as driving voltage, or electromotive force, for the reaction. Standard potentials and
equilibrium potentials of anodic and cathodic reactions are defined, together with
conditions for corrosion and for immunity. Reference electrodes are presented, which
allow to measure the potential as difference between a given electrode and a well
defined reference electrode that has the property of maintaining its potential constant.
Finally, electrochemical cells, as Daniell or concentration cells, are introduced.

https://doi.org/10.1007/978-3-319-97625-9_3
38 3 Thermodynamics of Aqueous Corrosion
3.1 Driving Voltage and Free Energy
A chemical reaction, such as a corrosion process, exemplified in Fig. 3.1 can be

described by a reaction of the following type:
aA þ bB þ ! cC þ dD þ ð3:1Þ
To this reaction, it is possible to associate the variation of a state function, called

free energy, G, which decreases as the reaction proceeds (i.e., there is a driving
voltage available for the occurrence of this process). This reduction, denoted ΔG, is
also named reaction affinity.
A positive driving voltage (−ΔG > 0, then ΔG < 0) is a necessary condition for
a reaction to occur. Conversely, the fading of the driving voltage (ΔG = 0) or the
presence of a negative driving voltage (i.e., ΔG > 0) is a sufficient condition to
exclude the possibility that the reaction will take place. In the first case (ΔG = 0),
the reaction is in a condition of equilibrium, whilst in the second case (ΔG > 0), the
system tends to evolve in the opposite direction to that indicated, unless there is the
intervention of an external energy.
These thermodynamic concepts are more easily understood when considering a
mechanical analogy, in which the system is a body placed on an inclined plane
(Fig. 3.2a). The direction of the spontaneous movement of the body can only be the
one that corresponds to a reduction of the potential energy, that is, toward lower
heights (i.e., there is a positive driving voltage given by the gravity force). The
equilibrium condition is reached when the plane is horizontal, which corresponds to
the zeroing of this work (Fig. 3.2b). Finally, the movement of the body in the
direction that corresponds to an increase of height cannot occur spontaneously:
instead, it is obtained only through the intervention of external forces (Fig. 3.2c).
It is worth remembering that the assessment of the free energy change, ΔG,
associated with any reaction, implies the knowledge of all chemical species
involved and their thermodynamic levels. These levels are: in the case of dissolved
species, their activities (i.e., their concentration modified by an appropriate cor-
rection coefficient, called activity coefficient, which takes into account environ-
mental effects); in the case of gaseous species, the fugacity (i.e., their partial
pressure modified by an appropriate correction coefficient, called fugacity coeffi-
cient, which takes into account environmental effects).
Fig. 3.2 The mechanical (a) (b) (c)

analogy of a corrosion
process: a spontaneous;
b equilibrium;
c non-spontaneous
G < 0 G = 0 G > 0
3.1 Driving Voltage and Free Energy 39
The free energy variation, ΔG, of Eq. 3.1 can be expressed as:
acC adD . . .
DG ¼ DG0 þ RTln ð3:2Þ
aaA abB . . .
where ΔG0 is the standard Gibbs free energy change involved in the reaction (i.e.,
when occurring at standard conditions, with unitary activity for species in liquid
and solid phase, and fugacity 1 atm for gaseous species), R is the universal gas
constant equal to 8.314 J/mol K, T is the absolute temperature, and, finally, aiI are
the activities of species, I, elevated to their stoichiometric coefficient.
3.2 Corrosion and Immunity Condition
A corrosion process is represented by the following reactions:
M þ A ! Mz þ þ ðz=aÞAa ðglobal reactionÞ ð3:3Þ
M ! Mz þ þ ze ðanodic reactionÞ ð3:4Þ
A þ ze ! ðz=aÞAa ðcathodic reactionÞ ð3:5Þ
Since a corrosion process is of electrochemical nature, the free energy variation,

ΔG, can be expressed through the electrical energy variation:
DG ¼ z F DE ð3:6Þ
where ΔE is the electromotive force (EMF) of the reaction, z and F have the known
meaning. In the following, ΔE is called driving voltage or potential difference.
The thermodynamic condition for a spontaneous process (ΔG < 0) becomes:
DG\0 ) DE [ 0 ð3:7Þ
that is, a positive driving voltage (ΔE > 0). From the expression of free energy
Eq. 3.2 by introducing the potential, the well known Nernst1 equation is
obtained (for its general formulation see Eq. 3.17).
For the anodic reaction:
zþ
=M RT ½Mz þ RT
EM ¼ E0 þ ln ; then Ea ¼ Ea0 þ ln½Mz þ ð3:8Þ
zF ½M zF
1
Walther Herman Nernst (1864–1941) was a German chemist. He received the Nobel Prize for
Chemistry in 1920.
For the cathodic reaction:
a RT ½Aa RT
EA=A ¼ E 0 ln ; then Ec ¼ Ec0 ln½Aa ð3:9Þ
zF ½A zF
The free energy variation, ΔG, is expressed by the potential as follows:
DE ¼ Ec Ea ð3:10Þ
hence, the condition for a spontaneous corrosion process is:
DE [ 0 ) Ec Ea [ 0 Ec [ Ea ð3:11Þ
that is, the equilibrium potential of the cathodic reaction must be more positive
(more noble) than the anodic process (metal oxidation).
Corrosion as an electrochemical process can be represented by the cell depicted
in Fig. 3.3, where the anodic reaction occurs on M, while the complementary
cathodic process takes place on N, in the electrolyte, e (the electrochemical cell is
indicated as: M/e/N). The potential difference between M and N ðEMN eq Þ can be
derived as the difference between potentials measured against a same remote ref-
erence electrode, R:
MN
Eeq ¼ Eeq
MR
þ Eeq
RN
¼ Eeq
MR
Eeq
NR
ð3:12Þ

where EeqMR
¼Eeq;a is the anodic equilibrium potential and EeqNR
¼Eeq;c is the
cathodic equilibrium potential, both measured against the same reference, R. It
results:
MN
Eeq ¼ DEMN ¼ Eeq;c Eeq;a ð3:13Þ
as already above obtained.
Fig. 3.3 Equilibrium

potential (E eq MN ) of the
corrosion system MN as sum
of anodic and cathodic R
equilibrium potentials
MR RN
Eeq Eeq
MN
Eeq
3.2 Corrosion and Immunity Condition 41
In conclusion:
• The necessary condition for the occurrence of a corrosion process is that the
driving force is positive. This occurs if the equilibrium potential of the cathodic
process, Eeq,c, is greater than that of the anodic process, Eeq,a
• The sufficient condition to prevent any corrosion process is that the driving force
is zero or negative. This occurs if the equilibrium potential of the cathodic
process, Eeq,c, is less than or equal to that of the anodic process, Eeq,a
• To evaluate the driving voltage it is necessary to know the equilibrium poten-
tials of the individual electrode reactions taking place on the surface of
materials.
3.3 Standard Potential
Let's consider the galvanic cell, M/e1//e2/H, at 25 °C obtained by coupling a metal,

M, in equilibrium with a solution, e1, of unitary concentration of metal ions, with a
reference electrode consisting of a platinised platinum wire2 immersed in a solution,
e2, of unitary acid concentration (pH = 0), bubbling hydrogen gas at a pressure of
1 atm. This electrode is called Standard Hydrogen Electrode (SHE). A salt bridge,
consisting of a glass tube filled with agar-agar gel saturated with KCl, electrically
connects the two solutions, e1 and e2, keeping them physically separated (Fig. 3.4).
The equilibrium reaction on the surface of metal M is:
M ! Mz þ þ ze ð3:14Þ
and the one on the platinum surface is:
2H þ þ 2e ! H2 ð3:15Þ
These two reactions, when the circuit is open, are in equilibrium.

The potential difference between terminals M and H, respectively in contact with
metal, M, and platinum, is the equilibrium potential of metal M measured toward
the standard hydrogen electrode, SHE, whose potential is taken conventionally
equal to zero at all temperatures. The standard potential of metal M at the tem-
perature considered is E0, i.e., the equilibrium potential at unitary concentration
(1 mol/L).
The list of standard potentials, E0, of the various elements, sorted by increasing
potential, is the so-called series of standard potentials (Table 3.1). Potentials are all
referred to the reduction reactions. It is conventional to refer to the term nobility
2
A platinum wire is subjected to anodic and cathodic cycles, which form a deposit of black
platinum powder on the wire surface to increase the effective surface. The platinum so treated is
called platinised platinum.
M MN
H
Eeq
H2
M
Pt
Mz+ H+ H2
H2 2H+ + 2e- H2
1 2
Mz+ Mz+
M Mz++ ze- H+ H2
Mz+ H2 = 1 atm
H+ = 1 mol/L
Fig. 3.4 Galvanic cell used for the measurement of the equilibrium potential of metal M versus
the standard hydrogen electrode (SHE)
Table 3.1 Standard potentials series

Electrode reactions E (V SHE) Electrode reactions E (V SHE)
− −
F2 + 2H + e ! 2HF
+
+3.030 Cu + e ! Cu
2+ +
+0.158
O3 + 2H+ + e− ! O2 + H2O +2.070 Sn4+ + 2e− ! Sn2+ +0.150
Co3+ + 3e− ! Co +1.842 2H+ + 2e− ! H2 0
Au+ + e− ! Au +1.680 2D+ + 2e− ! D2 −0.003
Mn3+ + e− ! Mn2+ +1.510 Fe3+ + 3e− ! Fe −0.036
Au3+ + 3e− ! Au +1.500 Pb2+ + 2e− ! Pb −0.126
MnO4− + 8H+ + 5e− ! Mn2+ + 4H2O +1.491 Sn2+ + 2e− ! Sn −0.136
PbO2 + 4H+ + 2e− ! Pb2+ + 2H2O +1.467 Ge4+ + 4e− ! Ge −0.150
Cl2 + 2e− ! 2Cl− +1.358 Mo3+ + 3e− ! Mo −0.200
Cr2O72− + 14H+ + 6e− ! 2Cr3+ + 7H2O +1.330 Ni2+ + 2e− ! Ni −0.250
O2 + 4H++ 4e− ! 2H2O +1.230 Co2+ + 2e− ! Co −0.280
CrO42− + 8H+ + 3e− ! Cr3+ + 4H2O +1.195 Mn3+ + 3e− ! Mn −0.283
Pt2+ + 3e− ! Pt +1.190 In3+ + 3e− ! In −0.342
Br2 + 2e− ! 2Br− +1.087 Cd2+ + 2e− ! Cd −0.400
HNO3 + 3H+ + 3e− ! NO + 2H2O +0.960 Cr3+ + e− ! Cr2+ −0.410
2Hg2+ + 2e− ! Hg22+ +0.920 Fe2+ + 2e− ! Fe −0.440
Hg2+ + 2e− ! 2Hg +0.851 Cr3+ + 3e− ! Cr −0.740
Ag+ + e− ! Ag +0.800 Zn2+ + 2e− ! Zn −0.760
Hg22+ + 2e− ! 2Hg +0.796 V3+ + 3e− ! V −0.876
Fe3+ + e− ! Fe2+ +0.770 Cr2+ + 2e− ! Cr −0.913
O2 + 2H+ + 2e− ! H2O +0.682 Nb3+ + 3e− ! Nb −1.100
Hg2SO4 + 2e− ! 2Hg + SO42− +0.620 Mn2+ + 2e− ! Mn −1.180
MnO4− + 2 H2O + 3e− ! MnO2 + 4 OH− +0.588 V2+ + 2e−! V −1.180
(continued)
3.3 Standard Potential 43
Table 3.1 (continued)

Electrode reactions E (V SHE) Electrode reactions E (V SHE)
I2 + 2e− ! 2I− +0.534 Ti3+ + 3e− ! Ti −1.210
Cu+ + e− ! Cu +0.522 Zr4+ + 4e− ! Zr −1.530
2NO2− + 4H2O + 6e− ! N2 + 8OH− +0.420 Ti2+ + 2e− ! Ti −1.630
SO42− + 6e− + 8H+ ! S + 4H2O +0.360 Al3+ + 3e− ! Al −1.660
Cu2+ + 2e− = Cu +0.340 Mg2+ + 2e− ! Mg −2.360
2NO3− + 6H2O + 10e− ! N2 + 12OH− +0.250 Na+ + e− ! Na −2.710
AgCl + e− ! Ag + Cl− +0.220 Ca2+ + 2e− ! Ca −2.860
SO42− + 2e− + 2H+ ! SO32− + H2O +0.170 Li+ + e− ! Li −3.050
depending on the position in the series: the more positive the potential, the higher
the nobility. It is worth noting that on the top of the scale there are the first metals
produced by man (in order gold, silver, then copper and iron) which are more noble,
while those on the bottom have been obtained only in recent times (aluminium,
titanium, magnesium, sodium).
3.4 Potential of an Electrochemical Reaction
To calculate the potential of an electrochemical reaction at any condition, it is

necessary to know the chemical species involved, as well as their thermodynamic
levels in terms of activity for dissolved species and fugacity for gas. For corrosion
systems, activities and fugacities are approximated to concentrations and pressures,
respectively, with the exception for concentrated solutions or when complexes or
high pressure systems are present.
For any electrochemical reaction as the one below, written as anodic:
aA þ bB þ ! cC þ dD þ þ ze ð3:16Þ
the equilibrium potential is given by the Nernst equation derived from Eq. 3.2:
RT acC adD
Eeq ¼ E 0 þ ln ð3:17Þ
zF aaA abB
E0 is the standard potential of the reaction at standard conditions (i.e., unitary

activity for dissolved species and fugacity 1 atm for gas), z is the number of
electrons involved and F is the Faraday constant.
The Nernst equation shorts to:
0:059 ac ad
Eeq ¼ E 0 þ log Ca Db ð3:18Þ
z aA aB
where 0.059 V is the term 2.3 RT/F at 25 °C (2.3 is the conversion coefficient from
natural to decimal-base logarithm).
When H+ (or OH−) ions participate in the reaction, it is useful to highlight the
effect of pH. Therefore, the above Eq. 3.14 becomes:
aA þ bB ! cC þ hH þ þ ze ð3:19Þ
and the equilibrium potential is:
h 0:059 ac
Eeq ¼ E 0 0:059 pH þ log aC ð3:20Þ
z z aA
From the above equation, it results that in an E-pH plot the equilibrium potential is
a straight line with slope 0.059 h/z. This is when the reaction involves H+ or OH−
ions, while it is worth to notice that it is a horizontal line when these ions do not
participate, according to Eq. 3.18.
3.5 Potential of Metal Dissolution Reaction
For a metal dissolution reaction, M ! Mz þ þ ze , the Nernst equation becomes:
2:3RT aMz þ
Eeq ¼ E 0 þ log ð3:21Þ
zF aM
where E0 is the standard potential of metal, M, az+ M is the ion concentration and aM.
is the metal concentration, where for pure metals aM = 1.
−6
Metal ion concentration az+M is assumed 10 mol/L, as suggested by Pourbaix,
for electrolytes not containing metal ions, as in the case of metals exposed to waters
or buried in soil. The equilibrium potential shorts to:
0:354
Eeq ¼ E 0 ð3:22Þ
z
3.5 Potential of Metal Dissolution Reaction 45
3.5.1 Corrosion and Immunity Conditions
For a general anodic reaction of metal dissolution as Eq. 3.4, the thermodynamic
condition to proceed toward anodic direction (corrosion) becomes E > Eeq, which
corresponds to the condition ΔG < 0, or ΔE = E − Eeq > 0. Conversely, if E < Eeq
(or ΔG > 0), the anodic reaction does not take place, instead it occurs in the
opposite direction. This condition is called immunity.
3.6 Potential of Cathodic Processes
Among possible cathodic processes, the rank of occurrence is established by the

equilibrium potential: the most noble process is the first, sequentially followed by
less noble ones, as in the following sequence (standard potential, V vs SHE, ordered
downward):
• Chlorine reduction to give chloride (+1.36 V)
• Oxygen reduction (+1.23 V)
• Copper ions reduction (+0.34 V)
• Hydrogen ion reduction (0 V).
In most of the corrosive environments, two cathodic processes occur, that is,
oxygen reduction and hydrogen ion reduction. Hence, in general, to assess the
corrosion of metals, it is useful to distinguish between acidic solutions and neutral
or alkaline solutions. Oxygen reduction always takes place, if present. Whereas,
hydrogen evolution occurs in acidic environments, at least for ferrous alloys. For
instance, for carbon steel exposed to natural environments such as water, soil,
atmosphere and concrete, the cathodic process is oxygen reduction, only.
Example 1
Let's consider a solution containing ferrous ions with a concentration
10−3 mol/L of Fe2+ ions at 25 °C. If an iron specimen (for instance a strip),
immersed in that solution, has a potential of −500 mV or −600 mV SHE,
respectively, what would you expect? Corrosion or deposition of iron?
Answer. Under standard conditions at 25 °C iron has an equilibrium
potential equal to −0.44 V SHE; therefore, in a solution with a concentration
10−3 mol/L of Fe2+ ions, the equilibrium potential is:
RT 0:059
Eeq ¼ E 0 þ ln aFe2 þ ¼ 0:44 þ ð3Þ ¼ 0:527 V SHE
zF 2
When the measured potential is −500 mV SHE, since

−500 mV > −0.527 V iron tends to pass into solution; instead, when the
potential is −600 mV SHE, iron ions tend to be deposited.
Example 2
A storage tank for fresh water is made of iron (carbon steel). Can you decide
whether corrosion takes place or not according to the potential measured?
Answer. If the measured potential is EM, and the equilibrium potential is
Eeq, there is corrosion if EM > Eeq, or immunity if EM < Eeq.
The equilibrium potential is calculated with the Nernst equation intro-
ducing the concentration of 10−6 mol/L of iron ions in the solution (corre-
sponding in the case of iron to 0.056 ppm). The equilibrium potential of
reaction Fe = Fe2+ + 2e− is
E eq ¼ 0:44 0:059=2 log 106 ¼ 0:62 V SHE:
It appears evident that the greater the difference between measured and
equilibrium potential, the greater the driving force available for the occur-
rence of the corrosion process.
3.6.1 Potential of Hydrogen Evolution Reaction
The hydrogen evolution process in acidic solutions is given by the reaction:
2H3 O þ þ 2e ! H2 þ 2H2 O ð3:23Þ
It can also occur in neutral or alkaline solutions when the metal is electronegative,
like aluminium or magnesium, by the following reaction:
2H2 O þ 2e ! 2OH þ H2 ð3:24Þ
The two reactions above are energetically equivalent and therefore characterized by
the same equilibrium potential.3 Assuming pH2 = 1 bar and aH2 O ¼ 1, according to
the Nernst equation, the equilibrium potential depends on pH as follows:
3
The combination of the equation of the hydrogen evolution reaction (H2O + e− = ½H2 + OH-,
reaction a) with the water dissociation reaction (H+ + OH− = H2O, reaction c) gives
H+ + e− = ½H2 (reaction b). Therefore, ΔGb = ΔGa + ΔGc. At equilibrium conditions ΔGc = 0,
therefore ΔGa = ΔGb, as well as the associated potentials with respect to the same reference
3.6 Potential of Cathodic Processes 47
Fig. 3.5 The equilibrium E (V SHE)

potential of most common 2
cathodic processes in function
of pH: oxygen reduction and 1.229 V
hydrogen evolution 0.815 V
1
0.401 V
0V b
0
-0.828 V
-1 -0.414 V
a
25 °C, 1 atm
-2
0 7 14
pH
0:059
Eeq ¼ E 0 þ log aH þ ¼ 0:059 log aH þ ¼ 0:8280:059 log aOH ¼ 0:059 pH
z
ð3:25Þ
In a potential - pH diagram, called Pourbaix diagram (Fig. 3.5), the equilibrium

potential of hydrogen evolution is given by the straight line a, having a slope of
−0.059 at 25 °C.
3.6.2 Potential of Oxygen Reduction Reaction
In aerated acidic solutions, the oxygen reduction reaction is the following:
O2 þ 4H þ þ 4e ! 2H2 O ð3:26Þ
and in neutral or alkaline aerated solutions it is:
O2 þ 2H2 O þ 4e ! 4OH ð3:27Þ
electrode. From an energy viewpoint, the processes (a) and (b) are equivalent. The potentials of the
two processes are mutually correlated through the ionic dissociation constant of water (at 25 °C
Kw = aH+ aOH = 10−14). For example, at pH 14, in conditions where both aH2 O ¼ 1 and
PH2 = 1 bar, depending on which process a) or b) reference is made, the following is obtained:
E b ¼ E 0b þ 2:3FRT log aH þ ¼ 0 þ 0:059 ð14Þ ¼ 0:828 V SHE
The two reactions are equivalent and therefore characterized by the same equilib-
rium potential.4 With reference to the standard conditions, pO2 = 1 bar, aH2 O ¼ 1
and 25 °C, the equilibrium potential is given by the Nernst equation:
Eeq ¼ 0:401 0:059 log aOH ¼ 1:229 þ 0:059 log aH þ ¼ 1:229 0:059 pH
ð3:28Þ
The equilibrium potential of the oxygen reduction reaction in the E-pH diagram
(Fig. 3.5) follows line b, which is parallel to line a of the hydrogen evolution
reaction. The equilibrium potential changes as the oxygen content—which deter-
mines oxygen partial pressure—varies. On the basis of Henry’s law, 1 ppm vari-
ation of the oxygen content determines a variation of equilibrium potential of
25 mV. Often, in practice, for 1 ppm oxygen content change, about 50 mV shift is
considered, which also includes some activation overvoltage contributions, as
discussed in Chap.5.
3.6.3 Applications of Thermodynamic Criteria
Thermodynamic criteria help determine whether a corrosion reaction can occur,

once equilibrium potentials of both cathodic and anodic processes are known.
De-aerated solutions. In acidic de-aerated solutions, i.e., in the absence of dis-
solved oxygen, the only possible cathodic process is the reduction of hydrogen ion
to give hydrogen evolution which takes place at the potential Eeq = −0.059 pH
(often taken as about 0). All metals with equilibrium potential Eeq,M more negative
than −0.059 pH can corrode; the more negative (less noble) the equilibrium
potential of the metal, the greater is the driving voltage. Examples of metals that
corrode in acidic de-aerated solutions (listed in descending order of nobility) are:
lead, tin, nickel, cobalt, thallium, cadmium, iron, chromium, zinc, aluminium,
magnesium. Instead, examples of metals that do not corrode in acidic de-aerated
solutions (listed in order of increasing nobility) are: copper, mercury, silver. In
neutral de-aerated solutions, in particular water for which the equilibrium potential
of hydrogen evolution is −0.414 V SHE, metals with equilibrium potential lower
than that—such as iron, chromium, zinc, aluminium, magnesium—can corrode.
Finally, in alkaline de-aerated solutions, where the hydrogen ion reduction reaction
has the equilibrium potential close to −0.828 V SHE, only zinc, aluminium and
magnesium can corrode among industrially used metals.
4
With similar considerations discussed in note 3, it can easily be proved that the two oxygen
reduction reactions (O2 + 4H+ + 4e− = 2H2O and O2 + 2H2O + 4e− = 4OH−) are equivalent
3.6 Potential of Cathodic Processes 49
Aerated solutions. In acidic aerated solutions, the equilibrium potential of the

oxygen reduction process is +1.23 V SHE; therefore, only metals with a greater
(more noble) equilibrium potential, such as gold or platinum, do not corrode, while
all others do. In neutral aerated solutions (Eeq = + 0.815 V SHE), all metals less
noble than silver can suffer from corrosion, while in alkaline aerated solutions
(Eeq = + 0.401 V SHE) this occurs for all metals less noble than copper.
Oxidizing species. In solutions containing oxidizing species, things change. For
example, in chlorine-containing solutions (Eeq = + 1.35 V SHE) silver can also
corrode, and in those containing fluorine (Eeq = + 2.65 V SHE) even gold does.
Potentialof an electrochemical reaction

Example 1
Let's consider the electrochemical reaction of zinc dissolution to give zincate:
Zn þ 2H2 O ! HZnO2 þ 3H þ þ 2e
The equilibrium potential is given by the Nernst equation (taking into

account water activity, aH2 O ¼ 1, as unitary):
2:3RT a a3 0:059 3
Eeq ¼ E0 þ log HZnO2 H ¼ E 0 þ logaHZnO2 0:059 pH
2F aZn aH2 O 2 2
Example 2
Let's consider the following redox reaction:
Mn2 þ þ 4H2 O ! MnO4 þ 8H þ þ 5e
The equilibrium potential is given by the Nernst equation (taking into

account water activity, aH2 O , as unitary):

E eq ¼ þ 1:507 0:094 pH þ 0:012 log ½MnO4 = Mn2 þ
Example 3
Finally, let's consider the following redox reaction:
Fe2 þ ! Fe3 þ þ e
The equilibrium potential is:

Eeq ¼ 0:77 þ 0:059 log Fe3 þ = Fe2 þ
3.7 Insoluble Products and Complexing Species
So far, we have considered metals which dissolve as ions while corroding.

However, sometimes chemical species that form insoluble corrosion products—for
example oxides, hydroxides or sulphides—are present. In these conditions, the
extremely low concentration of metal ion in solution lowers the equilibrium
potential from the standard potential drastically, changing the thermodynamic
condition. This occurs, for instance, with gold, silver, copper and many other metals
in cyanide or ammonia containing solutions and many other complexing species.
Let's take into consideration the case of silver in cyanide containing solutions,
where the following complexing reaction takes place: Ag+ + 2CN− ! Ag(CN)−2 .
The silver ion, Ag+, concentration is obtained from the complex stability constant:

Ks ¼ ½AgCN2 = ½Ag þ ½CN 2 ¼ 1021:2 ð3:29Þ
In a solution containing 0.1 mol/L of AgNO3 and 1 mol/L of KCN, the complex
concentration is 0.1 mol/L (i.e., the same as AgNO3), therefore the cyanide con-
centration is [CN−] = 1 − 2 (0.1) = 0.8 mol/L. The silver ion concentration in
solution is given by the complex stability constant:
½Ag þ ¼ ð0:1Þ=½ð0:8Þ 1021:2 ¼ 1022 mol=L.
The equilibrium potential is given by the Nernst equation applied to the elec-
trochemical reaction (Ag ! Ag+ + e−):
Eeq ¼ 0:8 þ 0:059 log ½Ag þ ¼ 0:8 þ 0:059ð22Þ ¼ 0:5 V SHE ð3:30Þ
In this condition, silver is less noble than copper and steel (iron).
3.8 Reference Electrodes
The potential is measured by connecting a voltmeter to the metal (or metal struc-
ture), also called working electrode and to a reference electrode which has the
property of maintaining its potential constant (Fig. 3.6). The positive terminal has
to be connected to the working electrode in order to obtain the correct sign of the
reading value.
3.8 Reference Electrodes 51
High
impedance +
voltmeter
Reference electrode
(e.g., Cu/CuSO4)
Reinforcement
Concrete
Fig. 3.6 Example of apparatus for potential measurement in concrete
Table 3.2 Reference electrodes used in laboratory and in industrial plants

Electrode Description Equilibrium reaction E (V
SHE)
Standard hydrogen H2(1 atm)∣H+(a = 1 M) 2H+ + 2e− ! H2 0
electrode (SHE)
Saturated calomel Hg∣Hg2Cl2, KCl (sat) Hg2Cl2 + 2e− ! 2Hg + 2Cl− +0.244
electrode (SCE)
Silver/silver chloride Ag∣AgCl, KCl (sat) AgCl + e− ! Ag + Cl− +0.200
(saturated)
Silver/silver chloride Ag∣AgCl, seawater AgCl + e− ! Ag + Cl− +0.250
(seawater)
Copper/copper sulphate Cu∣CuSO4 (sat) Cu2+ + 2e− ! Cu +0.318
electrode (CSE)
Zinc/seawater (ZN) Zn∣seawater Zn2+ + 2e− ! Zn −0.800
By convention, the potentials are referred to the standard hydrogen electrode

(SHE) taken as the zero reference. However, it is very unfeasible and therefore not
used, either in laboratory testing or for industrial monitoring. The most used ref-
erence electrodes are reported in Table 3.2. Figure 3.6 shows the most used ref-
erence electrodes for potential measurements of structures buried in concrete, which
is copper–copper sulphate.
Silver in presence of sulphides

In a sulphide containing solution, silver ions react with sulphides to give
highly insoluble Ag2S (solubility product Ks = [Ag+]2 [S2−] = 1.6 10−49).
The Nernst equation for the electrochemical reaction (Ag ! Ag+ + e−)
when sulphide ions are present is:
Eeq ¼ 0:8 þ 0:059 log½Ag þ

¼ 0:8 þ 0:059=2 log K s = S2
If, for example, sulphide [S2−] concentration in solution is 1 ppm, corre-

sponding to 3 10−5 M, it results: log (Ks/[S2−]) = log (1.6 10−49/
3 10−5) = −44.3. The equilibrium potential is then: = 0.8 + (−44.3)
0.059/2 = −0.51 V SHE, which is a value even more negative than the
potential of active steel (iron).
This case study explains the tarnishing of silver in sulphide containing
atmospheres.
Copper in concentrated hydrochloric acid
Copper immersed in concentrated pure hydrochloric acid corrodes rapidly
with the evolution of gas bubbles. This is not contrary to thermodynamics as
proved in the following explanation, making the necessary assumptions.
According to a chemical handbook’s data, the concentration of “pure” HCl
is 12.0 M. Assuming unitary activity coefficients, pH = −log[12] = −1.08.
The equilibrium potential of the hydrogen evolution reaction at pH −1.08 is
−0.059 pH= +0.064 V SHE
The equilibrium potential of +0.064 V SHE for Cu+2/Cu is reached if
copper concentration drops to [Cu2+] = 7.56 10−10 mol/L, as from Nernst
equation:
EeqðCu2 þ =CuÞ ¼ 0:064 ¼ 0:334 þ ½0:059=2 log½Cu2 þ :
This occurs because of the formation of copper-chloride complexants.
3.9 Electrochemical Cells
When coupling two metal-solution systems—for example, zinc and copper—each

one immersed in a solution of their sulphate salt with unitary concentration, sep-
arated by a porous membrane selectively permeable to the sulphate ions (this is the
Daniell cell), the equilibrium potential (i.e., the tension measured at open circuit) is
given by the difference of equilibrium potentials of each electrode.
By short-circuiting the two electrodes (Zn and Cu), the electrode reactions are,
respectively:
3.9 Electrochemical Cells 53
Zn ! Zn2 þ þ 2e ð3:31Þ
Cu ! Cu2 þ þ 2e ð3:32Þ
the global reaction is:
Zn þ Cu2 þ ! Zn2 þ þ Cu ð3:33Þ
Standard potentials of the two electrodes, zinc and copper, respectively, are:
E° = −0.76 V SHE (anode), and E° = +0.34 V SHE (cathode), therefore the open
circuit potential (i.e., in equilibrium condition) is (−0.76 − (+0.34)) = −1.1 V. The
driving voltage is, therefore, 1.1 V, which is available for the occurrence of the
above overall reaction.
3.9.1 Concentration Cells
In some corrosion processes, anodic and cathodic reactions are the same. In these
cases, the driving voltage derives from a chemical-physical unevenness that may
occur: in solution, in gas phase in contact with the electrodes and on the electrodes.
Uneven solution. Let's consider a cell formed by two identical electrodes made of
lead in contact with two aqueous solutions in which lead is soluble (for example
lead perchlorate or sulphamate) having different lead concentrations:
I; Pb=lead salt diluited; PbðdilÞ ==lead salt concentrated; PbðconcÞ =Pb; II
The equilibrium potential of the cell is 5:
Eeq III ¼ 0:059=2 log½PbI =½PbII ð3:34Þ
Therefore, lead in contact with a diluted solution behaves as an anode, corroding;

instead, lead in contact with a more concentrated solution acts as a cathode and then
lead deposits on its surface. The system proceeds toward the reduction of the
concentration difference between the two solutions.
5
Equilibrium conditions are achieved only if a membrane selectively permeable to anions separates
the two solutions. In the most common case in which the two solutions are in contact with each
other, the potential of the cell is Eeq,I–II = ta 0.059/2 log ([PbI]/[PbII]), where ta is the transport
number of anions.
Uneven oxygen concentration in solution. Let's consider a cell formed by two

identical electrodes made of a platinum wire immersed in two solutions with dif-
ferent oxygen content: C1 and C2 being C1 > C2. The electrode reaction is oxygen
reduction, Eq. 3.27. The equilibrium potential of the cell:
I; Pt=oxygen rich solution C1 ==oxygen poor solution C2 =Pt; II
is as follows:
Eeq;III ¼ 0:059=4 log C1 =C2 ð3:35Þ
The potential of electrode I is more noble than the potential of electrode II;
therefore, electrode I is cathode and electrode II is anode.
Uneven electrode composition. Let's consider a cell formed by two electrodes
made of cadmium amalgam; the first, I, with a higher Cd concentration and the
second, II, with a lower Cd concentration in contact with a cadmium solution:
I;½Cd; Hghigh Cd =CdSO4 solution=½Cd; Hglow Cd ; II
The cell reaction is: Cd ! Cd2+ + 2e−, and the cell potential is:
Eeq;III ¼ 0:059 log ½Cdlow =½Cdhigh ð3:36Þ
Since [Cd]low < [Cd]high, the equilibrium potential, Eeq,I,II, is negative.

Therefore, there is a driving force because Cd of electrode I dissolves, and on
electrode II it deposits from Cd2+ ions. All these examples show that the sponta-
neous tendency is the reduction of unevenness.
3:1 Assuming standard conditions for reactants and products, determine the
spontaneous direction of the following reactions by calculating the driving
voltage, ΔE:

Cu þ 2HCl ! CuCl2 þ H2 Cu þ 2H þ ! Cu2 þ þ H2
Fe þ 2HCl ! FeCl2 þ H2 Fe þ 2H þ ! Fe2 þ þ H2
2AgNO3 þ Fe ! FeðNO3 Þ2 þ 2Ag
Ag þ FeCl3 ! FeCl2 þ AgCl
2Al þ 3ZnSO4 ! Al2 ðSO4 Þ3 þ 3Zn
3:2 Write the cathodic and anodic reactions occurring for the uniform corrosion
of the following systems at standard conditions, where applicable:
(a) Aluminium in oxygen-free sulphuric acid

(b) Iron in oxygen-free ferric sulphate solution
(c) Carbon steel in aerated seawater
(d) Zinc-tin alloy in an oxygen saturated solution of CuCl2, SnCl4 and HCl
(e) Copper in deaerated seawater.
3:3 ΔE as well as cell voltage is positive for spontaneous corrosion. Can you
give an example of a cell with negative voltage? Describe the consequences
of such condition.
3:4 Calculate the standard potentials E0 and equilibrium potentials Eeq as func-
tion of pH for the following electrode reactions from standard ΔG0:
(a) Zn2 þ þ 2e ! Zn ðDG0 ¼ 147; 000 JÞ
(b) HZnO2 þ 3H þ þ 2e ! Zn þ 2H2 O ðDG0 ¼ 10; 400 JÞ
Report results on a E-pH diagram, the so-called Pourbaix diagram.
3:5 Let's consider the following air-saturated solutions:
(a) Diluted strong acid (pH = 3)
(b) Alkaline solution (pH = 13)
Indicate possible acids and alkalis making the above conditions, write
cathodic reactions, calculate the equilibrium potential and plot it as a function
of pH.
3:6 Calculate the difference between the equilibrium potential of reference
electrode Cu/CuSO4 (concentration 1 mol/L) and a carbon steel structure
buried in soil (iron concentration 10−6 mol/L). Suppose to measure the free
corrosion potential of the same structure in soil. Is this value different from
the equilibrium potential? Why? [Hint: refer to Chap. 6 for the definition of
free corrosion potential].
3:7 Gold does not corrode in aerated solutions, since its equilibrium potential is
more noble than the equilibrium potential of oxygen reduction. How gold
can be extracted from the sands that contain it?
3:8 Considering the following Table, check whether corrosion is possible or not
[Hint: metal ions content is always 10−6 mol/L]. If the answer is positive,
then estimate the driving force.
Metal Environment pH Corrosion (Y/N) Driving force

Fe Aerated neutral soil 7
Fe De-aerated acidic water 4
Fe Aerated concrete 13
Cu De-aerated neutral water 7
Al Aerated neutral soil 7
3:9 Calculate or give the general equation of the equilibrium potential of the
following reactions:
(a) Fe2+! Fe3+ + e− ([aFe3 þ ] = 0.5; [aFe2 þ ] = 10−6; E0 = + 0.77 V SHE)

(b) O2 + 4H+ + 4e−! 2H2O (pH = 3; pH = 7; pH = 12)
(c) 3Fe2+ + 4H2O ! Fe3O4 + 8H+ + 2e− ([aH2 O ] = 1; E0 = + 0.98 V SHE)
(d) Ni2+ + H2O ! NiO + 2H+ ([aH2 O ] = [aNiO] = 1)
(e) Ti + H 2 O ! TiO + 2H + + 2e − ([a T i ] = [aH2 O ] = [aTiO] = 1; E0 =
−1.306 V SHE)
(f) CuO + H2O ! CuO22− + 2H+ ([aCuO] = [aH2 O ] = 1)
Consider (2.3RT)/F = 0.059 V.
3:10 A room temperature (25 °C) solution contains 10−3 mol/L of ferrous ions. If
iron has a potential of −500 and −600 mV SHE, does it tend to corrode or
deposit?
3:11 Calculate the equilibrium potential of the reaction Fe2+= Fe3+ + e− knowing
that: [Fe3+] = 0.5 mol/L and [Fe2+] = 10−6 mol/L.
3:12 A carbon steel tank is filled with potable water. Based on the measured iron
potential in solution, is it possible to state whether corrosion takes place?
Bibliography
Bardal E (2004) Corrosion and protection. Springer-Verlag London Limited, UK

Milano (in Italian)
Pourbaix M (1973) Lectures on electrochemical corrosion. Plenum Press, London
Roberge PR (1999) Handbook of corrosion engineering. McGraw-Hill, London
Chapter 4
Pourbaix Diagrams
These diagrams embody a vast amount of pertinent information

in a small place.
U. R. Evans
Abstract In 1945, Marcel Pourbaix (1904–1998) proposed in the Atlas of

Electrochemical Equilibria in Aqueous Solutions the potential-pH diagram of ele-
ments in the presence of water, which is now called “Pourbaix diagram”. It uses
thermodynamic considerations to define potentials corresponding to the equilibrium
states of all possible reactions between a given element, its ions, and its solid and
gaseous compounds in aqueous solutions as a function of pH. This Chapter illus-
trates the basis of Pourbaix diagrams, how they are obtained, and shows examples
for the most important metals. Three areas can be identified in the diagrams:
immunity, corrosion and passivation, representing the fields of thermodynamic
stability of the metal, of its ions and of its oxides and hydroxides, respectively.

https://doi.org/10.1007/978-3-319-97625-9_4
58 4 Pourbaix Diagrams
Fig. 4.2 Pourbaix diagram, E (V SHE)

E-pH, for water: line a, 2
hydrogen evolution; line b, Oxygen evolution
oxygen reduction and acidity production
b
0 Water stability
-1
a
Hydrogen evolution
and alkalinity production
-2
0 7 14
pH
4.1 Oxygen Reduction and Hydrogen Evolution
Pourbaix diagrams graphically represent the thermodynamic conditions of immu-

nity, corrosion (Fig. 4.1) and passivation. All Pourbaix diagrams report the equi-
librium potential of the two most important cathodic reactions, i.e., oxygen
reduction and hydrogen evolution, which are pH dependent, as the Nernst equation
shows, and as already mentioned in Chap. 3:
Eeq;H2 ¼ 0:059 pH ð4:1Þ
Eeq;O2 ¼ 1:229 0:059 pH ð4:2Þ
Therefore, the two equations are represented by two parallel straight lines having a
slope of −0.059 V/pH at 25 °C and spaced 1.23 V. Figure 4.2 shows these two
lines denoted as line a and line b for hydrogen evolution and oxygen reduction,
respectively. At potentials above line b, water dissociates producing oxygen and
acidity (anodic reaction: 2H2O = O2 + 4H+ + 4e−); whereas, below line a, water
dissociates producing hydrogen and alkalinity (cathodic reaction:
2H2O + 4e− = H2 + 4OH−). The area between the two straight lines is the one of
electrochemical stability of water, in which the only possible reactions are: oxygen
reduction and hydrogen oxidation (if these two gases are available at metal surface).
The 1.23 V spacing between the two lines corresponds to the thermodynamic
potential of water decomposition, according to the reaction 2H2O = 2H2 + O2.
4.2 Metal Immunity, Corrosion and Passivation
Referring to metals, the Pourbaix diagram (E-pH) displays the zones of stability of
the chemical species involved as a function of potential and pH, namely: metal
(immunity zone), metal ions (corrosion zone), oxides and hydroxides (passivation
4.2 Metal Immunity, Corrosion and Passivation 59

E-pH, for metal dissolution 2
0 -3 -6
and passivation
M(OH)z
Passivation
1 z+
M
Corrosion
b
0 0
-3
-6
-1
M a
Immunity
-2
0 7 14
pH
and passivity zones). To avoid misunderstandings, it is worth highlighting the

difference between passivation (as Pourbaix calls it in his diagram) and passivity, as
used later: passivation indicates, generically, the formation of oxides on the surface
of a metal, while, if this oxide forms a continuous adherent and flawless layer, this
condition is called passivity. Figure 4.3 shows the general potential-pH equilibrium
diagram for the metal-water system, at 25 °C.
The equilibrium domains are defined by electrochemical or chemical reactions.
A chemical reaction is a reaction in which only neutral molecules and positively or
negatively charged ions take part, with the exclusion of electrons. Conversely, an
electrochemical reaction, besides molecules and ions, involves electrons.
In practical non-equilibrium conditions, stability zones as well as kinetics can be
different; for example, the Pourbaix diagram of iron as obtained experimentally in
laboratory in agitated, oxygenated water shows a wider passivity zone than the one
calculated from thermodynamics.
4.2.1 Equilibrium Between Immunity and Corrosion
On Pourbaix diagrams, the equilibrium potential of the dissolution process of a

generic metal (M ! Mz+ + ze−) is given by the Nernst equation:
0:059
Eeq;M ¼ E0 þ log aMz þ ð4:3Þ
z
This equation in the E-pH diagram gives a set of straight lines, parallel to the
abscissa, where each line corresponds to a value of the parameter log aMz þ , hence is
independent from pH as Fig. 4.4 shows. Each logaMz+ value identifies a line of

E-pH, for metal dissolution 2
1
Mz+
b
0 log [Mz+]
0
-2
-4
-6
-1
a
M
-2
0 7 14
pH
corresponding potential: for more noble potentials (i.e., above the line), metal
oxidation is the spontaneous reaction, while below the line the opposite occurs, that
is a cathodic reaction (reduction reaction) of an oxidized species of the metal,
typically metal ions, Mz+, reduced to metal, when present in the electrolyte.
Among the straight lines set, Pourbaix proposed to represent the one corre-
sponding to the concentration 10−6 mol/L of metal ions, Mz+, as separation
boundary of metal corrosion from metal deposition, called immunity. Such con-
centration, which derived from the analytical limit threshold of metal ions in so-
lution at the time these diagrams were first created, has the practical meaning of
absence of metal ions in solution. For instance, a concentration of 10−6 mol/L for
iron (steel) corresponds to 0.056 ppm, which, in the absence of a continuous
renewal of the electrolyte, does not represent an appreciable loss of metal.
Metal ions with different oxidation numbers. There are electrochemical
reactions that involve ions with a different oxidation number (or valence) as the
following:
Mx þ þ ze ! MðxzÞ þ ð4:4Þ
The corresponding equilibrium potential is given by the Nernst equation, as

follows:
0:059 a zþ
Eeq;M ¼ E0 þ log M ð4:5Þ
z aMðxzÞ þ
Figure 4.5 shows the Pourbaix diagram of a metal with two oxidation states. The
corresponding equilibrium potential is represented by a set of straight lines, again
parallel to the abscissa, where each line corresponds to a value of the ratio between
the activities of the two ions. The straight line corresponding to the unitary ratio
identifies two zones: above this line, the species with a higher oxidation number is
4.2 Metal Immunity, Corrosion and Passivation 61

E-pH, for a metal with two 2
oxidation states Mx+
(x>z)
M(OH)z
1 Passivation
Mz+
b
Corrosion
0
-1
a
M
Immunity
-2
0 7 14
pH
stable and the opposite applies below the line. For example, in the case of iron,
where two oxidation states apply, Fe2+ = Fe3+ + e−, the corresponding equilibrium
potential is expressed by:
aFe3 þ
Eeq;Fe3 þ =Fe2 þ ¼ 0:77 þ 0:059 log ð4:6Þ
aFe2 þ
4.2.2 Equilibrium Between Immunity and Passivation
The dissolution reaction of metal, M, leads to the formation of hydroxides, espe-

cially in neutral or alkaline solutions, according to the electrochemical reaction:
M þ zH2 O ! MðOHÞz þ zH þ þ ze ð4:7Þ
The equilibrium potential is given by the Nernst equation:
0:059 aMðOHÞz
Eeq;M ¼ E 0 þ log 0:059 pH ð4:8Þ
z aM
which shows that the equation of the equilibrium potential versus pH is a straight
line having the same slope of the cathodic process (hydrogen evolution, line a;
oxygen reduction, line b) as represented in Fig. 4.3. Below this straight line, there
is the immunity zone, while above it there is the zone for the formation of the
hydroxide, called passivation.
4.2.3 Equilibrium Between Corrosion and Passivation
The equilibrium condition between metal ions and hydroxides is defined by a

chemical reaction where no electrons are involved, as follows:
Mz þ þ zH2 O ! MðOHÞz þ zH þ ð4:9Þ
The equilibrium condition of this reaction, once T and P are fixed and assuming
aMðOHÞz ¼ aH2 O ¼ 1, is given by the following equation:
ðaH þ Þz
K ðT; PÞ ¼ ð4:10Þ
aMz þ
which leads to:
log aMz þ ¼ log K þ z log aH þ ¼ A z pH ð4:11Þ
Taking log aMz+ as the function parameter, the equilibrium condition (at 25 °C,
1 atm) is represented by a set of lines parallel to the ordinate axis. Let's consider the
line corresponding to the value of the parameter log aMz þ equal to −6 as shown in
Fig. 4.3. For pH higher than the one given by the equation, the stable species is
M(OH)z, while for lower pH the stable species is the metal ion Mz+.
The electrochemical passivation reaction (4.7) is the sum of two reactions: metal
dissolution reaction (M ! Mz+ + ze−) and chemical passivation (4.9). In other
words, the free energy of the metal-hydroxide equilibrium is the sum of the related
energy of the metal dissolution reaction and equilibrium metal ions-hydroxide. The
crossing point of the three domains on the Pourbaix diagram, as shown in Fig. 4.3,
defines the equilibrium between metal, hydroxides and metal ions: any change of
potential or pH causes the disappearance of one of them.
4.3 Amphoteric Metals
For amphoteric metals—for instance Al, Zn, Pb and others—metal dissolution

occurs in both acidic and alkaline solutions, therefore the Pourbaix diagram of an
amphoteric metal shows a further corrosion domain at alkaline pH, as Fig. 4.6
illustrates. Equilibrium lines ①, ② and ③ are defined according to the equations
described in Sect. 4.2. Corrosion in strong alkaline solutions occurs by either an
electrochemical or a chemical dissolution reaction, as discussed in the following.
4.3 Amphoteric Metals 63

E-pH, for an amphoteric metal 2
Mz+ M(OH)z MOk-z+k
2
1
Cor 2
rosi
on
Pass b
ivati
0 on
Co
5 rrosion
1 3
-1
a
M 4
Immunity
-2
0 7 14
pH
4.3.1 Electrochemical Dissolution in Alkaline Solution
The dissolution reaction of metal in alkaline solution (line ④ in Fig. 4.6) leads to
the formation of metal ions, according to the following electrochemical reaction:
ðk þ zÞ þ
Mþ H2 O ! MOk
k þ z þ ðk þ zÞ H þ ze ð4:12Þ
2 2
The equilibrium condition is given by the following equation (at 25 °C, aH2 O ¼ 1
and aM ¼ 1):
0:059 k+z
Eeq;M ¼ E0 þ log aMOk 0:059pH ð4:13Þ
z kþz
2
z
On the E-pH diagram, a straight line with slope −0.059 (k + z)/z defines the
equilibrium condition of reaction (4.12). For the system aluminium-water at 25 °C,
the electrochemical dissolution in alkaline solution occurs according to the fol-
lowing reaction:
Al þ 2H2 O ! AlO2 þ 4H þ þ 3e ð4:14Þ
with equilibrium potential Eeq = −1.376 − (0.059 4/3)pH = −1.376 – 0.079pH

(aH2 O ¼ 1, aAl ¼ 1 and aAlO2 ¼ 106 ).
The existence of an equilibrium potential would suggest the possibility to reach
immunity by applying a cathodic polarization (i.e., by applying cathodic protec-
tion). Instead, practice has proved that by applying cathodic protection to alu-
minium, the amphoteric dissolution inevitably takes place by a chemical dissolution
in accordance with the dissolution reaction (4.17).
4.3.2 Chemical Dissolution in Alkaline Solution
The equilibrium between the passivation and the dissolution domain at alkaline pH
(line ⑤ in Fig. 4.6) is defined by the chemical reaction:
þ ðz kÞ
MðOHÞz ! MOk
k þ z þ kH þ H2 O ð4:15Þ
2 2
The equilibrium condition is given by the following equation (at 25 °C, aH2 O ¼ 1
and aMðOHÞz ¼ 1):

1
pH ¼ log aMOkkþ z log K ð4:16Þ
k 2
Where K is the equilibrium constant of reaction (4.15). The equilibrium condition

(at 25 °C, 1 atm and fixed metal ions concentration) is represented by a set of
parallel lines to the ordinate axis. For the system aluminium-water at 25 °C, the
chemical dissolution in alkaline solution occurs according to the following reaction:
AlðOHÞ3 ! AlO2 þ H þ þ H2 O ð4:17Þ
4.4 Pourbaix Diagrams of Some Metals at 25 °C
In this section the most relevant Pourbaix diagrams are reported and commented.
Iron. The Pourbaix diagram of iron is reported in Fig. 4.7. Corrosion is possible at
low and high pH with formation of Fe2+ (or also Fe3+ at high potentials) and
HFeO2−, respectively. Iron is stable in the immunity zone and can resist corrosion
in passivation zone after the formation of Fe3O4 and Fe2O3 oxides, which form at
low and high potentials, respectively. In the presence of some species, such as Ca2+,
Mg2+ or sulphate, SO42−, the passivation zone broadens due to the formation of
protective layers.
Gold. Its Pourbaix diagram (Fig. 4.8) clearly shows that even in the presence of
oxygen, the stable species is gold as metal. This is because the equilibrium potential
relevant to the dissolution reaction Au+ + e− = Au, once fixed the gold ion, Au+, as
10−6 mol/L, is more noble than the equilibrium potential of the oxygen reduction
reaction. The behaviour changes in the presence of complexing chemical species, as
in the case of cyanides. Gold corrodes in cyanide solutions because of the formation
of complex AuðCNÞ2 , which has a complex stability constant of 2 1038. Gold
ions in solution are so low to give an equilibrium potential below the one of oxygen
reduction. This explains why sodium cyanide (NaCN) is used for exploiting gold
mines.
4.4 Pourbaix Diagrams of Some Metals at 25 °C 65

E-pH, for iron 2
1 Fe3+
Fe2+ Fe2O3 b
0
Fe3O4
-1
a
Fe HFeO2-
-2
0 7 14
pH

E-pH, for gold 2
Au(OH)3
1
b
Au
0
-1
a
-2
0 7 14
pH
Chromium. Figure 4.9 shows the Pourbaix diagram of chromium. It appears that
chromium shows a clear tendency to passivate (large passivation zone) and also a
possible corrosion in acidic solutions, even close to neutrality, and at noble
potentials. This behaviour extends to stainless steels also.
Copper and nickel. Pourbaix diagrams of copper and nickel are reported in
Figs. 4.10 and 4.11, respectively. The behaviour of nickel is very similar to that of
iron. As regards copper, it is important to highlight that it can corrode only in
aerated solutions.
Aluminium and zinc. Figures 4.12 and 4.13 show the Pourbaix diagrams of alu-
minium and zinc, respectively. Both metals show an amphoteric behaviour at low
and high pH, either in the presence of oxygen or in its absence, and have a
passivation range around the neutrality.

E-pH, for chromium 2
Cr2O42-
b
HCrO4- CrO42-
1
Cr3+
b
0 Cr(OH)3
Cr2+
-1
a
Cr
-2
0 7 14
pH

E-pH, for copper 2 Cu2O3 CuO2-
CuO22-
1
CuO
Cu2+ b
0
Cu2O
-1
Cu a
-2
0 7 14
pH

E-pH, for nickel 2
NiO2
Ni2O3
1 Ni3O4
2+
Ni
0 Ni(OH)2 b
HNiO2-
-1
a
Ni
-2
0 7 14
pH

E-pH, for aluminium 2
b
Al3+ Al(OH)3 AlO2-
0
-1
a
-2 Al
0 7 14
pH

E-pH, for zinc 2
1 Zn(OH)2
Zn2+
b
a
0
HZnO4-
-1
ZnO22-
Zn
-2
0 7 14
pH
Immunity, Activity, Passivity

Immunity. Only gold can be collected in nature as nuggets. When gathered,
its perfection and purity is recognized at first sight. No rust or other substance
can affect its weight. (Plinio, Nat. Hist., 32, 62)
Activity. Iron is humankind’s best and worst servant. It helps plough soil,
plant trees, trim shrubs, rejuvenate grapes, build houses, cut stones and other;
it is also a tool for weapons, outrages, and used in battles or as flying object
thrown by hand or war machines. The most adbominious thing for the human
spirit is when man provided it of wings for flying and hasten death. Its guilt is
not on nature; instead, it is the goodness of nature, which limits its power,
condemning it to rust and nothing gives more death than what is deadly for
human beings. (Plinio, Nat. Hist., 34, 139)
Passivity. Intelligent persons, unlike silly ones, rarely get ill and, if they
do, they heal rapidly as the rusted Corinth bronzes. (Cicero, Tusc., 4, 32)
Lead. Pourbaix diagrams of lead depend on the solution composition. Figure 4.14
show the diagram in pure acidic or alkaline solutions. Figure 4.15 reports the
diagram in the presence of carbon dioxide and carbonic acid solution. The diagram
in the presence of sulphates is depicted in Fig. 4.16.
The comparison of those diagrams highlights the influence of carbonate ions on
passivation behaviour due to the formation of insoluble salts. In the absence of
carbonate ions, the corrosion zone extends from acidic to alkaline pH: this is typical
of lead exposed to pure or demineralized water. When carbonate ions are present,
there is a passivation zone around neutrality (close to pH 7) due to the formation of
lead carbonate, PbCO3, which is highly insoluble. Because of this, lead ion, Pb2+,
concentration is below toxicity limits; for this reason, lead was used in the past for
household uses.
When sulphate ions are present, the passivation zone extends further although the
solubility product is sensibly lower than that of carbonate (pK PbSO4 ¼ 8 and
pK PbCO3 ¼ 13). At low pH, the corrosion zone disappears; at a very negative
potential when hydrogen evolution takes place, lead shows another form of
degradation due to the formation of hydrides; this also occurs on titanium.
Titanium. The Pourbaix diagram of titanium, shown in Fig. 4.17, indicates that Ti
would corrode in reducing acidic environments. In oxidizing solutions Ti passivates
through the full pH range.
Tungsten. The Pourbaix diagram for tungsten shows a different behaviour compared
to the others considered above, because in acidic media it forms a protective oxide,
while it dissolves in alkaline solution forming tungstate ions, as Fig. 4.18 shows.

E-pH, for lead 2
PbO2
Passivation
1
Pb2+
Corrosion b
0
Pb
-1 Immunity
a
PbH2
Hydrides
-2 formation
0 7 14
pH

E-pH, for lead in CO2 2
containing solutions PbO2
Passivation
1
Pb2+
Corrosion
b
0 a HPbO2-
Corrosion
-1 Pb
Immunity a
PbH2
Hydrides
-2 formation
0 7 14
pH

E-pH, for lead in 2
sulphate-containing solution PbO2
Passivation
PbSO4 b
a Passivation
0 2-
HPbO
Corrosion
-1 Pb
Immunity
PbH2
Hydrides
-2 formation
0 7 14
pH

E-pH, for titanium 2
b
TiO2
0
-1
Ti2+ a
-2 Ti
0 7 14
pH

E-pH, for tungsten 2
WO5 2-(?)
WO3
1 Corrosion
Passivation
b
0
-1
a
W
Immunity
-2
0 7 14
pH
4.5 Final Remarks
Pourbaix diagrams provide a thermodynamic framework, which is of particular

importance for the study of the aqueous corrosion of metals, because they provide
fundamental information on the so-called immunity or, instead, the possible corro-
sion or activity condition or passivation state, i.e., the separation of oxides,
hydroxides, alkaline salts with protection properties. In particular, the diagrams help
understand how corrosion or protection conditions vary with potential and pH, and
when a metal can be considered in immunity or in passivity conditions, and which
conditions fit with an active-passive behaviour, or when an active-passive transition
can take place, for example by varying the potential or instead the pH.
For the correct use of Pourbaix diagrams, the following limitations must be taken
into account. First, they cannot provide any information on the kinetics of corrosion
processes (i.e., the corrosion rate), since they represent chemical or electrochemical
equilibrium conditions and the existence field of involved species, only. Second, the
thermodynamic information can often be insufficient for practical applications. For
example, activities should be taken into account and not the concentrations of
species, therefore the diagrams are strictly applicable to dilute solutions and not to
concentrate ones. Furthermore, particular attention must be paid when some com-
plexing chemical species are present in the solution, which vary the concentration
of metal ions in solution because of the formation of complex or insoluble com-
pounds: in the presence of complex compounds the corrosion zone widens; instead,
in the presence of insoluble compounds, the passivation zone widens. However,
tailored diagrams are available for specific environments.
Finally, it has to be noted that the protection capacity of layers, even when their
formation does occur, depends on uniformity, flawless structure, electrochemical
properties and other, which does not allow to include in the Pourbaix diagrams, for
instance, the specific action of some particular anions, such as chlorides.
4.5 Final Remarks 71
Marcel Pourbaix on Pourbaix Diagrams

In the opening chapter of his book, Lectures on Electrochemical Corrosion
(Plenum Press, New York, 1973), Pourbaix illustrates three examples on the
matter. First example. The manager of a Danish laundry decided to soften the
water with the aim to limit the consumption of soap. This novelty provoked
the corrosion of the water supply piping, producing rust stains on clothes
during washing. Second example. It went even worse in a hospital where it
was decided to carry out the same treatment. The softened water provoked
corrosion on the distribution piping, partially made of lead, which hitherto
had resisted corrosion, aftermath leading to symptoms of lead poisoning in
patients. Finally, the third example. Before transporting a series of lead-acid
batteries, containing sulphuric acid, a moving company decided to replace the
acid with distilled water in order to eliminate any hazard deriving from the
presence of sulphuric acid. In a few hours the plates of the batteries were
destroyed.
4:1 In a corrosion process what is the range of potential by which a metal can
corrode? Can this range be indicated on the Pourbaix diagram?
4:2 Explain briefly the meaning of lines on a Pourbaix diagram, as well as the
regions between them and their practical utility.
4:3 Write Eqs. 4.15 and 4.16 for aluminium dissolution in alkaline solution.
Calculate the pH threshold for amphoteric dissolution.
4:4 How can the passivation region be used for practical applications? Give
some examples.
4:5 Calculate the concentration of sodium cyanide necessary for the gold dis-
solution (complex Au(CN)-2 has a dissociation constant of 2 1038). How
can this condition be shown on the Pourbaix diagram?
4:6 In natural environments (seawater, fresh water, soil, concrete, pure atmo-
spheric dew) which cathodic reactions take place for the corrosion of steel?
And for acid rains? Write the reactions. Find the corrosion status on Pourbaix
diagram.
spheric dew) which cathodic reactions take place for the corrosion of copper?
diagram.
spheric dew) which cathodic reactions take place for the corrosion of lead?
diagram.
spheric dew) which cathodic reactions take place for the corrosion of alu-
minium? And for acid rains? Write the reactions. Find the corrosion status on
Pourbaix diagram.
spheric dew) which cathodic reactions take place for the corrosion of zinc?
diagram.
Bibliography

Pourbaix M (1974) Atlas of electrochemical equilibria in aqueous solutions, 2nd edn. NACE
Cebelcor, Houston, TX
Chapter 5
Kinetics of Aqueous Corrosion
No more can we observe what’s lost at any time,

When things wax old with eld and foul decay,
Or when salt seas eat under beetling crags.
Lucrezio, De Rerum Natura, Book I, 319–327
Abstract This chapter presents the forms of energy dissipation involved in a

corrosion process when a positive driving voltage is available for corrosion to take
place, as defined by thermodynamics, and how they concur to determine the overall
corrosion rate. Dissipations are described in terms of overvoltage of the different
processes involved, which are classified as activation overvoltage (metal corrosion,
hydrogen evolution), represented by Tafel law, concentration overvoltage (oxygen
diffusion) and ohmic drop (electrolyte resistivity). The trend of the overvoltage for
an active-passive metal is also described in the different potential ranges, corre-
sponding to immunity, activity, passivity and transpassivity (or localised corrosion).
Fig. 5.1 Pietro Pedeferri’s

drawing on titanium: Duomo
of Milan (2006)

https://doi.org/10.1007/978-3-319-97625-9_5
74 5 Kinetics of Aqueous Corrosion
5.1 Driving Force and Corrosion Rate
The first question that thermodynamics asks for the prediction of corrosion
occurrence on a metal exposed to an aggressive environment is: “Is there an
available driving force for the corrosion process?” If the answer is no, thermo-
dynamics excludes corrosion occurrence. This is the case with gold, which is more
stable than its corrosion products (thankfully, otherwise we would not find nug-
gets!); it is also the case with metals such as silver, copper or their alloys, when
oxygen is absent.
Instead, if the answer is positive, and this is the case for most widely-used metals
in industry, corrosion may or may not occur significantly, depending on the
intervention of some frictions, which can slow down corrosion processes, as for
instance, when protective surface films can form (Fig. 5.1).
Therefore, when the answer to the first question is affirmative, there is the need
to answer a second question, which we define as kinetic: If there is a driving force,
how fast is the corrosion process? In the past, until the 1960s, the answer to this
second question was based on knowledge from previous experiences or empirical
evidence, while today it is based on knowledge of corrosion kinetics.
With reference to Fig. 2.2, the corrosion process is characterized by four partial
processes:
• The anodic process which releases electrons in the metal, Ia
• The cathodic process which consumes those electrons, Ic
• Electron transport within the metal from the anodic region to the cathodic one,
Im
• Current transport within the electrolyte, Iel.
These processes takes place at same rate:
I a ¼ I c ¼ I m ¼ I el ¼ I corr ð5:1Þ
Hence, the corrosion rate is determined by the slowest of the three partial processes,
out of the electron transportation in the metal. When the slowest process is the
anodic one, for instance because of passivation effects promoted by the environ-
ment, corrosion is said to be under anodic control; conversely, when the cathodic
process is the slowest one, corrosion is said to be under cathodic control; even-
tually, when the ohmic resistance in the electrolyte prevails, corrosion is said to be
under ohmic control.
5.2 Dissipations in Corrosion Systems 75
Fig. 5.2 Potential balance

for a corrosion process (from
Piontelli 1961) ε
Q P P' W' W Y
EYN
EMQ
EPP' EW'W
EQP EP'W' EWY
EMN
5.2 Dissipations in Corrosion Systems
Figure 5.2 helps locate driving force and dissipations which, as proposed by
Piontelli,1 can be identified as follows:
0 0 0 0
E MN ¼ EMQ þ E QP þ E PP þ E P W E W W E WY þ EYN ¼ 0 ð5:2Þ
EMN is zero being M and N short-circuited and points are identified as:
M anode connection
Q on the side of the anodic metal phase, adjacent to the interface M/e
P on the side of the electrolyte, adjacent to the interface M/e
P′ and W′ in an electrolyte region where chemical composition remains constant
regardless the circulation of current
W is as P on cathodic side
Y is as Q on cathodic side
N cathode connection.
By introducing the appropriate reference electrodes in those points, it is possible to
measure the relative tensions (i.e., the potential differences). Points P and P′ are
made of the same metal as electrode M and similarly for W′ and W which are equal
to N. These reference electrodes work in equilibrium conditions since they are not
affected by any exchanging current with the electrolyte (therefore there are no
dissipations). The significance of the measurements is the following:
• EP′W′ = EMN
eq equilibrium potential
• EMQ and EYN ohmic drop in the metallic conductor (often negligible)
1
Roberto Piontelli (1909–1971) was an eminent Italian electrochemist.
• EQP and EYW overvoltages of processes occurring at the anode and cathode,
respectively. Each overvoltage measures the dissipation inherent in anodic and
cathodic processes, respectively
• EPP′ (and similarly EWW′) includes two terms: ohmic drop between PP′ (or WW
′) in the electrolyte and concentration polarisation due to chemical modifica-
tions caused by the circulation of current.
In summary:
• (EMQ + EYN) is the ohmic drop in metal (negligible)
• (EQP − EYW) is the algebraic sum of dissipations occurring at electrodes, called
activation overvoltage, respectively anodic, E QP ¼ ga , and cathodic,
EWY ¼ EYW ¼ gc . These terms are associated with the energy barrier for the
charge transfer of the electrochemical reaction
• (EPP′ − EWW′) is the algebraic sum of dissipations occurring within the elec-
trolyte (anodic and cathodic zone) which contains an ohmic drop contribution
and a term due to the variation of chemical composition, called concentration
overvoltage.
5.3 Activation Overvoltage
5.3.1 Exchange Current Density and Tafel Law
For an electrochemical reaction, for example M = Mz+ + ze−, equilibrium condi-

tion determines two key parameters: the equilibrium potential, Eeq, as thermody-
namic parameter and the exchange current density, i0, as the kinetic one. Both
parameters can only be determined experimentally.
In an equilibrium condition, E = Eeq, the cathodic process occurs at the same
rate of the anodic one, equals to the exchange current density:
ia ¼ ic ¼ i0 at E ¼ E eq ð5:3Þ
If the metal is brought to a potential, E, different from Eeq, the rates of anodic and
cathodic processes, measured by current density, ia and ic, are different from the
exchange current density.
With reference to the electrochemical cell shown in Fig. 5.3, with a current
circulating between M and N, the dissipation which takes place at the anode is
given by EQP ¼ ga , where the point P within the electrolyte, e, is very close at
metal surface to zeroing the ohmic drop. P is a reference electrode made of the same
metal of the electrode M (this configuration was named by Piontelli as iso-elec-
trodic electrode). For the measurement, a high impedance voltmeter must be used
to minimize the current flowing in the measurement circuit; the positive terminal
must be connected to M.
5.3 Activation Overvoltage 77
Fig. 5.3 Measurement of

overvoltage in a corrosion cell
(from Piontelli 1961) ε
Q P W Y
EQP EWY
In practice, the measurement of overvoltage by means of an iso-electrode reference

electrode is sometimes difficult because certain metals do not exhibit a stable
potential. For this reason, non-iso-electrodic reference electrodes are used, such as
standard reference electrodes as listed in Table 3.2. The overvoltage measured by
means of a standard reference electrode (or non-iso-electrodic electrode) is given
by:
g ¼ E Eeq ð5:4Þ
where Eeq is the metal equilibrium potential (given by the Nernst equation) versus
the reference electrode used. According to Eq. 5.4, cathodic overvoltage is defined
as negative, while anodic overvoltage is defined as positive:
gc ¼ E Eeq \0 ð5:5Þ
ga ¼ E Eeq [ 0 ð5:6Þ
The activation or charge transfer overvoltage, experimentally measured by the

procedure discussed above, is associated with the transfer of a charge in the elec-
trochemical reaction and requires the overcoming of an energy barrier as in kinetics
of chemical reactions. Hence, the rate constant, k(T), follows the Arrhenius
equation:
H
kðTÞ ¼ Z e RT ð5:7Þ
where H is activation energy (in J/mol), T is absolute temperature, R is gas constant

and Z is a constant. Following the Arrhenius approach, Butler and Volmer2 derived
a general expression of current density as a function of overvoltage, called Butler-
Volmer equation:
2
John Alfred Valentine Butler (1899–1977) was an English physical chemist who developed
kinetic theories of the origin of electrode potentials and developed the general theory of over-
voltage with hydrogen and oxygen electrodes. Max Volmer (1885–1965) was a German physical
chemist, who made important contributions to electrochemistry, in particular on electrode kinetics.
He co-developed the Butler–Volmer equation.
ð1bÞzF g b zF g

i ¼ i0 e RT e RT ð5:8Þ
where g is overvoltage given by g ¼ E Eeq , i0 is exchange current density as

defined above, b (often taken as 0.5) is charge transfer coefficient, F is Faraday
constant and z is reaction equivalence. The Butler-Volmer equation states that the
exchange of current on the surface of an electrode takes place only if an activation
energy is exceeded, hence, dissipating a portion of the driving voltage.
In the event that overvoltage is very low, taking b ¼ 0:5 and remembering that
ex ffi 1 þ x, the Butler-Volmer equation approximates to a linear relationship:
RT
g¼ i¼ki ð5:9Þ
zFi0
In all other cases, however, the relationship between g and i is logarithmic and the
equation shortens to the Tafel law3:
g ¼ a b log i ð5:10Þ
where the + sign applies to the anodic processes (gis positive), while the – sign is
for cathodic processes (g is negative). Parameters a and b are defined as:
2:3 RT
a¼ log i0 ð5:11Þ
b zF
2:3RT
b¼ þ ð5:12Þ
b zF
Parameter a is a constant which depends on the exchange current density i0;

parameter b is a positive constant that assumes the meaning of a straight-line slope
of the function η−log i in a semi-logarithmic diagram, called Tafel slope. At room
temperature (298 K) and considering b ¼ 0:5 (symmetric behaviour), constant
b has a value of 59 mV/decade for bivalent reaction (z = 2) and 118 mV/decade for
monovalent reactions (z = 1), for example hydrogen evolution.
Overvoltage Correlations
Overvoltage depends on metal properties and temperature: for instance, it
decreases as temperature increases. The corresponding correlations for nor-
mal metals involve, on the one hand, low melting temperature, low hardness
and low mechanical properties, and on the other, a large crystal lattice size;
3
Julius Tafel (1862–1918) was a German chemist who worked in electrochemistry with Wilhelm
Ostwald.
conversely, inert metals are characterized by a high melting temperature, high

hardness, high mechanical resistance and small crystal lattice size. This
implies that there is a high affinity of atoms to the crystal lattice for inert
metals, whilst normal metals show the opposite, i.e., low affinity. The same
trend applies to the affinity of metal ions to the solution: weak for normal
metal, and high for inert metals.
Electrochemical inertia derives from the bond existing between metal ions,
produced at the electrode surface, either towards the crystal lattice or to the
solution, hence determining the rate of the electrochemical process.
Indeed, the transition from an initial condition, for instance crystal lattice,
to a final condition, that is, ionization, occurs through an intermediate con-
figuration in which initial bonds are partially broken whilst final bonds are not
yet completely defined. This corresponds to maximum energy, or the
so-called energy barrier. If bonds of both initial and final conditions are
weak, the intermediate configuration corresponds to a low energy barrier
(level slightly higher than the initial and final ones) and conversely, when the
bonds of both the initial and final conditions are very strong, the energy
barrier is high.
5.3.2 Potential-Current Density Diagrams (or Characteristic

Curves)
Figure 5.4 depicts the variation of overvoltage with current density according to the
Butler-Volmer equation for a general electrochemical reaction. Such curves are
called characteristics, anodic and cathodic, respectively. Figure 5.5 shows how
characteristic curves can be represented: Fig. 5.5a in a linear scale where the anodic
current is positive and the cathodic current is negative; Fig. 5.5b in a linear scale
where the anodic and cathodic are overlapped (both positive); Fig. 5.5c
semi-logarithmic scale, which is the most-used representation. By looking at the
latter figure, it appears that curves become straight lines when far from the equi-
librium potential (Tafel law).
When Tafel law applies, that is, for inert and intermediate metals, anodic and
cathodic overvoltages can be written in terms of exchange current density as
follows:

i
ga ¼ a þ b log i ¼ b log ð5:13Þ
i0

i
gc ¼ a b log i ¼ b log ð5:14Þ
i0
E
Anodic
curve
ηa
Eeq
ηc
Cathodic
curve
ic ia
Fig. 5.4 Schematic trend of anodic and cathodic overvoltage of metals
(a) E (b) E (c) E
ηa ηa ηa
Eeq
ηc
ηc ηc
ic ia log i
Fig. 5.5 Types of representation of characteristic curves
Figure 5.6 shows the plot of the potential as a function of experimentally measured
current density, iext = ia − ic or iext = ic – ia, and not as a function of ia and ic
(which cannot be measured directly, see also Chap. 6). Far from equilibrium, i.e.,
for a potential shift higher than ±50 mV from the equilibrium potential, measured
values match the extrapolated straight lines. Conversely, near equilibrium, i.e., for a
potential shift lower than ±10 mV from the equilibrium potential, there is a
deviation from the theoretical curve since the measured current, iext = ia − ic or
iext = ic − ia, strongly differs from either ic or ia. These experimental curves make it
possible to obtain:
• Straight lines which give the potential, E, as a function of anodic or cathodic
current densities, ia and ic, obtained by the extrapolation of the linear part of the
curve
• Exchange current density, i0, given by the crossing point of the two straight lines
at the equilibrium potential
• The slope b which allows to calculate the overvoltage, for instance
ga ¼ b log ia =i0 .
ia
Eeq
ic
i0 log i
Fig. 5.6 Trend for the polarization curve to find the exchange current density, i0, experimentally
Table 5.1 Tafel slope, b, and order of magnitude of exchange current density, i0, for metals (from
Piontelli 1961)
Metal classification Exchange current density, Tafel slope,
i0 (order of magnitude in mA/m2) b (mV/decade)
Inert Pt 1 Monovalent 120
Pd, Rh
W, Ta
Co, Ni
Fe Bivalent 60
Intermediate Cu, Ag 10 Monovalent 120
Bivalent 60
Normal Sn, Al, Be 104 b ≅ 0 (linear trend)
Zn
Pb, Hg
Table 5.1 reports exchange current density, i0, and Tafel slope, b, for most common
metals; it is worth noting that values of i0 differ significantly from inert to normal
metals.
5.3.3 Oxidation or Reduction of a Metal
The overvoltage associated to a metal dissolution process when immersed in a

solution containing its ions (i.e., a soluble salt) depends on the nature of the metal.
Its trend for metal working as anode (metal dissolution) or as cathode (metal
Fig. 5.7 Activation ηM

overvoltage of metals as a Inert
function of current density
(from Piontelli 1961) Intermediate
Normal
ic ia
deposition) is symmetrical (Fig. 5.7). Piontelli proposed the following classification

on the basis of the value of overvoltage:
• Normal metals, for which even at high current density, from both the anode side
and the cathode side, the overvoltage, gM , is less than 10 mV (metals at low
overvoltage). This class includes the low melting temperature metals: Cd, Hg,
Sn, Pb, Mg, Al and Zn (the latter only at the anodic side)
• Inert metals, for which even at small current density and in a wide range of
conditions, in the absence of polarizing current, overvoltage, gM , is greater than
100 mV (metals with high overvoltage). This class includes the high melting
temperature metals: Fe, Co, Ni, Cr, Mo, Ti, metals of the platinum group and
transition metals
• Intermediate metals, for which gM is between the two above-mentioned limits.
Examples of intermediate metals are: Cu, Au and Ag.
For normal metals, at low current densities (say, below 1 A/m2), the overvoltage of
the metal dissolution process depends linearly on current density (Eq. 5.8); for
intermediate or inert metals in all other conditions, the overvoltage-to-current
density dependence is logarithmic and follows Tafel law (Eq. 5.9).
It must be emphasized that, with the exception of normal metals (for which gM
zeros as i zeros), gM is not nil for intermediates and especially inert metals, even for
values of current density close to zero (Fig. 5.7). Accordingly, electrodes of these
metals, even for infinitesimal current flow, require the overwhelming of a threshold,
like the static friction in mechanics.
5.3.4 Hydrogen Evolution (Activation Overvoltage)
The activation overvoltage of hydrogen evolution, gH2 , can be measured as shown

in Fig. 5.3, as tension, EWY, when on electrode N the cathodic reaction is hydrogen
evolution. This overvoltage is strongly dependent on the nature of the metal, as
experimentally observed: there is a clear inverse correlation between overvoltage,
gM , related to the oxidation of metal, M, and overvoltage of hydrogen evolution,
Fig. 5.8 Reverse correlation ηH2 increasing

between metal dissolution
overvoltage and hydrogen Pt, Pd, Co, Fe, Ni, Ag, Cu, Sb, Bi, Al, Cd, Sn, Zn, Pb, Hg
evolution overvoltage (from
Piontelli 1961) ηM increasing
Hg, Pb, Sn, Cd, Zn, Al, Ag, Bi, Sb, Cu, Ni, Fe, Co, Pd, Pt
gH2 , taking place on it. On normal metals, characterized by a low overvoltage,

hydrogen evolution overvoltage is high, and the opposite occurs on inert and
intermediate metals, as summarized in Fig. 5.8. Since normal metals have a low
melting temperature and inert metals a high one, the following is a simple rule to
establish overvoltage contributions:
• Metals with a low melting temperature have low dissolution-related overvoltage
and high hydrogen evolution overvoltage
• Metals with a high melting temperature have high dissolution-related over-
voltage and low hydrogen evolution overvoltage.
For this reason, Piontelli suggested calling this correlation reverse correlation. The
strong influence of the nature of metal on hydrogen overvoltage explains the
influence of impurities present on the metal surface on corrosion rate in acidic
solutions, where the cathodic reaction is hydrogen evolution. For instance, pure
low-melting temperature metals with high hydrogen overvoltage such as Zn, Pb and
Al show an increase in the corrosion rate as the content of high-melting temperature
impurities, like Fe, Ni and others, increases. Moreover, the presence of cold work
deformation (by an increase in dislocation concentration on the surface) and surface
finishing can influence hydrogen overvoltage. Hydrogen overvoltage follows Tafel
law with a slope of 120 mV/decade; this leads to a variation of an order of mag-
nitude of current density when potential changes by about 120 mV (Table 5.2).
Correlations for Hydrogen Overvoltage

Hydrogen reduction reaction involves three steps:
• H3O+ + e− + M ! M−H + H2O with formation of atomic hydrogen
adsorbed on metal M
• H3O+ + e− + M−H ! H2 + H2O + M (electrochemical desorption) or
• 2M−H ! H2 + 2M (chemical desorption)
The slowest step determines the kinetic control of the overall hydrogen
evolution process. If the slowest stage is the first, the Tafel slope is 120 mV/
decade; if it is the second, i.e., an electrochemical process, the Tafel slope is
also 120 mV/decade; if it is the third, i.e., chemical desorption, the Tafel
slope is 30 mV/decade: the latter case occurs for metals of the platinum
group.
Table 5.2 Order of magnitude of exchange current density, i0;H2 M , of hydrogen on metal, M,
and order of magnitude of exchange current density, i0,M, of metal M
Metal classification Exchange current density, i0;H2 , on Exchange current density, i0,M
metal, M (order of magnitude in mA/ (order of magnitude in mA/
m2) m2)
Inert Pt 104 1
Pd, Rh 103
W, Ta 102
Co, Ni 10
Fe 1
Intermediate Cu, 10−1 10
Ag
Normal Sn, Al, 10−2 104
Be
Zn 10−3
Pb, Hg 10−4
The first stage applies when the M–H binding energy is high and, con-
versely, it is not favoured in the opposite case. It follows that hydrogen
overvoltage is high (i.e., exchange current density, i0, is low, as happens for
Pb, Cd, Tl or In) because binding energy is low and the formation of M–H is
not favoured.
However, when binding energy is very high, as in hydride-forming metals
(Ti, Ta or Nb) overvoltage becomes high again because the desorption stage
slows down. Figure 5.9 shows the so-called ‘volcano plot’, well known in
chemical catalysis.
Fig. 5.9 Volcano plot of

exchange current density, i0, 2
of hydrogen evolution as a Au,Cu Pt,Rh
log i0,H (mA/m2)
function of M–H binding Fe Ir,Re

energy (from Bianchi and Ni,Co
Mussini 1993) -2 Zn,Sn
Ag
Mo,Ti
2
Bi,Ga
Nb,Ta
Pb,Cd
Tl,In
-6
0 200 400
H-M bonding energy (kJ/mol)

5.3.5 Oxygen Reduction (Activation Overvoltage)
The oxygen reduction process involves two dissipation contributions: one corre-
sponding to the process of charge transfer to the metal surface and the other to the
transport of oxygen in the solution. In this paragraph, the first contribution is
discussed.
Overvoltage contribution associated with a charge transfer process depends,
intrinsically, on metal and also pH, presence of surface layers, current density and
follows Tafel law. Figure 5.10 shows the linear section of Tafel curves for various
metals at different pH values. Unlike hydrogen overvoltage, the Tafel slope for
oxygen reduction is generally higher. Therefore, it is in the order of hundreds of
mV even for current density tending to zero and especially in acidic environments.
The presence of surface films increases oxygen overvoltage on chromium, and
then on stainless steels, titanium, zirconium, as well as copper and nickel; instead,
oxygen reduction takes place more easily on gold, palladium, platinum and
graphite.
5.4 Concentration Overvoltage
Let's consider the galvanic cell M=e=N in Fig. 5.11 where the electrolyte, e, is
composed by a dissolved salt, MX. Any current circulation in the cell determines a
variation of the chemical composition in the electrolyte because mant processes
take place: electrochemical, electrophoretic, diffusive and convective. These
changes in chemical composition generate an overvoltage contribution, called
concentration overvoltage, and also concentration polarisation. Concentration
overvoltage is given by the measurement of EPP′, where P and P′ are two
E (V SHE) (a) E (V SHE) (b) E (V SHE) (c)

Acidic Neutral Alkaline
1.0 solutions 1.0 solutions 1.0 solutions
Pt
Au Pt Pt
0 0 0
Ni Ni Grafite
Grafite
Cr Zr Zr
-1.0 -1.0 -1.0
10 102 103 10 10 2
10 3 10 102 103
log i (mA/m2) log i (mA/m2) log i (mA/m2)
Fig. 5.10 Charge transfer overvoltage of oxygen reduction: a acidic, b neutral, c alkaline
solutions
Fig. 5.11 Meaning and

measurements of oxygen
IMN ε
concentration overvoltage M
Q P P' W' W Y
EPP'
iso-electrodes made of metal M. Position P′ is not perturbed by current circulation.

The measured potential, EPP′, is the sum of two terms:
0 0 0
E PP ¼ EI¼0
PP
þ IRPP ð5:15Þ
0
where EPPI¼0 is concentration polarization which can be measured by zeroing the
current in the cell; the measurement must be taken at the so-called instant-off
0
condition, i.e., very soon after current switch off, and IRPP is the ohmic drop in the
electrolyte between P and P′; RPP′ is the electrolyte’s ohmic resistance and I is the
current circulating in the cell.
PP0
Concentration polarization, EI¼0 , depends on several factors: current density,
elapsed time, initial composition of the electrolyte, e, and any other factor
influencing diffusive and convective processes (cell geometry, temperature, flow
regime). Eventually, it depends also on the nature of reference electrode used for P
and P′. As shown in Fig. 5.12, while applied current is constant, potential changes
with time. When the current is switched-off, measured potential changes as follows:
• Ohmic drop IRPP′ (between P and P′) zeroes in 10−6 s after switch-off. This
property is the basis of the on-off technique often used in the laboratory and in
the field for CP measurements
• Over a longer time, activation overvoltage, typically for hydrogen evolution,
zeroes in 10−3 s after switch-off. Compared to concentration polarization, as in
the point below, activation overvoltage fades practically instantaneously at
ohmic drop
E I
IRPP’
PP’
E I=0 I
t t
Fig. 5.12 Potential variation before and after current switch off
5.4 Concentration Overvoltage 87
• Within this very short time, from 10−3 to 10−6 s, there is no modification of
electrolyte composition as set up by the circulating current
• A slow potential modification takes place after current switch-off until the
electrolyte has recovered the initial composition through a diffusive process in
reverse direction. In other words, diffusive process is slow in nature.
In summary, according to the adopted definitions, overvoltage concentration in a

PP0 WW0
galvanic cell as the sum of anodic EI¼0 and cathodic EI¼0 contributions, represents
the instant variation of cell voltage before and after current circulation.
Polarity of Concentration Polarisation

If an external electromotive force, EMF, is applied to the galvanic cell,
M=e=N, with a current flow from M to N (M works as the anode and N as the
cathode), Mz+ concentration grows at the anodic region and decreases at the
cathodic one, while it remains unchanged at the intermediate region (P′).
Now, by switching the external power supply off and short-circuiting the
cell, an EMF is generated due to the concentration cell set-up because of
different concentrations of Mz+ in P and P′ then producing a current circu-
lation in the opposite direction. In fact, the electrode in contact with P (where
the concentration of Mz+ is increased) now tends to work as the cathode while
N works as the anode. Therefore, an EMF is measured between P and P′
which is in opposition to the previous external EMF; for this reason, it is
called back-EMF (refer to Chap. 3.8.1 for the concentration cell).
It has to be emphasized that, while overvoltage ensures energy dissipation,
which is necessary for the occurrence of electrode reactions, concentration
polarization represents, instead, an accumulation of energy through the for-
mation of a concentration cell. This stored energy, however, is not recovered
as electrical work, because it is dissipated through diffusion phenomena that
occur to make the solution more uniform.
Based on what is discussed above, both electrode overvoltage and con-
centration polarization contribute to increase cell voltage (i.e., absorbed
energy) when working as the user, while they contribute towards decreasing
cell voltage (i.e., obtained energy) when working as the generator.
5.4.1 Oxygen Reduction: Limiting Current
In the case of oxygen reduction as a cathodic process, concentration polarization

(also called overvoltage concentration) caused by oxygen diffusion in the
electrolyte can become particularly important, because of high concentration gra-

dients set up in the diffusion layer close to the electrode surface.
Let's first consider the case of a stagnant solution without convective flows. In
the electrolyte layer, a concentration gradient of oxygen forms next to the metal
surface. In fact, oxygen is consumed on the metal surface due to the corrosion
process. Hence, its concentration decreases on the metal surface, whereas it remains
constant in the bulk. This concentration gradient is within the so-called diffusion
layer or Nernst diffusion layer, d, as shown in Fig. 5.13, between metal surface II
and surface I in the electrolyte.
The concentration gradient in the diffusion layer gives rise to a concentration
polarization with opposite polarity to EMF set up by the corrosion process; this
overvoltage, gconc; O2 , can be expressed as follows (see Sect. 3.10.1):
RT C1 RT C2
gconc; O2 ¼ E II;I ¼ ln ¼ ln ð5:16Þ
zF C2 zF C1
where C2 is oxygen concentration on the metal surface and C1 is the oxygen

concentration in the bulk, i.e., outside the diffusion layer.
The oxygen diffusion rate, vD (moles/(m2 s)), in a stationary condition is gov-
erned by Fick law:
ðC1 C2 Þ
vD ¼ D ð5:17Þ
d
where D is the diffusion coefficient (m2/s), d is the diffusion layer thickness (m).
The oxygen consumption rate, vC (moles/(m2 s)), is given by Faraday law:
i
vc ¼ ð5:18Þ
zF
where i, z and F have the usual meanings.

In stationary conditions, oxygen consumption and diffusion rates are equal,
therefore:
Fig. 5.13 Diffusion layer I II

representation and Limiting ε N
concentration profile of diffusion
C1 layer
reducing species
I
C2
Homogeneous solution
δ
5.4 Concentration Overvoltage 89
i C1 C2
vc ¼ vD ¼ ¼D ð5:19Þ
zF d
D
i¼ z F (C1 C2 Þ ð5:20Þ
d
As a result, the current density in stationary conditions is proportional to the dif-

fusion coefficient, D, and the oxygen concentration gradient. Since, for a given
system, the oxygen concentration in bulk, C1, the diffusion coefficient, D, and the
diffusion layer thickness, d, are constant, current density, i, increases as oxygen
concentration, C2, decreases at the electrode surface. For metals with low potential,
for instance Fe and metals below it, the oxygen consumption rate reaches a max-
imum when C2 zeros. This maximum is the oxygen limiting current density, iL,
given by:
D
iL ¼ zF C1 ð5:21Þ
d
By introducing the relationship between concentrations C1, C2in the Eq. 5.16, the
current density, i, and the limiting current density, iL C2 ¼ zFdD ðiL iÞ;
C1 ¼ zFdD iL Þ, overvoltage concentration, gconc; O2 , is given by:
RT C2 RT iL i iL i
gconc; O2 ¼ ln ¼ ln ¼ 0:015 log ð5:22Þ
4F C1 4F iL iL
where the constant 0.015 applies at 25 °C.
5.4.2 Total Oxygen Overvoltage
The cathodic process of oxygen reduction deals with the sum of activation over-
voltage and concentration polarization; when the equilibrium potential of hydrogen
evolution is reached (E\Eeq;H2 ) the potential follows the Tafel law of hydrogen,
therefore, the potential cannot tend to −∞ as would be expected from Eq. 5.16 as
shown in Fig. 5.14.
Analytically, the cathodic overvoltage of oxygen reduction process is as follows:
• In the range between Eeq;O2 and Eeq;H2 , (1.23 V), the cathodic current, i, varies
from i0;O2 to iL and overvoltage is given by:
i iL i
g ¼ gact;O2 þ gconc; O2 ¼ b log þ 0:015 log ð5:23Þ
i0;O2 iL
Fig. 5.14 Cathodic E

characteristic of oxygen
reduction process Activation
overvoltage
Oxygen
reduction
Concentration
polarization
iL log i
where i0;O2 is the exchange current density for oxygen reduction which depends
on metal, b is the Tafel slope for oxygen reduction, often taken as 100–120 mV/
decade, and iL is the oxygen limiting current density, which depends on the
electrolyte and not on the metal
• For E\Eeq;H2 when current density exceeds the oxygen limiting current density
(i > iL), the overvoltage is:
i
g ¼ 1:23 þ gact;H2 ¼ 1:23 b log ð5:24Þ
i0;H2
where i0;H2 is the exchange current density for hydrogen evolution which
strongly depends on metal, b is the Tafel slope for hydrogen evolution and is
120 mV/decade, and iL is the oxygen limiting current density which depends on
the electrolyte and not on the metal.
It is worth noting that Eq. 5.24 applies to any pH. Figure 5.15 shows the resulting
cathodic characteristic obtained by summing currents of occurring cathodic pro-
cesses at each potential.
In summary, the cathodic curve is characterized by three intervals: i < iL where
activation overvoltage prevails; i approaches iL ði ffi iL Þ under diffusion control and
i > iL, where hydrogen evolution becomes predominant.
Fig. 5.15 Resulting cathodic E

characteristic of oxygen O +
2 2H
reduction and hydrogen Eeq,O 2 O + 4e -
2 4
evolution OH -
2H +
Eeq,H + 2e -
2
H
2
iL log i
5.5 Other Cathodic Processes 91
5.5 Other Cathodic Processes
Figure 5.16 reports cathodic curves for five cathodic processes, showing different
oxidizing power:
• ① hydrogen evolution
• ②, ③ oxygen reduction
• ④, ⑤ more noble cathodic processes as reduction of ferric ion to ferrous ion,
chlorine reduction or reduction of chromate.
The position and trend of curves depends on the metal and environment compo-
sition, the temperature and the flowing regime.
5.6 Passivation and Passivity
The corrosion resistance of metallic materials is strongly dependent on the surface

condition through the presence of oxides and corrosion products which eventually
define the corrosion behaviour in practice. There are many noteworthy examples of
corrosion resistance by passivation or passivity:
Fig. 5.16 Qualitative trend E (V SHE)

of cathodic curves for: ①
Hydrogen evolution; ②–③
Oxygen reduction; ④–⑤
Noble cathodic processes 1.6
High 5
1.2 ly ox
idizi
ng s
peci
es
0.8
4
O +
2 2H
2O + 4 -
e
0.4 4OH -
2 3
2H + +
0 2e -
H
2
1
10 102 103
log i (mA/m2)
• Low nobility metals such as aluminium, chromium, titanium, zirconium, tan-

talum, stainless steels and other high alloy steels resistant to many aggressive
environments
• Iron in concentrated but not in diluted sulphuric acid
• Titanium in oxygen-free sulphuric or hydrochloric acids but not in aerated ones
• Lead in diluted but not in concentrated sulphuric acid; in tap water but not in
distilled water
• Aluminium and stainless steel in nitric acid, but not in hydrochloric acid; it is the
opposite for silver
• Carbon steel in concrete but not in plaster (gypsum)
• Aluminium or lead in plaster, but not in concrete.
The formation of layers on the metal surface is called passivation; when the pro-
tection property of these layers leads to a practical halt of corrosion, this condition
is called passivity. In practical terms, passivation involves the formation of thick
layers, for instance in the order of tens of micrometres, while passivity occurs when
the layer is much thinner, in the order of nanometres. In the case of passivity, the
layer is called passive film.
Oxygen Limiting Current Density in Seawater

By applying Eq. 5.21 to seawater, where oxygen concentration does not
exceed 11 ppm, the diffusion layer thickness, d, varies in the range 0.1–
3 mm, depending on turbulence, and the diffusion coefficient, D, ranges
between 1.3 and 2.5 10−9 m2 s−1 for temperatures from 10 to 30 °C,
oxygen limiting current density, iL, seawater, ranges between 10 mA/m2
(stagnant water and oxygen content about 1 ppm) and 2 A/m2 (maximum
turbulence and aeration, such as near ship impellers).
5.6.1 Film Formation Mechanisms
Protective films on metal surfaces can form following two mechanisms: by pre-
cipitation of insoluble corrosion products or directly as a result of the anodic
reaction.
The first mechanism deals with metals of normal to intermediate electrochemical
kinetic behaviour and gives rise to thick layers, characterized by some porosity, a
defined crystallographic structure and poor conductivity. This behaviour is called
passivation and is typical for:
• Lead in sulphuric acid which spontaneously forms a layer of lead sulphate or
lead dioxide when an external voltage is applied
5.6 Passivation and Passivity 93
• Silver in chloride-containing solutions which forms a silver chloride layer

• Copper or bronze exposed to the atmosphere which form a basic copper car-
bonate layer, the so-called patina (from Latin, patina nobile); similarly, when
exposed to sea water, the formation of copper oxi-chloride (atacamite) occurs.
Patina can form spontaneously over a time span of possibly months to obtain
protection films, or can be produced artificially through accelerated processes
used in industry, such as phosphating of steel and zinc or patination of bronze.
The adhesion and protection properties of films depend on both metal and elec-
trolyte composition as well as on the compatibility with other forming deposits.
The second mechanism is more important and leads to so-called passivity. It
affects transition metals such as Fe, Cr, Mo, W, Ti, Zr, and alloys like stainless
steels. Until the 1970s, two theories were proposed: the first suggested that passivity
consists of a monoatomic layer of adsorbed oxygen; the second proposed the
formation of a metal oxide film. Later, new surface analysis techniques such as
AFM, Auger spectroscopy and electron microscopy clarified that, with few
exceptions, passive films are an oxide-type layer, 3-5 nm thick, with
semi-conductive properties.
For alloys, oxide film composition varies and rarely reproduces that of the alloy;
most often one element prevails, determining passivity. For instance, on the surface
of stainless steels, which have a minimum of 12% chromium content, there is an
enrichment in chromium to form a passive film, composed mainly of chromium
oxide (Cr2O3). Through this enrichment, stainless steels, although largely com-
posed of iron, behave like chromium: for instance, the field for the formation of
passive films widens as shown in Fig. 5.17, where Pourbaix diagrams of Fe and Cr
are overlapped.
Fig. 5.17 Overlapping of E (V SHE)

Pourbaix diagrams of Fe and 2
Cr (shadowed zone)
1 Fe3+
Fe2+ Fe2O3 b
0
Fe3O4
-1
a
Fe HFeO2-
-2
0 7 14
pH
Anodizing can cause some metal oxides to grow thicker as in the case of Al, on
which the oxide film thickness can be 2030 lm, about three orders of magnitude
thicker than spontaneous films. For Al, the thicker the passive film, the more
resistant it is to corrosion. There are opposite cases, for instance for stainless steels
where thicker film formed on the heat affected zone, HAZ, in welding (tinted zone)
or during high temperature rolling, are less resistant than passive thin films.
Historical Notes
Towards the end of the nineghteenth century, it was noticed that iron was able
to precipitate silver only from some solutions and not from others that are
apparently similar. Faraday, among others, resumed this phenomenon around
1840 in relation to studies on the passivity of iron, then called the condition of
non-reactivity of iron.
As represented in Fig. 5.18, the English scientist noticed how iron does
not suffer corrosion in concentrated (fuming) nitric acid, while in diluted acid,
obtained by adding the same quantity of water, it corrodes vigorously while
also producing bubbles of gaseous nitrogen oxides. He also observed that in
dilute nitric acid it did not corrode if previously immersed in concentrated
nitric acid, provided that the iron surface was not mechanically scratched. He
also noted that corrosion did not take place if connected to the positive pole of
a battery in a galvanic cell. On the basis of these observations, Faraday
attributed passivity to the presence of an oxide layer. In later decades it was
discovered that this phenomenon applies also to other metals such as bismuth,
tin and chromium.
It was also noted that chromium, unlike iron, only passivated by exposure
to air. Finally, at the beginning of the twentieth century, in 1911, Monnartz
highlighted that Fe–Cr alloys with a chromium content higher than 10.5%,
i.e., stainless steels, behaved similarly. This discovery transformed the pas-
sivity from a scientific curiosity to a phenomenon with huge industrial
implications.
H2 O
(a) (b) (c)
Fe Fe Fe
Fig. 5.18 Schematic illustration of Faraday experience on the passivity of iron: a nitric acid at
67%; b and c the solution obtained by diluting the same acid with an equal quantity of water
5.6.2 Oxide Properties
Passive films can be crystalline or amorphous, insulating or conductive (ionically or

electronically). For instance, aluminium oxide is a good insulator and isolates the
metal from the electrolyte; conversely, passive films formed on iron in alkaline
solutions, as well as on chromium, nickel and stainless steels have a high electronic
conductivity. Thus, they easily host the cathodic process, such as for instance,
oxygen reduction.
Electrolyte composition influences film growth: for instance, halogens hinder
formation of oxides, making them defective, other anions which produce insoluble
products favour passivity (for example phosphates).
Potential and pH determine the field in which films form, as shown in the
Pourbaix diagram. For instance, iron corrodes in gypsum plaster (pH < 7) and
passivates in concrete (pH > 13); for lead it is the opposite, since it passivates at pH
7 and dissolves at pH 13, as occurs for amphoteric metals.
5.6.3 Active-Passive Metals
The typical anodic characteristic of an active-passive metal is shown in Fig. 5.19.

Four zones are identified, indicating distinct corrosion behaviour:
• Immunity, E < Eeq, in which metal does not corrode; instead, it deposits from its
ions if present
• Activity, Eeq < E < Ep, in which metal dissolves. In this range, Epp is primary
passivation potential, which copes with the maximum anodic current, icp, called
critical passivation current density and Ep is passivity potential
• Passivity, Ep < E < Etr, in which metal is passive. Etr is transpassivity potential
or oxygen evolution potential or pitting potential, Epit. The dissolution rate
corresponds to passivity current density, ip, which is very low, about 10−6 lower
than icp
• In oxidising-chloride containing environments, at potential higher than pitting
potential (E > Epit) passive film locally breakdowns and localised corrosion can
initiate
• Transpassivity or oxygen evolution (E > Etr). In this zone, noble anodic pro-
cesses take place, such as oxygen evolution or the production of high valence
ions such as chromate and bi-chromate (Cr2O3 + 5H2O ! 2CrO42
−
+ 10H+ + 6e−).
If passive film is insulating, i.e., has ionic conductance only, it cannot transport
electrons for electrodic processes like oxygen evolution. Therefore, passive film can
grow, reaching very high (noble) potentials, for instance of 100 V and more. On
Etr Transpassivity
Passivity
Ep
Epp Activity
Eeq
Immunity
log i
ip i0,M icp
Fig. 5.19 Anodic characteristic of an active-passive metal
E (a) E (b)
Increasing potential Increasing potential
Decreasing
potential Decreasing
potential
log i log i
Fig. 5.20 Hysteresis effect on anodic characteristic for Fe–Cr alloys: a %Cr below 13%; b %Cr
above 13%
titanium, very thick films can be obtained at 100–200 V in some electrolytes, giving
rise to a new phenomenon produced by the perforation of the film (anodic spark
oxidation).
The anodic curve varies in accordance with the potential sweeping direction, as
shown in principle in Fig. 5.20a. Instead, Fig. 5.20b shows two different curves for
Fe–Cr alloys with a Cr content higher or lower than 13%, respectively. Once
formed, the passive film shows a persistency which helps reach protection condi-
tions by applying cathodic protection by passivity (refer to Chap. 23).
5.6.4 Passivity-Related Parameters
The passivation and passivity behaviour of a metal depends on a number of

parameters, which are derived from the anodic polarization curve obtained from
testing. These parameters are:
• Critical passivation current density, icp; tendency to passivation increases as
critical passivation current density decreases
• Passivity current density, ip; passivity is more stable as the passivity current
density lowers and the passivity interval widens
• Primary passivation potential, Epp
• Passivity potential, Ep
• Transpassivity potential, Etr (or pitting potential, Epit)
• Passivity interval (Etr − Ep), which defines the extension of passivity.
Beyond the composition of the metal, environmental properties, such as tempera-
ture, acidity and chloride concentration, influence the curve shape as schematically
depicted in Fig. 5.21. All these parameters must be measured at experimental
conditions as close as possible to operating conditions, because they cannot be
derived from metal composition (pure metal or alloy; annealed or cold worked;
surface finishing), environment composition (in particular the presence of halogens)
and temperature. In order to have a rough orientation of main parameters for
stainless steels, a reference is Lazzari 2017.
Oxide Memory
Experience has shown that operating conditions at the moment of film for-
mation from bare metal surface are of great importance to obtain a film with
high and constant protection properties; in other words, a sound film formed
at the beginning will also be the same later even if conditions change slightly;
Fig. 5.21 Influence of the E

stainless steel composition of
and environmental conditions
(T, pH, Cl) on the shape of the
active-passive anodic curve
CI-, T
PREN, pH
CI-, T
PREN, pH
Ep
Ni
ip icp log i
conversely, a bad film will not improve successively even if new favourable
operating conditions are set up. A remarkable example is given by the startup
of a heat exchanger made of copper alloys where the cooling fluid is sea-
water: if the metal surface is bare, clean and cold with well aerated seawater,
the passivation film forms with high protection properties; if startup is carried
out on load (i.e., when operating at temperature) the film shows poor pro-
tection properties also in the next operating conditions.
Pietro Pedeferri exploited the memory of titanium oxides to obtain artistic
and decorative results, as shown in Fig. 5.22: dark and silvery lines corre-
spond to films with different properties, such as structure, corrosion resistance
and colour, obtained by anodizing titanium surface at different initial
potentials to imprint the early properties of the oxide.
As Pedeferri explained, this imprinting effect can be exploited for artistic
purposes and for obtaining the required protection properties, since oxide film
obtained at the beginning will also maintain its property thereafter.
Fig. 5.22 Artistic use of oxide memory of titanium by P. Pedeferri (1968)

5:1 Draw the anodic curves for Fe and Zn dissolution in oxygen-free acidic
solution and the cathodic curves for hydrogen evolution. Discuss whether
they may change in time and how.
5:2 Suggest an interpretation why the passivity current density of stainless steels
exposed to H3PO4 is lower than that in sulphuric acid.
5:3 Suggest an interpretation why the passivity current density of stainless steels
exposed to strong alkali is higher than that in HCl.
5:4 A steel plate is exposed to seawater in equilibrium with the atmosphere at
room temperature, pH 8.3, water velocity 1 m/s.
(a) Determine the equilibrium potential of O2 reduction reaction
(b) Calculate the limiting current density of the oxygen reduction
reaction when there is no deposit on the steel surface
(c) Calculate the oxygen permeability (or also the deposit efficiency)
after a couple of years, when a layer of rust and calcium car-
bonate, 1 mm thick, builds up if an average corrosion rate, de-
termined by thickness measurement, is 0.02 mm/year.
5:5 Describe and explain how the corrosion rate of steel depends on temperature
in the following systems:
(a) Open system and equilibrium between water and atmosphere
(b) Closed system (for instance a boiler circuit).
5:6 Consider the following statement: corrosion occurs if the sum of the moduli
of anodic and cathodic overvoltages exceeds the driving voltage (i.e., the
difference between equilibrium potentials of cathodic and anodic reactions).
Do you agree with this statement?
5:7 Which parameter would you consider necessary to draw the anodic curve for
an active, low melting temperature metal? And for a high melting temper-
ature metal?
5:8 Which parameter would you consider necessary to draw the cathodic curve
when only activation polarization applies? And when there is a concentration
polarization such as in the case of oxygen reduction?
5:9 Which are the parameters you must know to draw the anodic curve of an
active-passive metal?
5:10 Draw an anodic polarization curve for an active–passive metal. Define and
indicate on the figure all characteristic potentials, potential regions and
current densities.
Alessandro Volta and the Ohm’s Law

In the letter sent to Van Marum (22nd June 1802 4), Volta showed that, not
only he had clearly identified the physical factors that govern the circulation
of current in the pile (i.e. the tension, the current and the conductivity), but
also that he knew the quantitative relationship that linked them. In the same
letter, Volta also described the principle of the first Faraday law (see box in
Chap. 2).
In the best-known passage, that we quote here in the original text, is set out
the Law that Ohm was to deduce more than twenty years later, exactly as we
state it today.
«La rapidité de courant électrique est in raison composée de la tension
électrique et de la liberté ou facilité du passage dans toutes le parties de la
chaine ou cercle». («We can conclude that the speed of the electrical current
and consequently the strength of the shock felt is in proportion to the elec-
trical tension and to the freedom or ease of passage through all the parts of the
chain or circuit»).
To demonstrate how clear in Volta’s mind were the laws governing the
functioning of galvanic chains, we quote another passage from the same
letter.
«The electrical tension corresponds exactly, as our electrometric experi-
ments demonstrate, to the number of metallic pairs of the pile, placed in a
convenient order, at the rate of about 1/60 of a degree on my leaf-electrometer
for each pair, if they are made of copper and zinc. The ease of passage of the
electrical fluid depends on the permeability or the conductive capacity of the
moistened disks made of pasteboard, cloth or similar material, interposed
between the metallic pairs. Thus, assuming that the pile is formed of 120
pairs, it will always give a reading of 2 degrees on my electrometer, and will
also charge to 2 degrees a Leyden jar and a battery of any size, whether the
disks are rather dry or very wet, whether they are large or small, whether they
are steeped in pure water or a saline solution, etc.
It will simply take the current a little longer to traverse these disks when
pure water is used, and the smaller and drier these disks are. So, this delay,
this decrease in speed of the current means that the shock given by the pile
will likewise be less strong and either imperceptible or nonexistent.
Let's provide another example with this pile of 120 pairs: are the inter-
posed pasteboard disks about one inch in diameter and not very moist? No
noticeable shock will be obtained; nevertheless, it will charge the electrom-
eter to 2 degrees, and in a few seconds it will charge to 2 degrees a battery
which, thus charged, will provide a good shock. Now, let the interposed
4
The letter is part of Volta’s correspondence with the Dutch physics Van Marum, who has a
powerful scrubbing electric machine in Rotterdam. Unfortunately, Van Marum, unlike what he did
with previous letters, does not make it public. The letter was only disclosed in 1905 when
J. Bosscha published the correspondence Volta-Van Marum.
pasteboard disks be sufficiently moistened with pure water: the electrical

tension will still be 2 degrees but a weak shock will be felt beginning from the
20th pair.
Substituting the small pasteboard disks of about 1 inch in diameter with
others of 8 or 10 inches which are well moistened with pure water (and so
large metal plates are also used), the shock will be considerably stronger and
already perceptible at the sixth or seventh pair: even so, the electrical tension
has not increased; the larger size of the moistened disks has merely facilitated
the passage of electrical fluid. Next, let small pasteboard disks be bathed in a
saline solution, preferably ammonium muriate, a much less imperfect con-
ductor than pure water (and so small metal plates are also used): an incom-
parably greater and almost unbearable shock will be obtained, even though
the electrical tension is still 2 degrees, and a barely perceptible shock will be
felt at the third or even second pair. Finally let the large disks be soaked in
this same saline solution, and interposed between the large metallic pairs:
nothing will be gained in electrical tension, which will still be 2 degrees for
120 of these pairs, but much will gained in the speed of the current, that finds
the greatest ease of passage across these large and very good conductors. And
from here we go on to the marvellous effects obtained from the scintillation
and fusion of wires and metallic sheets subjected to this current, created from
just a small number of these pairs, and to the most amazing results that you
have achieved with a device of 200 pairs. But why does the shock, which
heretofore had gained in strength thanks to the more complete soaking with
water, to a greater extension of the disk surface soaked in this water, and
above all to the substitution of water with a good saline solution, gain nothing
or almost nothing more from the great size given to the disks soaked in this
same liquid, while the speed of the electric current increases because of this,
to the point at which it produces the fusions referred to? I explained this
problem to you in my letter from Geneva, and I discussed it more thoroughly
in a continuation of the memoir that I read to the Institute of Paris, only the
first part of which was published in the Annales de Chimie, and the remainder
will not be late in coming.
For the time being, I need only remind you that when one wants to prove a
shock, the body of the man is inserted in the circuit and the longer is his body
and the thinner his arms, the worse a conductor he will be, and he will be far
less permeable to the electrical fluid than the disks of the pile soaked in salt
water; the man’s body, I say, greatly slows the electric current, which in this
case is no longer capable of melting the metallic wires which are closed in a
circuit by the man, who touches one end of the pile with one hand, and the
opposite end with the other hand. I believe that the shock gains in strength as
the electrical fluid passing through the moistened disks of the pile encounters
less resistance, just as long, however, as the obstacle is greater than that of the
human body that must be crossed. But when the greatest obstacle is the man’s
body, and it is the body which limits the speed of the current, this speed
cannot be increased by further facilitating the current path in other parts of the
circuit, namely in the moistened disks.
Pietro Pedeferri, Pianeta Inossidabili, 4, 2002.
Bibliography
Bianchi G, Mussini T (1976) Elettrochimica. Masson Italia, Milano

Bianchi G, Mussini T (1993) Fondamenti di elettrochimica: teoria ed applicazioni. Masson Italia,
Milano
Lazzari L (2017) Engineering tools for corrosion. Design and diagnosis. In: European federation of
corrosion (EFC) series, vol 68. Woodhead Publishing, London, UK
Milano (in Italian)
Pourbaix M (1973) Lectures on electrochemical corrosion. Plenum Press
Shreir LL, Jarman RA, Burstein GT (1994) Corrosion. Butterworth-Heinemann, London, UK
Chapter 6
Evans Diagrams
Jupiter, father and king, I hope that my weapon is put to rest

and falls apart with rust.
And that nobody tries to hurt a peace-lover like me!
Orazio, Serm., 2, 1, 43
Abstract This chapter deals with the potential-current density diagrams, also called
Evans diagrams, which relate the variation of potential of a reaction—either anodic or
cathodic—with the current density exchanged in the process, starting from its equi-
librium potential in the corresponding environmental conditions. These diagrams
allow to identify the corrosion working conditions, Ecorr and icorr, where the anodic
and cathodic processes proceed with the same rate. The cases of active and active–
passive metals are described. Ohmic drop can also be represented on the diagram,
modifying corrosion rate. Both corrosion conditions and the imposition of a polar-
ization are discussed with reference to the modification of the electrode working
condition that they cause. Finally, experimental polarisation curves are introduced.

https://doi.org/10.1007/978-3-319-97625-9_6
104 6 Evans Diagrams
6.1 Introduction
When corrosion occurs at the surface of a metal, two electrochemical processes take
place, an anodic and a cathodic process, each one characterized by a different
equilibrium potential. The potential of the metal, called corrosion potential, Ecorr,
which can be easily measured, is necessarily intermediate between the two equi-
librium potentials. At this potential, anodic and cathodic processes proceed with the
same rate called corrosion current or corrosion current density, icorr, when referred
to a unitary surface area (Fig. 6.1).
The potential-current density (E − log i) diagram that shows how potential
changes as the current density of each process (anodic and cathodic) varies, hence
identifying corrosion working conditions, is called the Evans diagram. It is named
in honour of the English scientist Ulick Richardson Evans (1889–1980) who had
first proposed it.
6.2 Evans Diagrams of Active Metals
Let’s consider the Evans diagram shown in Fig. 6.2 for zinc corrosion in an
oxygen-free acidic solution. The processes that take place at the surface of zinc are:
Zn ! Zn2 þ þ 2e ð6:1Þ
2H þ þ 2e ! H2 ð6:2Þ
E
i0,H
Eeq,H 2
2
2H +
+2
e- c
H
2
Ecorr
-
e
2+ +2
Zn a
Eeq,Zn Zn
i0,Zn
icorr log i (mA/m2)

10-9 10-6 10-3
Fig. 6.2 Evans diagram of zinc in acid solution

6.2 Evans Diagrams of Active Metals 105
This diagram summarizes that:

• The corrosion condition, corresponding to Ecorr and icorr, is identified by the
crossing point of the characteristic overvoltage curves of the two processes
• The corrosion current density, icorr, is determined by the condition at which the
available driving voltage, DE, equals the sum of dissipations—or absolute
values of overvoltage—taking place at the anode and the cathode, ηa and ηc:
DE ¼ Eeq;c Eeq;a ¼ Eeq;H2 Eeq;Zn ¼ ga þ jgc j ð6:3Þ
where Eeq,c is the equilibrium potential, of the cathodic process (hydrogen evolu-
tion, Eeq;H2 ); Eeq,a is the equilibrium potential of zinc dissolution, Eeq,Zn. The ohmic
drop in the solution, as well as in the metal, is negligible
• The free corrosion potential, Ecorr, is closer to the cathodic equilibrium potential
when dissipations take place mainly at the anode. The opposite occurs when
dissipations prevail at the cathode.
Evans diagrams are very useful to illustrate the influence on the corrosion current
density, icorr, and the corrosion potential, Ecorr, of the following factors:
• Figure 6.3 shows the influence of the oxidizing power. As it increases, both the
potential and the corrosion rate increase. For example, with a 60 mV/decade
slope of anodic overvoltage, an increase in corrosion potential by 120 mV, due
to a more oxidizing cathodic process, cause the corrosion rate to increase by two
orders of magnitude
er
g pow
d izin e
-
oxy z+ +z
ng M
re asi
Ecorr,3 Inc M
Ecorr,2
Ecorr,1
icorr,1 icorr,2 icorr,3 log i
Fig. 6.3 Corrosion conditions of an active metal: influence of the oxidizing power
• Figure 6.4 shows the influence of the exchange current density, i0, of the
cathodic process. As it decreases, the corrosion rate is also lowered because the
cathodic overvoltage increases
• Figure 6.5 shows the influence of the oxygen limiting current density, iL. As the
agitation or the fluid velocity of the electrolyte increases, both the corrosion
potential and the corrosion rate increase.
Figure 5.16 of previous chapter, illustrates the cathodic curves of five cathodic
processes with different oxidizing power, namely: ① hydrogen evolution; ②, ③
oxygen reduction for two different concentrations of oxygen; ④, ⑤ high oxidizing
power processes, for example, reduction of chromates or reduction of ferric ions to
ferrous ones. When overlapping these five cathodic curves on the anodic curve of
an active–passive metal, as shown in Fig. 6.6, the resulting corrosion rate varies.
For instance:
• In the absence of oxygen or other oxidizing species, hydrogen evolution is the
only possible cathodic process; accordingly, the corrosion condition is repre-
sented by point A as the intersection of the anodic curve, active region, and
cathodic curve ①
• In the presence of oxygen the cathodic process is given by curve ②. Two
corrosion conditions can arise, as established by intersection points B and C: if
metal is active when immersed in the solution, corrosion condition is B; con-
versely, if metal is previously passivated and then immersed in the solution, it
works stably in point C. The intersection at Flade potential is disregarded since
it does not represent any real corrosion condition
• By increasing oxygen content or turbulence of the solution, the oxygen limiting
current density, iL, can increase so significantly that the cathodic curve (curve
③) can intersect the anodic curve in the passive interval only (point D). It is
i0,H i0,H
Eeq,H 2-Zn/Hg 2-Zn comm
2
2H + 2H +
+2 +2
e- e-
H H
2 2
Ecorr,Zn comm
Ecorr,Zn/Hg -
e
2+ +2
Zn
Zn
Eeq,Zn
i0,Zn
log i (mA/m2)
10-9 10-6 10-3 icorr,Zn/Hg icorr,Zn comm
Fig. 6.4 Corrosion conditions of an active metal: influence of exchange current density, i0,
(amalgamated and commercial zinc in acidic solution)
6.2 Evans Diagrams of Active Metals 107
O +
2 2H
2 O + 4e -
4OH -
Increasing agitation
Ecorr,3
Ecorr,2
Ecorr,1 -
2+ + 4e
2M
2M
iL,1 iL,2 iL,3 log i
Fig. 6.5 Corrosion conditions of an active metal in an aerated solution: influence of agitation on
iL
Fig. 6.6 Possible corrosion E (V SHE)

conditions of an active–
passive metal
1.6
F
5
1.2
E
0.8 D
4
0.4 C
2
3
0 1
B
10 102 103
log i (mA/m2)
important to compare the two passive conditions indicated by C and D. Both are
stable from the electrochemical point of view, but they are not equivalent from
an engineering perspective. In fact, in the first case, if the protective film is
locally damaged, for example, mechanically, the metal inside becomes active
(point B); instead, in the second case, the passive film heals spontaneously after
local breakdown (point D)
• In the presence of strong oxidizing species (curve ④) the corrosion potential
shifts to higher values, while remaining within the passivity range (point E)
• Corrosion occurs (point F) in the presence of stronger oxidizing species that are
able to bring the material in the transpassive zone (curve ⑤).
6.3 Corrosion Conditions in the Presence

of an Ohmic Drop
In a low conductivity environment, when anodic and cathodic surfaces are sepa-
rated, the ohmic drop sensibly reduces the driving voltage and the corrosion current,
as stated by the following balance:
DE ¼ Eeq;c Eeq;a ¼ ga þ gc þ woh ¼ ga þ gc þ IR ¼ f ðI Þ ð6:4Þ
as summarized in Fig. 6.7. The galvanic chain of Fig. 6.8 facilitates the under-
standing of how to measure the ohmic drop, woh, in the electrolyte, as well as the
absolute values of electrode overvoltage, ηa and ηc. The ohmic drop, woh, can be
calculated by the first Ohm’s law, once the circulating current, I, and the electrolyte
electrical resistance, R, are known.
In the presence of an ohmic drop in the electrolyte, corrosion potential is not
uniquely defined, since it varies in the interval (Eeq,c + ηc) − (Eeq,a + ηa) so that
potential measurements depend on the reference electrode location: close to the
anode, to measure anode potential, Ea, and conversely close to the cathode, to
measure cathode potential, Ec. When a reference electrode is placed in between the
Eeq,c
C c
A a
Eeq,a
R IR
Icorr I
Fig. 6.7 Anodic and cathodic curves and ohmic drop in the electrolyte with constant resistance, R
6.3 Corrosion Conditions in the Presence of an Ohmic Drop 109
a IR c
Fig. 6.8 Principle of short circuited galvanic chain
anode and the cathode, an intermediate value is measured (between A and C of

Fig. 6.7).
The Evans diagram helps determine how driving voltage, DE = Eeq,c − Eeq,a, is
dissipated by examining the shape of overvoltage curves. Schematic cases depicted
in Fig. 6.9 show which dissipation contribution determines the corrosion rate and
the type of control: cathodic, anodic and ohmic, respectively.
(a) E (b) E (c) E

Ecorr
Ecorr Ecorr
icorr log i icorr log i icorr log i
(d) E (e) E
Ecorr
Ec
IR
Ea
icorr log i icorr log i
Fig. 6.9 Different types of kinetic control of a corrosion process: a cathodic overvoltage; b anodic
overvoltage; c cathodic diffusion control; d anodic passivation; e ohmic control
6.4 Multiple Cathodic Processes
So far, corrosion processes have dealt with a single anodic and cathodic process;
when multiple processes take place, the mixed-potential theory applies, which states
that:
X X
Ia þ Ic ¼ 0 ð6:5Þ
since there cannot be an accumulation of electric charges. Assuming the ohmic drop
to be negligible, the corrosion potential is again the one at which Eq. 6.5 fits, i.e.,
where resulting anodic and cathodic curves cross. Figure 6.10 illustrates the cor-
rosion condition when two cathodic processes take place: reduction of ferric ions
and hydrogen evolution. Resulting curves are obtained by the following procedures
based on the Eq. 6.5:
• The anodic curve starts from the lowest potential, i.e., the equilibrium potential
of metal, M, and only fits metal oxidation. In principle, there could be the anodic
process of hydrogen oxidation if hydrogen gas was present at the metal surface.
The dashed line is the resulting anodic curve (sum of two processes)
• The cathodic curve starts from the highest potential, i.e., the reduction of ferric
ions, then followed by the hydrogen evolution when hydrogen equilibrium
potential is reached; metal deposition could also follow if metal ions were
present in the solution. The dashed line is the resulting cathodic curve (sum of
three processes).
E
-
3+ +e
Eeq,Fe3+/Fe2+ 2+ Fe
Fe
Global
Fe 3+ anodic
+e- - curve
+ + 2e
Fe 2+ 2H
H2 -
Eeq,H + e
2 M +
M
Ecorr
Global
2H + cathodic
Eeq,M +2 curve
e-
M ++ e - M
H
2
i0,Fe3+/Fe2+ i0,M i0,H log i

2
Fig. 6.10 Corrosion condition of a metal when cathodic processes are hydrogen evolution and
reduction of ferric ions
6.4 Multiple Cathodic Processes 111
Corrosion potential and corrosion rate are given by the crossing point of resulting
anodic and cathodic curves.
6.5 Imposed Polarization
Let’s consider a freely corroding metal, M, for example iron in an acidic solution.
On its surface, both anodic and cathodic processes take place at the same rate, icorr;
the anodic process is iron dissolution (Fe ! Fe2+ + 2e−) and the complementary
cathodic process is hydrogen evolution (2H++ 2e− ! H2). The corrosion potential,
Ecorr, is then given by the intersection point of the two characteristics, which follow
Tafel law (Fig. 6.11).
Let’s now consider what happens if an external current, ie, is applied in the
anodic or cathodic direction. The metal potential shifts to a potential higher, E1, or
lower, E2, than Ecorr, respectively. The anodic process rate, i.e., the dissolution of
iron, ia,Fe, and the cathodic process rate, i.e., hydrogen evolution, ic;H2 , change from
corrosion current density, icorr, according to the electro-neutrality condition, as
stated by the following relationships:
ic;H2 ¼ ia;Fe þ ie for a cathodic polarization ð6:6Þ
and
ia;Fe ¼ ic;H2 þ ie for a anodic polarization ð6:7Þ
If a cathodic external current, ie, is applied, so that iron is cathodically polarized, the
potential becomes more negative or less noble, and shifts to the potential value E2
Eeq,H
2
polarization
More noble
Anodic
ie = ia,Fe - ic,H 1
E1 2
Ecorr ia,Fe
2
E2 ic,H
polarization
ie = ic,H - ia,Fe 2
Less noble
Cathodic
Eeq,Fe
i0,Fe i0,H ia,Fe icorr ic,H log i

2 2
Fig. 6.11 Potential-current density plot, E-logi, in the presence of cathodic or anodic polarization
as a result of the application of an external current
where the difference between the cathodic process (hydrogen evolution) rate and the
anodic oxidation rate of the metal is given by:
ie ¼ ic;H2 ia;Fe ð6:8Þ
Therefore, the corrosion rate of iron is now identified by point ②.

Similarly, if an anodic external current, ie, is applied, so that iron is anodically
polarized, its potential becomes less negative or more noble, then reaching potential
E1 to satisfy the relationship:
ie ¼ ia;Fe ic;H2 ð6:9Þ
Therefore, the corrosion rate of iron is now identified by point ①.

In conclusion, by applying an external current, polarization is obtained in
accordance with the current direction: anodic (i.e., E > Ecorr) or cathodic (i.e.,
E < Ecorr) causing an increase or a decrease of the corrosion rate, respectively.
6.6 Experimental Polarization Curves
Anodic and cathodic curves that have been described so far are not the ones that are
obtained experimentally, although derived from them. In laboratory testing, it is not
possible to separately measure the different anodic or cathodic currents involved,
but only the current a metal coupon can exchange with the electrolyte; indeed, what
can be measured is only the algebraic difference of the two currents, i.e.,
I = ±(ia − ic)S, where S is the coupon surface area.
Eeq,H
2
Ecorr
Eeq,M
Limiting current density

of hydrogen evolution iL,H
2
i0, M i0,H iL,H log i

2/M 2
Fig. 6.12 Theoretical (dotted lines) and experimental polarization curves of an active metal in
oxygen-free acidic solution
6.6 Experimental Polarization Curves 113
Figure 6.12 shows experimental curves and theoretical ones (dotted lines) for an
active metal exposed to an oxygen-free acidic solution. Curves overlap when one of
the two practically zeros, as easily shown by the relationship: I = ±(ia − ic)S when
ia or ic fades. The corrosion rate is given by the crossing point of extrapolated lines
from the Tafel region of measured curves. For comparison, experimental and the-
oretical curves (dotted lines) for an active metal exposed to an aerated acidic
solution are reported in Fig. 6.13, where curves obtained in aerated neutral solution
are plotted in Fig. 6.14.
Eeq,O
2
Eeq,H
2
Ecorr
Eeq,M
i0,H i0,M i0,O log i
2/M 2/M
Fig. 6.13 Theoretical (dotted lines) and experimental polarization curves of an active metal as
iron in aerated acidic solution
Eeq,O
2
Ecorr
Eeq,M
Eeq,H
2
i0,M i0,H i0,O /M log i

2/M 2
Fig. 6.14 Theoretical (dotted lines) and experimental polarization curves of an active noble metal
as copper in aerated neutral solution
Figures 6.15, 6.16 and 6.17 show experimental curves and theoretical ones
(dotted lines) for an active–passive metal when the cathodic process is more or less
noble, then ranging from an active to a transpassive region. To obtain theoretical
polarization curves from experimental plots, automatically gained by modern
potentiostats, it must be predicted how a metal will behave when exposed to a
particular environment.
Eeq,H
2
Ecorr
Eeq,M
i0,H i0,M log i

2/M
Fig. 6.15 Theoretical (dotted lines) and experimental polarization curves of an active–passive
metal in oxygen-free neutral solution
Eeq,O
2
Ecorr
Eeq,H
2
Eeq,M
i0,O i0,M i0,H log i

2/M 2/M
metal in aerated neutral solution
6.6 Experimental Polarization Curves 115
Eeq,H
2
Ecorr
Eeq,M
i0,H2/Me i0,M log i
metal in oxygen-free acidic solution
6:1 Draw the cathodic polarization curve in neutral aerated stagnant solution
(T 25 °C; pH 7; 6 mg/L oxygen) from the equilibrium potential of oxygen
reduction to −1.2 V SHE. Consider proper values of the exchange current
density and Tafel slope.
6:2 Draw Evans diagrams and evaluate the corrosion potential and the corrosion
rate for the following corrosion systems (consider the ohmic drop as
negligible):
• Copper in seawater assuming that copper is active
• As above, instead assuming that copper passivates
• Iron (mild steel) in fresh water assuming iron is active
• As above, instead assuming that iron (as in stainless steel) passivates
• Copper in deaerated neutral soil
• Stainless steel in neutral deaerated freshwater
• As above, in deaerated seawater.
6:3 Draw the Evans diagram of iron (steel) in neutral aerated solution (T 40 °C;
pH 7; v 2 m/s; 5 mg/L oxygen). Determine the corrosion potential and cor-
rosion rate (in lm/y). Calculate anodic and cathodic overvoltages. Consider
proper values of the exchange current density and Tafel slope.
6:4 Draw Evans diagrams of iron in a NaCl solution at pH 3 in two conditions:
• Aerated solution (air bubbling)
• De-aerated (oxygen free)
• Determine the corrosion current density and specify the cathodic pro-
cesses in the two conditions. [Consider exchange current density, i0, for
Fe: 1 mA/m2; H+: 1 mA/m2; O2: 0.5 mA/m2; oxygen limiting current
density, iL, 250 mA/m2.]
6:5 Provide an example of each type of kinetic control of a corrosion process:
(a) cathodic overvoltage; (b) anodic overvoltage; (c) cathodic diffusion
control; (d) anodic passivation; (e) ohmic control
6:6 What are the relationships between Ia, Ic, Ec, Ea, ia, ic in a free corrosion
condition in the presence of ohmic drop?
6:7 Draw Evans diagrams in the following case studies.
a. Iron in 70% (15 mol/L) nitric acid, spontaneous passivation occurs (case
I)
b. Iron in 20% (4 mol/L) nitric acid, immersed as active (case II)
c. Iron in 20% (4 mol/L) nitric acid, immersed as passive (previously
immersed in 70% nitric acid (case III)
d. Iron in 0.1 N = 0.1 mol/L nitric acid (case IV).
Cathodic reaction is: HNO3 + 3H+ + 3e− = NO + 2H2O, with standard
reversible potential E0 = 0.96 V (SHE). (For simplicity, assume that NO
partial pressure is unitary). Assume same exchange current density and
same Tafel slope.
Which state do you think aluminium and chromium would adopt if they
were exposed to dilute acid as in case IV? Which state would copper and
nickel adopt?
6:8 Consider the experimental polarization curve of an active metal in
oxygen-free acidic solution reported in Fig. 6.12. Why the curve deviates
from the theoretical one?
6:9 Consider the experimental polarization curve of an active metal in
oxygen-free acidic solution reported in Fig. 6.12. At which potential (with
respect to free corrosion condition) Tafel slope of hydrogen evolution should
be determined in your opinion?
6:10. With reference to Figs. 6.15, 6.16 and 6.17, please describe
metal-to-environment characteristics deducible from the shape of the
experimental/theoretical curve.
Ulick Richardson Evans

Evans was born in Wimbledon in 1889 and was educated at Marlborough
College, 1902–1907, and King’s College, Cambridge, 1907–1911, where he
read for the Natural Sciences Tripos, specializing in chemistry. He then began
research on electrochemistry at Wiesbaden and London, and after the First
World War, he returned to Cambridge where he spent the rest of his life
researching and writing prolifically on corrosion and the oxidation of metals.
U. R. Evans was described in the Biographical Memoirs of Fellows of the

Royal Society as the “Father of the modern science of corrosion and pro-
tection of metals”. His major contribution to the subject involved placing the
electrochemical nature of corrosion on a firm foundation. His first paper in
this area was published in 1923, which was followed in 1924 by his book
“Corrosion of Metals”, the first text book devoted to the subject. He con-
tinued to publish research papers for the next 50 years, as well as updating his
classic text.
Excerpt from Ulick Richardson Evans, An Introduction to Metallic

Corrosion, Edward Arnold, London, UK, 1948.
The chronological sequence of scientific discovery is rarely the logical one.
To arrange the facts of metallic corrosion historically would conceal the true
interconnection existing between them, and thus deprive them of significance.
Nevertheless, in view of the prevailing interest in the History of Science,
many readers may welcome a short narrative showing how knowledge of the
subject discussed in this book has grown. The note which follows should
serve to indicate some names and dates associated with the advance of
understanding, but it must be remembered that the credit for any particular
discovery cannot be assigned to a single year or to a particular person. If a
recent investigator is cited as the discoverer, objection may fairly be raised by
the quotation from older papers of passages which seem to contain the germ
of the idea; yet to allot the entire credit to early investigators may be unjust to
later ones, who have established as facts what had previously been mere
suggestions. At the Dawn of History, the first metals to be used were those
which were either found native, or could easily be reduced to the elementary
state; such metals do not readily pass into the combined state, and their
corrosion can have raised no serious problems.
But with the introduction of iron, the problem of its corrosion must have
presented itself, although it is an undoubted fact that some of the iron pro-
duced in Antiquity is to-day more free from corrosion than much of that
manufactured in later years. This may have been due partly to the fact that
iron reduced with charcoal contained less sulphur than modern steel, but it
may also be connected with the absence of sulphur compounds from the air in
the days before coal was adopted as a fuel; for it is often the conditions of
early exposure which determine the life of metal-work. Whatever the cause,
ancient iron has in some cases remained in surprisingly good condition for
many centuries; the Delhi Pillar is the example which has excited most
interest, but others could be quoted.
Bibliography

Hoar TP (1961) Electrochemical principles of the corrosion and protection of metals. J Appl Chem
11:121–130
Hoar TP, Mears DC, Rothwell GP (1965) The relationships between anodic passivity, brightening
and pitting. Corros Sci 5:279–289
Wagner C, Traud W (1938) On the interpretation of corrosion processes through the superposition
of electrochemical partial processes and on the potential of mixed electrodes. Z Electrochem
44:391
Chapter 7
Corrosion Factors
In corrosion science the number of affecting factors is

often high and rarely easy to rank.
Roberto Piontelli (1909–1971) Italian eminent electrochemist
Abstract Corrosion processes involve metal and environment properties through a

variety of factors. From the metal side, chemical composition and microstructure
play a major role. Chemical composition is also fundamental to define the elec-
trolyte aggressiveness, together with its pH, temperature and the possible presence

https://doi.org/10.1007/978-3-319-97625-9_7
120 7 Corrosion Factors
of bacteria. Other relevant operating conditions are pressure, fluid velocity, pres-
ence of mechanical stresses and exposure time. Even though is not easy to depict a
general trend on how these factors influence corrosion, a rational approach is
proposed for the interpretation, based on thermodynamics (equilibrium potential)
and kinetics (Evans diagrams).
7.1 Metal Affecting Factors
Various factors related to metals influence corrosion processes:

• Composition, presence of impurities, phases and constituents
• Crystalline structure, constituent phases, lattice defects, surface finishing grain
boundary precipitates and mechanical stresses (Fig. 7.1).
In the following, also the influence of modification of chemical composition on
surface is considered.
7.1.1 Modification of Metal Surface Composition
Let’s consider an alloy consisting of two metals M and N exposed to an electrolyte

in which Mz+ and Nz’+ ions are present. Anodic processes are the following:
M ! Mz þ þ ze ð7:1Þ
0
þ
N ! Nz þ z 0 e ð7:2Þ
Equilibrium potential of each metal is respectively:

RT
M
Eeq ¼ EM
0
þ ln½aMz þ ð7:3Þ
zF
RT h i
EN
eq ¼ E 0N þ 0 ln aNz0 þ ð7:4Þ
zF
The two anodic processes take place at an equilibrium condition, which implies the
same potential:
M
Eeq ¼ Eeq
N
ð7:5Þ
Assuming same valence, i.e., z = z′, it results that:
RT ½aNz þ
0
EM EN0 ¼ ln ð7:6Þ
zF ½aMz þ
7.1 Metal Affecting Factors 121
Fig. 7.2 Anodic polarization E

curve of Fe and Cr in
sulphuric acid 1 N
3
Fe
2
Cr
1
log i
It results that differential corrosion of the two metals occurs until equilibrium
condition is reached, given by the above relationship, through the consumption of
less noble metal. For example, for copper–zinc alloys the difference between
standard potentials is 1.1 V. Therefore, Zn to Cu ion concentration ratio at equi-
librium is of the order of 1/10−37, hence, only Zn corrodes.
Kinetics may change the practical behaviour. Let’s consider an iron/chromium
alloy, which forms a solid solution. To predict corrosion in sulphuric acid, anodic
overvoltage can be considered, as shown in Fig. 7.2. In the potential interval ①,
chromium is active and less noble, then corroding; in interval ③, chromium is
transpassive and less noble, then again corroding. Conversely, in interval ②, the
passivity current of chromium is much lower than that of iron, therefore, the iron
dissolution rate is higher; thus, accordingly, the alloy surface enriches in chromium,
thereby strengthening passivity.
7.1.2 Nobility by Alloying
Corrosion resistance can be improved by changing the metal composition in order

to increase nobility, or increase the overvoltage of cathodic and anodic processes, as
discussed below. This paragraph does not address other interventions to increase
resistance to localized corrosion, such as pitting, intergranular, SCC, hydrogen
damage and flow-induced corrosion that are considered elsewhere.
The addition of a more noble element increases the nobility of an alloy. An example
is Monel, a nickel-based alloy containing about 30% copper, which increases the
equilibrium potential from −0.25 V SHE of pure nickel to about −0.07 V SHE, since
copper is more noble. Prediction of this alloying effect is given by the calculation of
equilibrium potential as the weighted average. For example, the standard potential of
a-brass, a solid solution copper–zinc alloy with composition about 70% Cu and 30%
Zn, standard potential is: E0a-brass ≅ +0.34 0.7 − 0.76 0.3 ≅ + 0.01 V SHE.
Table 7.1 Corrosion rate of Fe content (%) Corrosion rate

commercial aluminium as a
(g/m2 d) (mm/y)
function of iron content in
20% HCl solution at 26 °C 0.002 6 0.8 (1 µm/d)
0.01 112 15 (1 µm/h)
0.03 6500 880 (1 µm/min)
0.12 36,000 4,860 (10 µm/min)
0.8 190,000 25,690 (1 µm/s)
7.1.3 Overvoltage of Cathodic Processes
Metal composition strongly influences the overvoltage of hydrogen evolution in

acidic solutions for normal or intermediate metals. The addition of impurities or
noble precipitates having low hydrogen overvoltage, as in the case of Al–Cu alloys
(3–5% Cu) used in the aerospace industry, causes a localized attack when inter-
metallic CuAl2 precipitates at grain boundaries. Zn, Al and Mg alloys exhibit same
behaviour with high melting temperature impurities with a low hydrogen over-
voltage (Table 7.1); conversely, to reduce corrosion, high hydrogen overvoltage
elements like Cd, Sn or Hg, even if only on the surface, as obtained by metal
displacement, should be added.
7.1.4 Cathodic Alloying
In the 1950s, Nikon D. Tomashov (1905–1990) proposed an elegant and intriguing

method for setting up an anodic protection effect (ref. Chap. 19) on titanium by
adding a noble metal to form a solid solution. This is known in literature as “noble-
metal alloying”, and in the following, it is called cathodic alloying. Figure 7.3
shows the passivating effect of the addition of platinum on titanium in an acidic,
oxygen-free solution. The galvanic effect is achieved by adding a small amount of
Pd, 0.5% max, in a solid solution of titanium, which brings free-corrosion potential
in the passive interval even in an oxygen-free solution. Figure 7.3 shows how
cathodic alloying works: by reducing the overvoltage of hydrogen evolution
through the higher exchange current density of Pt or Pd, the critical passivation
current density is also exceeded. This is called anodic protection effect by cathodic
alloying and is applicable if:
• The base metal is an active–passive one
• Equilibrium potential of hydrogen evolution, Eeq;H2 , is more noble than the
passivation potential, Ep, of the base metal
• Cathodic alloying elements are more noble than the base metal and they form a
solid solution.
Based on the above requirements, titanium and chromium alloys, for instance
stainless steels, are possible candidates with Pt and Pd.
7.1 Metal Affecting Factors 123
Eeq,H
2
2
Ti Cathodic
global
Ep characteristic
Epp
1
Ti/Pd
icorr,Ti/Pd icorr,Ti log i
Fig. 7.3 Anodic protection effect by cathodic alloying with Pd (or Pt)
E
Eeq,H
2
2
Ecorr Cathodic
4 3 global
H characteristic
2 on
Ta
1
H
2 on
Pt
iH iH icorr,Ta log i
2,Ta 2,Pt
Fig. 7.4 Comparison between pure tantalum and Pt-alloyed tantalum
Similar cathodic alloying is applied to tantalum to avoid hydrogen-related

damage instead of reducing corrosion. Ta suffers from hydrogen embrittlement (see
Chap. 14) when exposed to highly corrosive environments in which the corrosion
rate is considered acceptable, for instance less than 10 lm/y. By alloying with Pt,
the corrosion condition moves from ① to ② as shown in Fig. 7.4, so that
molecular hydrogen evolution takes place on Pt, mainly (point ③), while the
corrosion rate of Ta remains unchanged (i.e., passivity current density) and the
hydrogen evolution rate on Ta fades (from ① to ④), then avoiding hydrogen
embrittlement. A small Pt content is sufficient because of the huge difference in the
exchange current density, i0,H, for hydrogen evolution on Ta versus Pt.
Fig. 7.5 Silicon content E (V SHE)

influence on the anodic
behaviour of iron in sulfuric 3 20% Si
acid 1 N at 25 °C 16% Si 12% Si
8% Si
2
Mild steel
1 Alloys Fe-Si
in H2SO4 1 N
20% Si
0 8% Si
16% Si 12% Si
-1
1 3 5
i (A/m2)
7.1.5 Reduction of Anodic Areas
In a non-homogeneous metal, the anodic component should be dispersed in a

cathodic matrix so that after the initial rapid corrosion attack, the surface enriches
with the cathodic component or passivating element. For example, this effect occurs
in grey cast iron where after an initial corrosion of iron, which is anodic, the surface
enriches with silicon, enhancing passivation. Also selective corrosion attack may
lead to a similar effect as in the case of brass on which zinc corrodes initially hence
the surface enriches with copper (more noble and with passivating propriety). The
opposite does not work, because a cathodic component dispersed in an anodic
matrix cannot spread on the surface as the anodic component continues corroding.
7.1.6 Passivation Induced by Alloying
When adding a component easy to passivate to an alloy, the alloy does the same.
Two typical examples are the addition of chromium or silicon to iron. Figure 7.5
illustrates the effect of the addition of Si on steel in sulphuric acid. Figure 7.6 shows
the influence of the addition of some elements to iron on susceptible parameters, as
ip, icp, Epp, Ep e Etr; the influence depends on content.
7.2 Environment Affecting Factors
From a corrosion viewpoint, most relevant environment-related properties, either in

bulk or on a metal surface, are:
• Conductivity (determined by total dissolved solids)
• pH
7.2 Environment Affecting Factors 125
Fig. 7.6 Influence of E

alloying elements on the
anodic characteristic of iron in
sulfuric acid solution 1 N at Etr Cr, Mo
25 °C Ni, Si
Mo, V
Cr, Ni, W
Ep Cr
Ni
Epp Cr
Ni, Ti, Mo
Cr, Mo, V, Ti, Nb, Ni
ip icp log i
• Oxygen content
• Other oxidizing species (for instance chlorine)
• Bacteria.
Typically, acidity and oxygen content in bulk are important for sustaining the
cathodic process, while pH at metal surface determines the passivating tendency.
It is worth mentioning that some cathodic processes would be possible in
principle because of their noble potential, but exhibit very slow kinetics. These
processes are:
• SO42− + 4H++ 2e− ! H2SO3 + H2O with E° = +0.17 V SHE (in acidic
solutions)
• ClO4− + 2H++2e− ! ClO3− + H2O with E° = +1.19 V SHE (in acidic
solutions)
• 2NO2− + 3H2O + 4e− ! N2O + 6OH− with E° = +0.15 V SHE
• 2NO3− + 4H++2e− ! N2O4 + 2H2O with E° = +0.81 V SHE.
Although the reduction of NO2− is a less noble reaction than the reduction of NO3−,
it is kinetically more active.
7.2.1 Conductivity
An electrolyte has an electrical conductivity due to the presence of ions (anions and
cations) as a result of the dissociation of dissolved salts. For fresh water, in practice,
conductivity is a function of TDS (total dissolved solids) and temperature through
the following practical relationship (Lazzari 2017):

S 1 ð1 þ 0:02DT Þ TDSðg/LÞ
r ¼ ffi ð7:7Þ
m qðXmÞ 9
where TDS is total dissolved solid (g/L) and DT is temperature variation from 25 °C.
Conductivity has a direct influence on the corrosion rate, especially on localized
corrosion where a macrocell mechanism sets up: the higher the conductivity, the
higher the corrosion rate, provided a cathodic process is present.
7.2.2 pH
For various metals, the corrosion rate is strongly pH dependant as Fig. 7.7 shows.
Type a trend characterizes amphoteric metals such as Al, Zn, Pb and Sn, which
suffer corrosion either in acidic solutions (for instance, aluminium and zinc form
Al3+ and Zn2+ cations, respectively) or in alkaline solutions (aluminium and zinc
dissolve as AlO2−, and ZnO22− anions, respectively). The type b trend applies to
metals such as Fe, Ni, Co, Cr, Mn, which passivate in neutral or higher pH solu-
tions. Finally, the type c trend applies to noble metals, such as Au or Pt, which resist
corrosion in both acidic and alkaline solutions.
7.2.3 Differential Aeration
Evans’ experience helps illustrate the influence of non-homogeneous oxygenation.

A cell composed of two compartments, each hosting an iron or mild steel strip,
(a) (b) (c)

Crate
Crate
Crate
0 14 0 14 0 14
pH pH pH
Fig. 7.7 Trend of corrosion rate of metals with pH; a amphoteric metals (Al, Zn, Pb, Sn);
b metals passivating in alkali (Fe, Ni, Co, Cr, Mn); c noble metals (Au, Pt). Adapted from Speller
(1926) and Piontelli (1961)
communicating through a porous plug, is filled with a neutral solution (Fig. 7.8).
Oxygen and nitrogen bubble separately in each compartment. By connecting the
two strips by an ammeter, the current flows from the strip of the oxygenated
compartment (positive pole, cathode) to the other (negative pole, anode). The
cathodic strip, because of the alkalinity produced by the cathodic reaction (i.e.,
oxygen reduction) passivates, as shown in Fig. 7.9. Initial conditions, before the
short-circuiting of the two strips, are ① for a low oxygen zone and ② for a high
oxygen zone. After coupling: zone ① starts working as the anode (i.e., less noble
electrode) and zone ② as the cathode. Point ① moves to point ③ as the final stable
anodic corroding zone while point ② shifts to ④ passivating and becoming a stable
final cathodic zone for oxygen reduction.
By interchanging the two gas flows, corrosion reverses: the passivated one starts
corroding and the one that was corroding passivates. This type of corrosion, called
differential aeration, occurs where oxygen concentration zeros, such as under
deposits or in cavities, because the solution cannot be continuously replaced. It
often takes place on buried structures (pipings, tanks) where soil is characterized by
Fig. 7.8 Evans experiment Ammeter

of differential aeration O2 N2
A
Porous plug
Fig. 7.9 Evans diagram for E

differential aeration ① low
oxygen zone (initial); ② high
oxygen zone (initial); ③
anodic corroding zone (final)
④ cathodic zone (final)
ECATH 4
ΔE
EAN
Ehigh O2
3
Elow O2 2
1
log i
Low permeability High permeability

to O2 to O2
Pipeline Anodic zone Cathodic zone
Clay Sand
Fig. 7.10 Differential aeration corrosion on a buried structure in non-homogeneous soil
a different permeability to oxygen (Fig. 7.10): in zones where soil is less permeable
to oxygen (clayey soil) corrosion occurs, while aerated zones (sandy soil) behave as
a cathode.
Although not strictly a differential aeration, it is worth mentioning the case of so
called corrosion at liquid line, which occurs on a partially immersed metal or inside
partially empty pipes: corrosion attack localizes at the three-phase,
metal-electrolyte-air contact, i.e., at the liquid line, where oxygen is easily available
and corrosion products are less protective due to the non-homogeneous exposure
condition. Corrosion attack is more intensive when liquid height changes, for
example in frequently operated tanks because oxygen access is facilitated.
7.2.4 Salt Formation/Precipitation
The corrosion process leads to a production of metal ions at the anode and
hydroxyls at the cathode; accordingly, low solubility salts may precipitate on the
anode and the cathode if specific ions are present in the aggressive environment.
The following compounds may form:
• Soluble corrosion products, such as chlorides or alkali sulphates, which con-
tribute to increase corrosion rate through the lowering of electrolyte resistivity
and because there is no protection effect by the corrosion products being soluble
• Insoluble salts on the cathode, such as zinc, calcium and magnesium hydroxides
or basic salts, which contribute towards decreasing the corrosion rate by a
barrier effect
• Insoluble salts on the anode, such as phosphates and carbonates, which con-
tribute towards passivating the metal, and then contributing towards decreasing
the corrosion rate by passivation.
7.2.5 Cation Displacement
Cations present in the electrolyte can give rise to a corrosion attack because of:
• Self-displacement if metal cation concentration is not uniform
• Displacement, if noble metal cations are present.
Self-displacement occurs when metal ion concentration is not uniform (for
example, due to the presence of cracks, cavities or recesses, in which the solution
has concentrated). Metal potential is more positive where the solution is more
concentrated, therefore an electromotive force, EMF, sets up, given by:
RT C1
EMF ¼ DE ¼ EC1 EC2 ¼ ln ð7:8Þ
zF C2
where EC1 and EC2 are metal potential in the concentrated solution, C1, and in the
diluted one, C2, respectively, and z is cation valence. Accordingly, a current flows
from the diluted less noble (i.e., anodic) zone to the concentrated more noble (i.e.,
cathodic) zone. As illustrated in Fig. 7.11a, self-displacement shows the tendency
to fill a cavity rather than to deepen it. For comparison, Fig. 7.11b shows the
current path of a corrosion attack due to differential aeration: in this case, the cavity
is anodic.
A curious case of self-displacement occurs in concentrated solutions of heavy
metals, lead or tin, as they tend to stratify by gravity. For example, by dipping a
wire of lead in a stagnant concentrated solution of lead sulphamate or perchlorate,
where previously lead ions stratified (i.e., higher concentration at the bottom) an
attack occurs on the upper side where the solution is diluted, and metal deposition
takes place at the bottom where the solution is more concentrated. This phe-
nomenon, known for centuries, gives rise to attractive dendritic-type deposits called
by alchemists Saturn’s tree for lead and Diana’s tree in the case of tin. Given the
small available EMF, this phenomenon only occurs with normal metals, such as
lead and tin.
Displacement occurs when a metal, M, is immersed in a solution containing cations

of a more noble metal, N: according to thermodynamics, noble metal deposits
(cathodic reaction Nz+ + ze− = N) and those less noble dissolve (anodic reaction
M = Mz+ + ze−). This displacement reaction occurs easily for normal metals; for
example, cadmium displaces tin; cadmium and tin displace lead; cadmium, tin and
lead displace with mercury; aluminium can displace copper.
Instead, at least at room temperature, the displacement process of inert or
intermediate metals does not occur, even when a significant driving voltage is
available. For example, let’s consider the series zinc (E0Zn = −0.76 V SHE), nickel
(E0Ni = −0.25 V SHE) and copper (E0Cu = +0.34 V SHE). At standard conditions,
zinc should displace nickel and nickel should displace copper; instead, because of
overvoltage on nickel, displacement does not occur. In practice, nickel’s behaviour
is more noble with copper, thereby not displacing copper, and less noble than zinc,
(a) (b)
Fig. 7.11 Morphology of the attack caused by: a cation concentration cells; b differential aeration
thereby not being displaced by zinc. In short, in cation displacement, what matters
is practical nobility given by the expression:
RT aMz þ
E ¼ E0 þ ln gI¼0 ð7:9Þ
zF aM
ηI=0 is anodic (+) or cathodic (−) overvoltage at zero current, having the meaning
of a starting friction loss, which is negligible for normal metals while it can exceed
100 mV for inert ones; on the other hand, at elevated temperatures, displacement
reaction becomes possible since friction loss decreases.
In chemical plants, concerns about displacement reactions arise when ions of
mercury, silver or, more often, copper are present. Mercury forms from salts used as
catalysts as a result of cathodic reduction supporting the anodic process of iron
dissolution. Copper ions can form as copper or its alloys corrode in some parts of
the plant. Copper deposits on a less noble material, in particular, of aluminium
components where it triggers localized attacks by galvanic corrosion. In some
circumstances, copper can deposit by the effect of CP.
7.2.6 Microorganisms
Corrosion caused by microorganisms, called MIC, Microbiologically Induced

Corrosion, is often encountered in several industrial plants: production, transport
and storage of hydrocarbons; fire-fighting systems; water cooling circuits; sewage
treatment plants; marine and buried structures, beneath fouling or in clayey and
swampy soils.
The first step of this corrosion process is the formation of so-called biofilm,
which consists of microorganism colonies stuck on metal surfaces by self-produced
gel, which locally modifies pH and oxygen availability to enhance conditions for
bacteria to thrive. Biofilms are a few tens of microns thick, generally characterized
by two layers, where the inner layer, adherent to metal, is almost oxygen-free.
Bacteria can be divided into two families:
• Aerobic such as Cladosporium resinae, Thiobacillus thiooxydans, Thiobacillus
ferroxidans, Gallionella, Sidercapsa, Spheaerotilus, which lower pH thereby
promoting acid-related corrosion attacks
• Anaerobic as Desulfovibrio desulfuricans also called sulphate-reducing bacteria,
SRB.
Among aerobic bacteria, it is worth mentioning Cladosporium resinae that
causes corrosion of aluminium fuel tanks in the presence of condensate water by
lowering pH then causing aluminium passivity breakdown. Thiobacillus thiooxy-
dans and Thiobacillus ferroxidans are oxidizing bacteria, which oxidize sulphur,
sulphides and other sulphur containing compounds to give sulphuric acid at con-
centrations as high as 3%.
The most common anaerobic MIC takes place on carbon steels and low alloy
steels due to sulphate-reducing bacteria, SRB (Desulfovibrio desulfuricans,
Fig. 7.12), which catalyse the reduction of sulphates to sulphides in a local
oxygen-free condition and a sulphate content exceeding 100 ppm. This model was
firstly proposed by Von Wolzogen and Van der Vlugt (1934).
Frequent Case Study of MIC

It is often reported that MIC is the root cause of localized attacks on stainless
steels, typically in hydro-testing of piping and equipment. Caution should be
taken before attributing the cause of corrosion to MIC because the morphology
is very similar to the one in the absence of bacteria. Generally, there are two
possible scenarios: piping remained full after hydro-testing or was drained.
In the former, MIC would appear to be the only possible cause, since
corrosion was unexpected based on operating conditions (namely, low
chloride content in the water used for testing). In the latter, instead, if
Fig. 7.12 MIC mechanism Anaerobic

on carbon steel in the Localized corrosion on iron
presence of SRB (in anaerobic SBR
waters and soils) FeS S- + 4H O
2
Hydrogenase
enzyme
SO4- + 8H+ + 8e-
Fe2+
e-
drainage was not accurate, most likely the cause was pitting due to a local
increase of chloride concentration in stagnant water in the plant and high
oxygen availability from the entrapped air.
A Unified Model for MIC

MIC has been recognized as responsible for localized corrosion on either
active or active–passive metals. In both cases, a necessary condition is
required: the occurrence of a cathodic process.
For localized corrosion of active metals, typically carbon and low alloy
steels in anaerobic environments, the cathodic process is the reduction of
sulphate ion to sulphide. This cathodic reaction, although as noble as oxygen
reduction in neutral solutions, cannot take place spontaneously if not catal-
ysed because of its slow kinetic. The most known catalyser is given by SRB
metabolism, as proposed by Von Wolzogen and Van der Vlugt in 1934. In
short, an enzyme, idrogenase, allows the reduction of sulphate to sulphide:
SO42− + 8H+ + 8e− ! S2− + 4H2O. Indeed, this reaction also occurs in
nature in sulphate enriched anaerobic environments, where the oxidation
reaction is carbon to carbon dioxide; if SRB find metallic iron available, the
thermodynamically preferred reaction becomes iron oxidation.
For localized corrosion of stainless steels, i.e., the active–passive metals
suffering a MIC attack, two more conditions are necessary besides the
requirement of a cathodic process, i.e., a chloride content sufficient to locally
breakdown the passive film and a cathodic potential exceeding pitting po-
tential. As far as the cathodic process is concerned, oxygen reduction is the
one recognized in aerated waters where, in seawater, biofilm causes cathodic
potential ennoblement. In aerated freshwater, where biofilm does not form,
the potential ennoblement, mandatory for pitting initiation, is exerted by
manganese oxidizing bacteria, MOB, which colonize Mn3+/Mn2+ by their
metabolism. The standard redox potential of Mn3+/Mn2+ is +1.51 V SHE, i.e.,
more noble than oxygen standard potential, is a value easily exceeding the
pitting potential of most used stainless steels in the presence of a very low
level of chlorides (for instance a few tens of ppm).
From Lazzari (2017)
Stainless steels (Figs. 7.13 and 7.14) may suffer pitting corrosion in chloride
containing waters when contaminated by bacteria in an aerobic condition, where
oxygen is necessary for the pitting propagation. In seawater, aerobic bacteria that
colonize the surface of stainless steels form a biofilm that raises the potential by
about 200–300 mV compared to that in sterilized seawater, then allowing pitting
initiation (E > Epitting). In freshwater, what increases the potential is the presence of
aerobic Leptospirillum oxidans bacteria, called MOB (manganese oxidizing
Fig. 7.13 MIC mechanism Aerobic

on stainless steels in the Pitting on stainless steel
presence of biofilm (typically O2 + Biofilm + Chlorides
in seawater) 4OH-
Biofilm O2 + 4e- + H2O

Mez+
e-
Fig. 7.14 MIC mechanism Aerobic

on stainless steels in the Pitting on stainless steel
presence of MOB (typically in O2 + MOB + Chlorides
freshwater)
4Mn3+ + 4OH- 4Mn2+ + 2H2O + O2
O2+ MOB
4Mn3+ + 4e- = 4Mn2+

Mez+
e-
bacteria) which produce the manganese couple, Mn3+/Mn2+, having a noble stan-
dard potential +1.51 V SHE sufficient to trigger pitting initiation. A manganese
concentration as low as 2 lg/L and a chloride content of only 40 mg/L is sufficient
for that bacterium to initiate pitting of AISI 304 stainless steel, as has occurred in
many European rivers (Rhine, Seine and others).
7.3 Metal/Environment Affecting Factors
7.3.1 Temperature
Although a corrosion process is the result of a series of elementary processes,

namely, electrochemical (electrode reactions), chemical (homogeneous reactions)
and physical (solubility and diffusion), the corrosion rate depends on temperature
through a complex law, neither exponential, as typical for chemical reactions (re-
action rate doubles every 10 °C increase in temperature), nor linear as in some
physical processes. Indeed, when the prevailing elementary process is gas solubility
in the solution, the corrosion rate may even decrease as the temperature increases.
Fig. 7.15 Corrosion rate of Crate

mild steel with temperature (mm∙y-1)
in: ① water in equilibrium
with atmosphere; ② in closed 2
circuit with constant oxygen 0.5
content (Speller 1926)
0.2 1
40 60 100
Temperature (°C)
We have already seen that as the temperature increases the diffusion coefficient
increases while the oxygen solubility in water decreases, then zeroing at boiling
temperature. Accordingly, in the case of oxygen-related corrosion, the corrosion
rate follows the trends shown in Fig. 7.15: (curve ①) for open circuits (water
exposed to the atmosphere) and (curve ②) for closed circuits where oxygen
remains entrapped in the plant and therefore, available even at high temperature. In
closed circuits, the corrosion rate doubles about every 25 °C increase.
In acidic solutions, where the cathodic process is hydrogen evolution, the cor-
rosion rate increases as the temperature increases by following an exponential trend.
For active–passive metals, dissolved oxygen helps passivity therefore, an increase
in temperature reducing the dissolved oxygen contributes to weaken the passivity
film. For example, this is the case of stainless steel, titanium or other active–passive
metals in non-oxidizing acids, such as sulphuric or hydrochloric acid.
Non-uniform temperature conditions favour the localization of corrosion on
higher temperature zones which become anodic, as typically observed in boilers
and heat exchangers.
7.3.2 Condensation
Local variations of physical-chemical conditions are important from a corrosion

viewpoint. Most important is water condensation caused by temperature decrease or
pressure increase which leads to severe corrosion, as in chimneys where carbonic
acid and also sulphuric acid form, when sulphur is present in fuel. Another common
example is water condensation in gas wells containing carbon dioxide where the
corrosion rate can be very high. Critical parameter is dew point temperature/
pressure, which determines the water condensation condition. In the case of sul-
phuric acid formation, dew point temperature at atmospheric pressure can be much
higher than boiling water temperature, for instance around 140 °C because of the
formation of concentrated sulphuric acid.
7.3 Metal/Environment Affecting Factors 135
7.3.3 Corrosion Products and Deposits
The presence of deposits (scales, corrosion products, debris, dirties) may be either
beneficial or harmful. The protective action is linked to the ability to form a barrier
which separates the metal surface from the environment. The protection properties
of such a barrier depend on a variety of characteristics: solubility, state (uniform,
non-uniform, crystalline or colloidal), porosity, hygroscopic nature (in the case of
atmospheric corrosion) and electrical conductivity. The latter is the most important
since:
• Electronic conductivity, as shown by magnetite and sulphides, can cause
galvanic-like corrosion
• Ionic conductivity, as in the case of cuprous oxide of copper, almost neutralises
the barrier effect
• Insulating properties are always beneficial: in this case the metal surface can
scarcely support anodic or cathodic processes. For example, this is the case of
Al alloys whose corrosion resistance enhances when thick oxide films form.
On the other hand, a scale can enhance crevice corrosion or differential aeration
corrosion, or corrosion-erosion when a local turbulence is set up downstream or
upstream of the deposit, or local overheating as is typical in heat exchangers.
7.3.4 Flow Regime
Flow regime affects corrosion in different ways. In oxygen diffusion control, as the
flow rate increases, for instance from v1 to v4 as shown in Fig. 7.16, the corrosion
rate of an active metal increases up to a limit represented by point ④. Conversely,
as shown in Fig. 7.17, for an active–passive material, an increase in the flow rate
can facilitate passive film formation. Indeed, the corrosion rate increases from point
① to ② and up to ③, where the corrosion rate reaches a maximum, then drops to
point ④ when the flow rate exceeds v4 and metal passivates. An increase of flow
rate is also beneficial when it contributes to avoid stagnant conditions that are
hazardous for pitting. More generally, the high flow rate regime is dangerous when
leading to corrosion-erosion conditions which are enhanced in the presence of
suspended hard solids (mechanical wear effect) (see Chapter 16).
7.3.5 Active–Passive Related Parameters
Whether an active–passive metal, for example stainless steel, operates in a passive

or active condition depends on both the metal and the environment and it can be
Crate
4 E
3
Ec
2
2
1 4
1 3 Increasing
velocity
Ea
v1 v2 v3 v4 v log i
Fig. 7.16 Effect of electrolyte velocity on the corrosion rate of an active metal
Crate E
3
Eeq,O2 4
1 2 3
4 1
Increasing velocity
Eeq,M
v1 v2 v3 v4 v log i
Fig. 7.17 Effect of electrolyte velocity on the corrosion rate of a passivating metal
determined by examining anodic curves on Evans diagrams. As reported previously

in par. 5.6.3 and 5.6.4, parameters defining active–passive corrosion behaviour are:
• Passive interval, between passivity and transpassivity potentials, Ep and Etr,
respectively
• Passivity current density, ip, which measures the corrosion rate within passive
interval
• Critical passivation current density, icp, which defines the ease to passivate.
Preferred corrosion behaviour is when the passivity current density, ip, is low,
passive interval, Etr–Ep, wide and critical passivation current density, icp, is low.
The importance of these parameters is illustrated by the two examples depicted in
Figs. 7.18 and 7.19.
Figure 7.18 schematically shows the anodic curves of some iron-chromium
alloys in a dilute acidic solution exposed to air; it is also reported the cathodic curve
of the oxygen reduction process in a stagnant condition. By increasing the chro-
mium content from 10 to 12%, the corrosion condition shifts from point ① to point
② with a corrosion rate reduction of about three orders of magnitude. It is clear that
passivity is achieved if the chromium content exceeds the threshold of about 12%,
which is historically the condition to assess stainless steel.
Fig. 7.18 Evans diagram for E (V SHE)

Fe–Cr alloys in dilute aerated
sulphuric acid solution 2
0.4
0 10 Cr
18 Cr 12 Cr
1
10 100
log i (mA/m2)
Fig. 7.19 Evans diagram of a E (V SHE)

ferritic and an austenitic
stainless steel in aerated 5%
sulphuric acid solution
0.4
17 Cr
0
18 Cr - 10 Ni
10 100
log i (mA/m2)
Let’s evaluate the corrosion resistance of two stainless steels, one ferritic (17%
chromium) and the other austenitic (18% chromium, 10% nickel), in an aerated 5%
sulfuric acid solution with or without the addition of oxidants. As depicted in
Fig. 7.19, both stainless steels show a comparable passivity current density; how-
ever, ferritic stainless steel shows a much higher critical passivation current density
(a big nose). Therefore, to set up passivity, a robust cathodic process is required that
enables the surpassing of the nose at the primary passivation potential. In practice,
in dilute sulphuric acid, oxygen alone makes austenitic stainless steel passive, while
this is not the case for a ferritic one; in addition to oxygen, a stronger oxidizer is
necessary, for example, Fe3+ or NO3−, even in low concentration.
Wollaston’s and Pallade’s Jokes

One of the first tasks of electrochemists was the ranking of metals by nobility,
far before it was linked to the corrosion behaviour. Volta in 1793 proposed a
first rank and a few years later Ritter discovered that alloying even with small
content changed the nobility of a metal. He wrote: “By dissolving a thin leaf
of tin in mercury, its nobility moves from high position between gold and
silver to low position where reactive metals fall”. He then concluded: “It
seems difficult to establish the content limit below which tin addition doesn’t
change the position of mercury in the potential series”.
Ostwald reported that Ritter was pushed to study the influence on nobility
by an anonymous advertisement in an 1803 London newspaper, which
announced the discovery of a new metal, not yet named, sold by a
well-known metal shop at the prize of one shilling per grain.
Chevenix, a famous chemist of the period most likely for his emphatic
writing rather than his research, confirmed the properties of the new metal.
However, he added, that it was not new, instead a Pt–Hg alloy, where mer-
cury was so strongly linked that it could not be freed even by extreme
heating. Moreover, he said that it was easily produced from a platinum so-
lution, neutralized by mercury oxide, reduced by ferrous sulphate to a black
powder and eventually melted, and voila, the new metal. As the anonymous
discoverer was told that, he published a second advertisement promising
20 lb to whoever was able to obtain the new metal from platinum and
mercury. Obviously, nobody claimed the prize—not even Chevenix.
Now, Wollaston, a Davy’s assistant, revealed that he was the discoverer
and the person responsible for the advertisement, and how during the
experiments to produce malleable platinum, he obtained the new metal along
with another metal, which he had already named rhodium. Chevenix had to
admit his mistake, but not before trying to give vent to righteous indignation
on Wollaston’s behaviour not befitting a scientist. Ritter broke into this
controversy. He found that the metal provided by Chevenix stood over
platinum in the nobility scale and not between platinum and mercury as one
might have expected from their alloy. He also found that it behaved exactly
like the new metal on sale in the mineral shop. In short, he found that the
material supplied by the arrogant chemist for examination did not come from
its mergers but from the shop where he had bought it.
Like the asteroid discovered just a year before, the new metal was named
Palladium, in honor of the Greek goddess Pallas who was produced from
Zeus’ brain. Besides rhodium, Wollaston also discovered the metal which is
able to give titanium the precious feature to withstand both oxidizing and
reducing environments, and a few years ago to have been raised to the honour
(or perhaps to the dishonour?) of the news because of nuclear cold fusion.
And if I were not convinced that some hitherto unknown phenomenon to
some extent really happens in this ghost process, and had I not had respect for
Fleischmann and Pons, particularly the former who I got to know personally,
it would be easier to joke and say that this metal, as well as Chevenix,
mocked even the two “inventors” who believed that humanity’s energy
problem was solved. Unless it was Pallas, the goddess of science, to have
done so.
Special Corrosion Products

In 1967, under the direction of Professor Roberto Piontelli I was investigating
the corrosion behaviour of copper in copper sulfamate solutions because
measured corrosion rates were much higher than expected. While we were
looking for possible root causes of this anomaly, we obtained white cuprous
corrosion products, as needle-like crystals, as soon as sodium or potassium
ions were added. Surprisingly, they did not alter in air: a real rarity, because
cuprous salts, in general, are not stable.
X-ray diffraction analysis and chemical composition revealed two new
compounds: copper–sodium and copper–potassium sulfamate, respectively.
We found how to produce them in large quantities at low cost by stimulating
copper corrosion by injecting a direct or alternating current, then we decided
to file a series of patent applications, including their use, in place of copper
sulphate in fighting the blight of vineyards. “The fungicide activity of cuprous
ions is certainly greater than cupric ones,” we said, and “by using potassium
salt, the new product, once the primary fungicide action is finished, could turn
into a fertilizer.” In short, a brilliant idea, way more, a sure hit, and definitely
also a case of beneficial corrosion!
Because in sulfamic acid, unlike sulphuric acid, it was possible to soak
hands safely, no doubts arose about any possible dangerous action to veg-
etables. In any event, we had sent samples for testing to the Institute of
Pathophysiology of the University of Pavia: in any case, an official certifi-
cation would have been required to start commercialization and collect roy-
alties. Meanwhile, to shorten experimentation time, we decided to hold our
own testing. I prepared some salts and we planned homework: Professor
would take them and convince his gardener to sprinkle them on hydrangeas in
his villa in Santa Margherita Ligure, Italy; I, more modestly, had to give them
to my uncle, Antonio, and have them tried on one row of vineyards and on a
potato field in Mese, Valchiavenna, Italy.
We succeeded, but a week later a disaster happened.
The new product destroyed Professor’s hydrangeas and my uncle’s
vineyards and potato field in a few days. Indeed it also burned the zucchini in
the garden because, either to please his nephew or for the pride of collabo-
rating in a prestigious research study of the glorious Politecnico, my uncle,
careless, decided to widen the testing—that can really be called “in field”.
After one month, the now useless response of the University of Pavia was
received on a letterhead and with stamp duty: the new salts were officially
declared lethal even towards more resistant shrubs. In short, new stuff that
was able to compete with defoliants which, in those days, were used in
Vietnam.
The gardener and my uncle were not surprised by the later verdict from the
University of Pavia because they immediately understood that the fungicide
was actually a herbicide. Unfortunately, the idea that the advancement of
science may also require personal sacrifice did not even touch them. On the
contrary, from the day of the foul incident, they were bitter and did not hide
it. The first repeatedly informed the professor of what he thought. Every time
he met him he added a sarcastic: “Here is the Professor” to a sort of greeting.
Dearest uncle never missed the chance to ask his nephew sarcastically if the
research at the Politecnico was always so interesting and useful. And when
one day the naive nephew told him that potato cultivation in Valtellina and
Valchiavenna was probably introduced by Alessandro Volta, as had occurred
near Como, he replied: “It could be; it means that at that time electrochemists
helped to raise potatoes. Today, grass does not grow where they walk.”
So, the Professor and I for some months, every Monday, on arrival at the
Institute after the weekend, confessed to each other with complicity what he
in Santa Margherita, and I in Valtellina, had to suffer over the weekend. And
there were jokes about it. In the end, it could have been worse. If instead of a
fungicide we had discovered, say, an anti-flu, we could have been tempted to
test it on them. Indeed, seeing as they were feeling so bad, perhaps we had
found it! And we laughed. A little tight-lipped because of the truth.
Pietro Pedeferri’s memory
7:1 Discuss the effect of the addition of platinum on titanium in acidic, oxygen
free solution by means of Evans diagram.
7:2 Consider the values of corrosion rate of commercial aluminium in
hydrochloric acid reported in Table 7.1. Propose an interpretation.
7:3 A controlling corrosion factor is the presence of corrosion products. What
properties are typical for a passivating oxide film? Mention examples of
various types of surface films/surface layers.
7:4 Demonstrate and comment this sentence: “Given the small available driving
force, this phenomenon (Saturn’s tree or Diana’s tree) occurs with normal
metals, such as lead and tin, only”.
7:5 Discuss the mechanism of a cation displacement reaction.
7:6 Discuss the effect of electrolyte velocity on an active metal and on a pas-
sivating metal.
7:7 Inside a water pump, maximum corrosion rate was found when the flow rate
was increased to about 0.1 m3/s. At higher flow rates, the corrosion rate
decreased. What is your interpretation?
7:8 Based on experience, the corrosion rate on carbon steel caused by
sulphate-reducing bacteria, SRB, (for instance in some soils or in pipes
containing stagnant water) can reach 1 mm/y. Try to justify this value based
on an electrochemical mechanism.
7:9 What is the effect of manganese oxidizing bacteria on stainless steels cor-
rosion in freshwater?
7:10 Corrosion by differential aeration happens on iron (i.e., mild steel) and not on
copper and copper alloys. Give a comprehensive interpretation/justification.
Bruno Mazza
Bruno Mazza (1936–2004) was undoubtedly the person who most influenced
the corrosion group that has formed in the mid-60s at Politecnico di Milano,
with Sinigaglia and Pedeferri. It was not because of his works in corrosion, still
important but not as much as those in electrochemistry, or because he taught
for a couple of years a corrosion course, so his lesson imprinting is echoed in
the first part of this handbook: Bruno was for thirty years the moral guide of the
group. He graduated in 1961 (gold medal as the best Italian graduate of the
year). In 1965 he was appointed as Lecturer of Electrochemistry and in 1968
the Board of Faculty of Engineering asked the Ministry of Education to assign
a full professor position for him, who was nearly 30. But 1968 student
movement came so his idyll with Faculty turned into conflict. What happened
with academic authorities can be understood by taking into account that
Faculty rejected any comparison with students and, in opposite direction,
Bruno was fascinated of their demand for change and hope for a world of
justice and solidarity. They decided to cut off his career by withdrawing the
position. He could maintain the teaching because Parliament approved the
conservation of the status quo. After nearly two decades he had the satisfaction
of having the chair previously denied, he became director of the department
and was called to fill some of the highest offices of the University. All the
group remembers of Mazza the scientist, the serious and charm teacher, the
commitment, the honesty, the courage, the consistency, the availability, the
gentleness, the respect of persons. And also the masterful lesson, handouts on
which many learned electrochemistry, the patience for explaining and making
things clear, so hundreds of engineers remember his teaching.
Roberto Piontelli
Professor Piontelli (1909–71) was an eminent electrochemist of international
prominence who contributed the foundations of modern electrochemistry. In
1949, together with major European and American scientists of this sector, he
founded the CITCE, later named ISE, the International Electrochemical
Society. M. Pourbaix, who was the first chairman, recognized in his paper
“The birth of CITCE, in Electrochimica Acta, XVI (1971), pp. 173–175) the
key role of Piontelli. Pourbaix asked Piontelli to write the preface of his
famous book Atlas of electrochemical equilibria in aqueous solutions, pub-
lished in 1966. Since he graduated in 1930s, he greatly contributed to sim-
plify the electrochemistry that was, as often he said, entangled by conventions
of sign instead interested of the interpretation and understanding of complex

phenomena. In 1948, as director at Politecnico di Milano (Milan, Italy), he set
the discipline on a chemical-physical basis and improved his experimental
methods. During 1950s, with reference to Linus Pauling approach on elec-
tronegativity of metals, he proposed a theory on the correlation between
structure and electrochemical behaviour of metals, now known as
anti-correlation. On the experimental side, he determined the anodic and
cathodic behaviour of polycrystalline and monocrystalline metals, investi-
gating the associated corrosion and protection problems. On the theoretical
side, he gave an important contribution to thermodynamics and kinetics of the
pile and wet corrosion processes. It is interesting to read what Piontelli wrote
on the research methodology in the field of electrochemistry and corrosion,
mirroring the Baconian philosophy. “Only the activity of the bee is suitable
for electrochemistry,” paraphrasing the English philosopher, hence there is no
need for “ant-type researchers” who “collect” and “use” the measurement
data without bothering to understand what happens in their systems, neither
“spider-types”, who build their theories as their own nets regardless the
nearby reality. The “bees suck nectar from flowers of gardens and fields” and
then rework it to transform it into honey. “In a transversal discipline such as
electrochemistry and corrosion, only on a solid phenomenological platform
both the tower of the most daring theoretical speculation and the more
modest yet robust and efficient building of rational technology can be erec-
ted”. He proceeded by building the mosaic of the electrochemical behaviour
of metals composed of generalization of observation results, calculations,
studies, meditations, recognition of essential factors and their interrelation-
ships in a final rational frame. His motto was “it is preferable to make a small
contribution to a great problem that the most complete success in responding
to an occasional question”. Then he entered into specific problems of the
industry and electrochemical applications. Convinced that—in sectors such as
these “born on empiricism and often still his devoted subjects”—the solution
of fundamental problems must rest “on chemical-physical and theoretical
premises”, he worked to transform dominant technology based on experience
and common sense in “rational technology”. Finally, closing the cycle,
suggestions or cues are taken from the industrial reality to reset the teaching
and research work. The volume “Elements of the theory of wet corrosion of
metallic materials” (Edition Longanesi, Milan, Italy, 1961) was the first
major Italian volume on corrosion, often considered as beautiful as difficult to
understand. In addition to his book on corrosion, he published Lezioni di
termodinamica chimica, Milano, 1961 as well as more than three hundred
papers, collected in R. Piontelli, Scientific papers: 1935–1971, Milano 1974.
In Piontelli, the scientist and the researcher of electrochemical science
coexist, enriched by the teaching in an engineering faculty. This gave him the
best position to verify the gap between the ants operating in the industrial
world without knowing what happens in their cells and spiders nested in the
academies often ignoring what was going on in the real world. This condition
allowed him to transfer knowledge or methodologies from the laboratory to
the industry and from field experiences to the research. In 1958, some col-
leagues of the CITCE, through their respective national academies, proposed
him for the nomination of Nobel Prize for Chemistry.
Bibliography
Lazzari L (2017) Engineering tools for corrosion. Design and diagnosis. European Federation of
Corrosion (EFC) Series, vol 68. Woodhead Publishing, London, UK
Milan, Italy (in Italian)
Speller FN (1926) Corrosion. Causes and prevention. McGraw-Hill, London, UK
Von Wolzogen Kuhr CAV, Van der Vlugt SS (1934) Graphitization of cast iron as an
electrochemical process in anaerobic soil. Water (Den Haag) 18:147–165
Winston Revie R (2000) Uhlig’s corrosion handbook, 2nd edn. Wiley, London, UL
Chapter 8
Uniform Corrosion in Acidic
and Aerated Solutions
Memories bring diamonds and rust.

Joan Baez
Abstract In this Chapter, the causes and consequences of uniform (or generalized)
corrosion are described. This is the simplest form of corrosion, which affects the whole
metal surface, and is characterized by the spatial coincidence of anodic and cathodic
areas. Corrosion rates range in a very large interval, depending on the environmental
conditions, and the phenomenon is easily observed and easily predictable, especially
if compared with localized corrosion forms. Here the main conditions leading to

https://doi.org/10.1007/978-3-319-97625-9_8
146 8 Uniform Corrosion in Acidic and Aerated Solutions
uniform corrosion are detailed, from acidic environments to aerated neutral solutions,
with reference to the different classes of active and active–passive metals. Moreover,
examples of algorithms used to express corrosion rate are provided.
8.1 Introduction
Uniform corrosion, also called generalized corrosion, affects the entire exposed
surface of active metals in contact with an aggressive environment because anodic
and cathodic zones coincide. The main cases of metals suffering generalized cor-
rosion are:
• Carbon steel when exposed to the atmosphere, or immersed in neutral or acidic
solutions, in carbonated concrete, in soil and sea water
• Aluminium in low and high pH solutions
• Stainless steel in acidic solutions (Fig. 8.1)
• Carbon steel in CO2-containing environments (sweet corrosion)
• Zinc in acidic solutions
• Lead throughout the entire pH range when insoluble corrosion products, such as
carbonates or sulphates, do not form.
Despite the name, this corrosion form is often not uniform either at the microscopic
or at the macroscopic scale. For example, internal corrosion in carbon steel
pipelines carrying hydrocarbon containing CO2, called mesa corrosion because it is
reminiscent of the mesa landscape in the region across Texas and Mexico; or the
case of antiquities on which generalized corrosion highlights the inhomogeneous
structure. Corrosion rate varies widely from very low values, some lm/y, to tens of
mm/y depending on the metal and the aggressive environment. Figures 8.2, 8.3 and
8.4 show some examples of uniform corrosion.
Fig. 8.2 Generalized corrosion occurred in 24 h on a carbon steel tube erroneously etched with a
non-inhibited 10% HCl solution
8.1 Introduction 147
Fig. 8.3 Uniform corrosion of a carbon steel nail, which remained for 150 years in a wooden
beam. The curved zone outside the beam suffered a more pronounced thinning
Fig. 8.4 The effect of expansion of corrosion products by generalized corrosion
In some cases uniform corrosion is beneficial, for example in:

• Surface roughening of orthopaedic implants to facilitate bone integration
(Fig. 8.5)
• Metallographic attack by etching to highlight a microstructure (Figs. 8.6, 8.7
and 8.8)
Fig. 8.5 Roughness on

titanium orthopaedic implant
obtained by generalized
corrosion
Fig. 8.6 Picture of a curious

dendritic structure of a silver
sample obtained by etching
• Surface polishing
• Etching for metal carving to produce moulds, prints and matrices for artistic use
• Pickling for metal surface cleaning (for removal of oxides and some of first
metal layer).
Some Consequences of Uniform Corrosion

Although generalized corrosion causes the greatest amount of corrosion
products, it is in general less insidious than localized corrosion because
corrosion rate (i.e., thickness loss rate) is often low and predictable, with good
accuracy, and is easily monitored during operating; nevertheless, attention
should be paid to its consequences.
For example, corrosion products exert an expansive action because their
volume is much greater than that of the corroded metal. This is shown in
Fig. 8.4, where corrosion products between two steel profiles led to the
8.1 Introduction 149
Fig. 8.7 Micrograph of an AISI 304 stainless steel after metallographic etching
Fig. 8.8 Micrograph of a duplex stainless steel after metallographic etching
failure of welds, and the same happens to carbon steel inserts in ceramic or
stone, thus causing cracking. Some historians attributed the fall of the Roman
Empire to the consequences of lead corrosion.
8.2 Acidic Solutions
Tafel law allows the calculation of a metal corrosion rate with good approximation,
for instance in the case of ferrous alloys (carbon and low alloy steels) and zinc in
acidic solutions, where the predominant cathodic reaction is hydrogen evolution.
Typical acidic solutions present in industry are: strong acids, carbonic acid,
hydrogen sulphide and organic acids.
The model proposed here, already adopted in Lazzari (2017), can be named
“Tafel-Piontelli model” (see De Giovanni 2017) for active metals such as iron and
zinc in acidic solutions and where the cathodic process is hydrogen evolution; it
simply consists of considering the Evans diagram on the basis of two conditions:
• Anodic overvoltage of active metal dissolution is negligible (according to the
Piontelli’s classification)
• Cathodic process of hydrogen evolution follows Tafel law.
Figure 8.9 shows an example of the Evans diagram for two metals in an acidic
solution with the same pH (hence, the same equilibrium potential of hydrogen
evolution reaction) and assuming the Tafel slope to be near zero (b ≅ 0) for metal
dissolution reaction. This means that the free corrosion potential of the metal is
taken as its equilibrium potential. This approximation is acceptable when the
cathodic reaction is hydrogen reduction only (i.e., oxygen-free/chlorine-free acidic
solutions).
The equilibrium potential at room temperature of the metal is given by Nernst
equation:
i0,H i0,H
2-M2 2-M1
Eeq,H
2
i0,M
Eeq,M 1
1
i0,M
2
Eeq,M
2
icorr,M icorr,M log i

2 1
Fig. 8.9 Evans diagram to determine corrosion rate in acidic solutions based on Tafel-Piontelli
model
8.2 Acidic Solutions 151
0:059
E eq;M ¼ E 0Mz þ þ log aMz þ ð8:1Þ
z
where M could be Fe or Zn or other active metals, for instance Cu in

Cu-complexant solutions. The cathodic curve, i.e., the Tafel straight line for
hydrogen evolution is given by Tafel law:
i
g ¼ bH2 log ð8:2Þ
i0;H2
which can be rewritten as follows:

g
i ¼ i0;H2 10bH2 ð8:3Þ
where bH2 is the Tafel slope for hydrogen evolution equal to 0.12 V/decade, i0;H2 is
the exchange current density for hydrogen evolution on the metal (see Table 5.2), η
is given by Eeq;H2 Ecorr , where Ecorr is taken as Eeq,M, hence:
0:059
g ¼ DE ¼ 0:059 pH ðE0 þ log½Mz þ Þ ð8:4Þ
z
An empirical equation for iron can be derived taking into account the influence of
temperature and velocity of the fluid as follows (Lazzari 2017; Kreysa and Schütze
2006a, b):
T25 ð z log½M
0:059 pH E 0 þ 0:059 Þ
zþ
C rate;acid ¼ 1:2 i0;H2 ð1 þ vÞ 2 20 10 0:12 ð8:5Þ
where the required parameters are:

• i0;H2 (exchange current density of hydrogen evolution on the considered metal,
in mA/m2)
• v (fluid velocity in m/s)
• pH of the acid solution
• az+
M (metal ion concentration in the diffusion layer, i.e., at the interface)
• T (temperature in °C).
To use Eq. (8.5) in practical applications, there is the need to input metal ion
concentration, az+
M , which is in practice the only unknown or uncertain variable. For
different types of acidic solutions, the suggested az+ M values are reported in
Table 8.1. The model is the same for organic and complexant acids; metal ion
concentration is derived from the complex constant. Since metal ion concentration
in equilibrium with the complexant is quite low, the corrosion rate is high although
the pH is close to neutrality.
Table 8.1 Parameters for the calculation of corrosion rate in different acids (from Lazzari 2017)
Active Exchange current density of Metal ion M2+ concentration [a2+
M ] mol/L
metal or hydrogen evolution on Strong Organic Hydrogen Carbonic
alloy metal M; i0;H2 M ðmA=m2 Þ acids acids sulphide acid
(H2S) (H2CO3)
Zn 10−3 0.1–1a 10−10 10−12 10−6
Cu 10
Fe 1 10−6–
(ferrous 10−9
alloys)
a
In the presence of HCl, copper-chloride complexes form, after which the concentration of copper
ions drops to 10−15 mol/L
8.2.1 Strong Acids
In the presence of strong concentrated acid solutions, such as nitric acid, sulphuric
acid, or hydrochloric acid (pH lower than 1), very high corrosion rates are expected
on Zn and Fe.
Table 8.2 shows calculated values taking the metal ion concentration to be in the
range 0.1–1 mol/L in stagnant conditions for Zn, Fe and ferrous alloys. Copper is
corroded only in pure hydrochloric acid (HCl 12 mol/L, pH < 0), since
copper-chloride complexes form, reducing the concentration of copper ions to
10−15 mol/L. Corrosion rates of some hundreds of micrometres per year up to
1 mm/y are expected.
8.2.2 Carbonic Acid
Carbon steel and low alloy steels corrode in carbonic acid containing media, as is
well known in the oil and gas industry. The approach used is typically empirical
and equations used to estimate the corrosion rate, starting from the very first by de
Table 8.2 Calculated corrosion rates for iron and zinc in strong acids and copper in HCl
Temperature °C Fe Zn Cu
0
E (V SHE) −0.44 −0.76 0.34
a2+
M (mol/L) 1–0.1 1–0.1 10−15
M; i0;H2 M ðmA=m2 Þ 1 0.001 10
Crate (mm/y) pH = 0 25 5–8 2–4 0.07
50 9–18 7–14 0.08
100 39–80 85–174 0.12
Waard and Milliams, are derived from laboratory testing. The de Waard and
Milliams base equation (dWM) is the following:
1710
log C rate;dWM ¼ 5:8 þ 0:67 log pCO2 ð8:6Þ
T þ 273
where Crate,dWM is corrosion rate (mm/y), T is temperature (°C) and pCO2 is carbon
dioxide partial pressure (bar). Some empirical coefficients are used (see Chap. 24)
to either mitigate or increase the calculated corrosion rate when temperature
exceeds a so-called scaling temperature and pH is lower than the equilibrium value.
The general Eq. (8.5) can be used by introducing the pH of carbonic acid
solution given by the following relationship as a function of CO2 partial pressure,
pCO2 :
h i
pH ¼ log 104 ðpCO2 Þ0:5 ¼ 40:5 log pCO2 ð8:7Þ
where pCO2 is expressed in bar. By introducing in Eq. (8.5) i0,H2 = 10−3 A/m2 and
−7
a2+
Fe close to 10 mol/L and pH in accordance with Eq. 8.7 and reversing in a
logarithm form, the following simplified equation for low velocity flows is
obtained:
logCrate;CO2 ffi 0:015ðT 25Þ þ 0:8 log pCO2 ð8:8Þ
where Crate is corrosion rate (mm/y), T is temperature (°C), v is fluid velocity (m/s)
and pCO2 is carbon dioxide partial pressure (bar). This equation is valid for tem-
perature up to about 80 °C because iron passivates at higher temperature.
Table 8.3 compares results obtained by the Tafel-Piontelli model and de Waard
and Milliams base equation for temperature below 100 °C. The good match con-
firms the reliability of the model because results of de Waard and Milliams equation
have been confirmed experimentally.
Corrosion Mechanism in Carbonic Acid

There is a variety of references on this matter. In short, the most cited and
accepted mechanism for the corrosion of carbon steels in carbonic acid is the
following:
• Corrosion rate in carbonic acid, although it is a weak acid, is one order of
magnitude higher than the one in a strong acid at the same pH (3–6)
• This is attributed to the presence of more than one cathodic reaction
besides hydrogen reduction
• Other cathodic reactions would be the direct reduction of either bicar-
bonate ion or undisassociated carbonic acid:
Table 8.3 Comparison of the calculated corrosion rates of steel in carbonic acid obtained from
−6
the model (a2+
Fe = 10 mol/L) and the de Waard and Milliams base equation in stagnant
conditions
pCO2 ¼ 1 bar pCO2 = 2 bar pCO2 = 5 bar pCO2 = 10 bar
T Model deW & M Model deW & M Model deW & M Model deW & M
(°C) (mm/y) (mm/y) (mm/y) (mm/y) (mm/y) (mm/y) (mm/y) (mm/y)
25 1.0 1.2 1.7 1.8 3.6 3.4 6.3 5.4
50 2.4 3.2 4.1 5.1 8.6 9.4 15.0 15
75 5.6 7.7 9.8 11.5 20.4 22.6 35.5 36
H2 CO3 þ 2e ¼ H2 þ CO2

3
2HCO
3 þ 2e ¼ H2 þ 2CO3
2
As shown in previous paragraphs, the same corrosion rates as those from

testing (from which the de Waard and Milliams equation was derived) are
obtained on the basis of the corrosion theory:
• The cathodic reaction is hydrogen reduction (to give hydrogen gas)
• The free corrosion potential approximates iron equilibrium potential,
governed by the solubility product of FeCO3 which is 2 10−11 at room
temperature and decreases strongly as temperature increases.
In conclusion, it seems that there is no need to cite exotic mechanisms or
empirical models derived from testing. Indeed, results obtained from exper-
imental tests confirm those calculated by a theoretical model, valid for strong
or weak or organic acid, hydrogen sulphide and carbonic acid.
from Lazzari (2017)
8.2.3 Hydrogen Sulphide
Hydrogen sulphide (H2S) dissolves in water forming a weak acid which decreases
the solution pH to about 6. With this pH, the corrosion rate of ferrous alloys would
be low to negligible in an oxygen-free solution, while experience shows that the
corrosion rate is considerable because insoluble FeS forms. By inputting
−12
a2+
Fe = 10 mol/L into Eq. 8.4, corrosion rate would be surprisingly high
(Table 8.4) since the solubility constant is 10−24. Observed corrosion rates are
−9
obtained by inputting a2+Fe = 10 mol/L; this takes the protection effect (barrier
type) of the FeS layer into account.
Table 8.4 Calculated a2+ T Crate

M
corrosion rates for ferrous
(mol/L) (°C) (mm/y)
alloys obtained at pH = 6 in
the presence of H2S Hydrogen Sulphide (H2S) 10−12 25 5.4a
50 9.6a
100 30a
a
True corrosion rates are much lower because of the formation of
FeS which is a protective product
8.2.4 Organic Acids
Organic acids (for example, formic acid, acetic acid, citric acid) severely corrode
ferrous alloys, with very high corrosion rates—although the pH is close to neu-
trality. Even stainless steels in reducing conditions (i.e. in the absence of oxygen)
may suffer a strong corrosion rate. Organic acids form complexes with the metal
resulting in metal ion concentration, derived from the complex constant, in equi-
librium with the complexant being quite low, in the range of 10−10 mol/L. The
proposed model predicts well the expected corrosion rate values (Table 8.5 for
ferrous alloys).
8.2.5 Corrosion of Passive Metals
In acidic solutions, passive metals can show:

• Depassivation (i.e., oxide dissolution) then behaving as an active metal fol-
lowing the model summarized in Fig. 8.9
• Passivity without risk of localized corrosion (i.e., chloride content is below the
critical threshold content and free corrosion potential is below pitting potential)
• Passivity with the potential risk of localized corrosion (i.e., chloride content is
above the critical threshold content but free corrosion potential is below pitting
potential).
Uniform corrosion may occur if depassivation takes place. This occurrence is
possible if pH is below depassivation pH which, for low grade stainless steels, is
Table 8.5 Calculated a2+ T Crate

M
corrosion rates for ferrous
mol/L °C mm/y
alloys in organic acids
(obtained at pH = 6) Organic acids 10−10 25 1.8
50 2.8
100 7.3
no Cl
with Cl
Eeq,H
2
Ecorr
Eeq,M
i0,M i0,H -M icorr,M log i

2
Fig. 8.10 Evans diagram of passive metals in acidic solutions
about 2, and much lower for higher nickel-based alloys. The uniform corrosion rate
can be predicted by the model discussed above.
As illustrated in Fig. 8.10, two conditions exist if there is no de-passivation:
• Absence of chlorides. The passivity current density of most common passive
metals (i.e., stainless steels, nickel-based alloys, titanium alloys and others) is
lower than the exchange current density of hydrogen evolution. Therefore, the
free corrosion potential is the equilibrium potential of hydrogen evolution (i.e.,
−0.059 pH) and the driving voltage for hydrogen evolution is zero (this means
that the hydrogen evolution rate equals the passivity current density)
• Presence of chlorides. Due to the presence of chlorides, the passivity current
density may exceed the exchange current density of hydrogen evolution, leading
to a free corrosion potential that is lower than the equilibrium potential of
hydrogen evolution. As a rule of thumb, since the passivity current density in the
presence of chlorides is in the same range as the exchange current density of
hydrogen evolution, the free corrosion potential is as a maximum about 100 mV
more negative than the hydrogen equilibrium potential (Tafel slope is 120 mV/
decade).
8.3 Aerated Solutions
The cathodic processes in aerated near-neutral solutions are oxygen reduction,

followed by hydrogen evolution when potential drops below its equilibrium
potential; this occurrence depends on the metal involved. For instance, if the metal
is noble, like copper or silver, the only possible cathodic reaction is oxygen
8.3 Aerated Solutions 157
reduction (if chlorine is also present, this would be first) even in acidic solutions; if
the metal is iron and pH exceeds neutrality, again the only practical cathodic
process is oxygen reduction (and also chlorine reduction, when present); if the
metal is more electronegative, such as in the case of zinc, both reactions, i.e.,
oxygen reduction and hydrogen evolution, take place.
8.3.1 Oxygen Limiting Diffusion Current
When oxygen reduction takes place below the field of activation overvoltage,
diffusion is the control factor of oxygen availability through the oxygen limiting
diffusion current density, iL, which is governed by Fick law, as seen in Chap. 5:
D
iL ¼ 4 F C1 ð8:9Þ
d
where D is diffusion coefficient, F is Faraday constant, C1 is oxygen concentration

in the bulk and d is diffusion layer thickness. The latter parameter does not depend
on the metal; rather, it depends on the turbulence of the solution. In aerated
near-neutral solutions, the corrosion rate for mild steel coincides with iL, hence, its
knowledge is of primary importance in applications.
Oxygen dissolves in aqueous solutions when in contact with the atmosphere; in
natural waters it is also present due to photosynthesis. Oxygen solubility in water
varies and depends on temperature and salinity. Oxygen content in seawater
(salinity about 35 g/L) varies from 9 mg/L at 0 °C, to 6 mg/L at 30 °C, 3 mg/L at
60 °C, and zero at 100 °C (at the pressure of 1 bar). As salinity increases, oxygen
solubility decreases until zero above 150 g/L; in the Dead Sea, which is saturated
with salt (more than 200 g/L), there is no dissolved oxygen and therefore there is no
life and no iron corrosion. In natural water, photosynthesis and fouling may de-
termine anaerobic, over- or under-saturation local conditions; the absence of oxy-
gen, which would be ideal to impede corrosion, instead favours
microbiological-related corrosion.
The values of parameters of Eq. 8.9 can be approximated as follows:
• The diffusion layer thickness, d, in a stagnant condition varies between 0.5 and
3 mm for minimum and maximum oxygen content (from 1 to 11 ppm)
• The diffusion layer thickness, d, in a flowing condition varies by a parabolic law
with water velocity, v
• The diffusion coefficient D (m2/s) varies with temperature by the following
relationship: log D [cm2/s] = − 4.410 + 773.8/T − (506.4/T)2. As rule of
thumb, it doubling every about 25 °C of temperature increase starting from
2.25 10−9 (m2/s) at 25 °C (1.97 at 20 °C; 4.82 at 60 °C)
• Faraday constant, F = 96485 C.
Eeq,O
2
Turbulence
increase
i0,O iL i’L i’’L log i

2
Fig. 8.11 Qualitative representation of the influence of turbulence on the cathodic curve
By introducing the relevant parameters in Eq. 8.9, iL (mA/m2) is expressed by

the following empirical equation:
T25 pffiffiffi
iL ffi 10 2 25 ½O2 1 þ v ð8:10Þ
where [O2] is the oxygen content in water in mg/L ( ppm), v is water velocity (m/s)
and T is temperature (°C). Changes of oxygen content in water determine a double
variation:
• Oxygen limiting current density increases as turbulence (i.e., water velocity)
increases (Fig. 8.11)
• Equilibrium potential changes by about 50 mV every 1 ppm variation of oxygen
content, through Henry law for oxygen partial pressure (Fig. 8.12).
8.3.2 Presence of Chlorine
The presence of chlorine gives rise to a more noble cathodic process, which takes
place first:
Cl2 þ 2e ! 2Cl ð8:11Þ
chlorine, like oxygen, is a gas that dissolves in water, but unlike oxygen it partially
dismutes. Therefore, the fraction available for diffusion is about 30% (chlorine
diffusion coefficient is 1.38 10−9 m2/s at 25 °C and, like oxygen, it doubles every
25 °C). According to this, Eq. 8.10 can be revised by also introducing the chlorine
E’’eq,O
2
E’eq,O
2
Eeq,O
2
Oxygen
content
increase
i0,O iL i’L i’’L log i

2
Fig. 8.12 Qualitative representation of the influence of oxygen content on the cathodic curve
content, taking into account the different diffusion coefficient and valence (8 g of
oxygen are equivalent to 35 g of chlorine); eventually, it becomes:
T25 pffiffiffi
iL ffi 10 2 25 f½O2 þ 0:04 ½Cl2 g 1 þ v ð8:12Þ
where oxygen limiting current density, iL, is in mA/m2, [O2] and [Cl2] are oxygen
and chlorine concentrations in water in mg/L (ppm).
8.3.3 Dimensionless Number Approach
In a flowing condition, the diffusion layer thickness, d, can be calculated by using

the classic hydrodynamic approach based on the Sherwood (or Nusselt) dimen-
sionless number, which gives:
/ /
Sh ¼ ¼ iL ð8:13Þ
d 4FD½O2
where / is called the characteristic dimension, for example, the pipe diameter; the
meaning of other parameters is known. The Sherwood number is a function of
Reynolds (Re) and Schmidt (Sc) dimensionless numbers, as follows:
/m t
Sh ¼ 0:023 Re0:87 Sc0:33 Re ¼ Sc ¼ ð8:14Þ
t D
where / is characteristic dimension (m); v is water velocity (m/s); t is kinematic

viscosity (m2/s) and D is diffusion coefficient (m2/s). Oxygen limiting current
density, iL (A/m2) is given by the Sherwood number as follows:
Sh
iL ¼ 4FD½O2 ð8:15Þ
u
It is of practical interest the comparison of results obtained by applying the

empirical Fick equation (Eq. 8.10) and the dimensionless number approach. For
instance, on the basis of the following input data:
• Oxygen content 10 ppm (mg/L) = 0.3 mol/m3
• Temperature: ambient
• Water velocity: 1; 2; 3 m/s
• Viscosity: 0.001 m2/s
• Diffusion coefficient: 2 10−9 m2/s
• Size of characteristic dimension: 0.5 and 1 m.
The comparison of the results is very good (scattering below ±20%). For
example, 241 mA/m2 against 212 and 232 for a velocity of 2 m/s and size diameter
1 or 0.5 m respectively.
8.3.4 Corrosion of Noble Metals
Figure 8.13 shows some examples of the corrosion behaviour of noble metals (i.e.,
with an equilibrium potential that is more noble than hydrogen equilibrium
potential) in aerated solutions. Metal ③, which is the least noble, practically works
under diffusion control; hence, the corrosion rate coincides with oxygen limiting
current density.
Metals ① and ② work in the region of activation overvoltage: in these cases, the
corrosion rate is determined by the overvoltage once the equilibrium potential of
oxygen is fixed (which is given by pH and oxygen concentration), and hence by the
nature of metal involved. In Fig. 8.13 the working condition is represented by
points ① or ①′ depending on overvoltage: for instance, for metal 1 the free
corrosion potential is high when oxygen overvoltage is low (i.e., a high exchange
current density) or, instead, is low when oxygen overvoltage is high (i.e., a low
exchange current density).
8.3.5 Corrosion of Non-noble Metals
Metals are defined as “non-noble” when the free corrosionpotential of the active
behaviour is below the equilibrium potential of hydrogen evolution. In practice, the
i0,O -M
2
Eeq,O
2
1
1’
2
2’
Eeq,M
3
i0,M icorr,M log i
Fig. 8.13 Corrosion rate representation of noble metals in aerated solutions
non-noble metals start from lead, and are then followed by tin, nickel, iron, zinc,
aluminium and magnesium. Chromium and titanium should also be considered if
they were active; instead, since they passivate, then they work like noble metals. In
aerated solutions, non-noble metals work below the activation overvoltage region as
shown in Figs. 8.14 and 8.15.
The working conditions represented in Fig. 8.14 by points ①, ② and ③ are
determined by the nobility of the metal: metals ① and ② are sufficiently noble not
to work in hydrogen evolution conditions. Instead, metal ③ can support both
cathodic reactions, that is, oxygen reduction first followed by hydrogen evolution.
Figure 8.15 shows how the corrosion rate for metal ① increases as the oxygen
limiting current density increases.
Eeq,O
2
2
Eeq,M
3
i0,O -M i0,M iL log i

2
Fig. 8.14 Corrosion rate representation of non-noble metals in aerated solutions

Eeq,O
2
1’’
1’
1
Eeq,M
i0,O -M i0,M icorr,M log i

2
Fig. 8.15 Corrosion rate of non-noble metal in aerated solutions at increasing oxygen limiting
current density
8.3.6 Corrosion of Passive Metals
Unless localized corrosion occurs, such as in pitting, crevice, interstitial and stress
corrosion cracking, passive metals in aerated, near-neutral or alkaline solutions
behave like noble metals, thus exhibiting a noble free corrosion potential and a very
low corrosion rate coinciding with the passivity current, ip, as depicted in Fig. 8.16.
When critical passivation current density, icp, exceeds oxygen limiting current
density, iL, there is the possibility of another “stable” working condition, repre-
sented by point ②, as depicted in Fig. 8.17. Working conditions ① and ② rep-
resent two final stable and mutually exclusive conditions determined by the initial
passive or active condition: in fact, the initial condition they are in at the start will
be maintained. This behaviour can be interpreted in the light of catastrophe or chaos
theory, by which the system evolves towards two opposite stable conditions, pas-
sive or active, as a function of the initial state only.
The measurement of potential gives a clear indication of the metal state: passive
if potential is noble, or active if near the equilibrium potential. In aerated solutions,
passive metals exhibit a noble potential and for this reason, this state is said to be of
practical nobility.
When Incorrect Repairs Cause Damage

Considering the damage caused by the corrosion of iron inserts inside stones,
one of the most commonly reported examples is the damage that occurred on
the monuments of the Acropolis in Athens after some irresponsible restora-
tion works that were carried out at the turn of the XX century up to the
Second World War. In 1943 John Meliades, Superintendent of the Acropolis
monuments, wrote: “The damage to monuments at the Acropolis, and in
Eeq,O
2
Eeq,M
i0,M i0,O -M ip iL log i

2
Fig. 8.16 Corrosion conditions of passive metals in aerated solutions
Eeq,O
2
Eeq,M
2
i0,M i0,O -M ip iL i log i

2 cp
Fig. 8.17 Corrosion conditions of passive metals with a critical passivation current density higher
than the oxygen limiting current density
particular the Parthenon, is due to the criminal way in which marble ele-
ments were assembled with unprotected iron inserts.”
This type of attack, unfortunately, also affected Italian artefacts. In an
article entitled “Restoration of the Cathedral” (in La lettura, No. 1, 1936,
pp. 61–65, Milan, Italy), Carlo Emilio Gadda, an Italian writer, wrote: “At the
top of the Duomo di Milano, a harmonious command gathered and lined up
on the aligned cusps: a Donatellian cohort of saints, white martyrs […] and
Filipino-designed ogives for all the dreams and prayers over the centuries. At
the moment, the ogives are not a cause of concern, but the saints are
anchored to the spire’s capital through an iron pin (which sustains them like
a plinth). The weather, filtering through the commissure support, is causing
the iron to oxidize and swell up. By doing so, the plug has functioned as a
wedge and has cracked and sometimes split the pedestal: theoretically, the
saints’ statues can fall off with a stronger than usual gust of wind and the
disintegration of the specific section. […] The same occurrence is prevalent
in other decorative elements. The specious fastigium with ogival arches,
ending in an acute tasselled triangle, interspersed with cusps (the pediment
which in jargon is called “falconatura”) is maintained by a continuous key
iron ligament: this key or pass-through, like a long stick on which stuffed
birds of gentle beak to lardons and sage leaves were alternately placed, has
swelled over the years like rusty iron forgotten in roofs and is splitting the
load-bearing parts of the ornamentation’s statically vital points. This makes
it necessary to change the tunnel elements: iron is the Cathedral’s disease.”
Today titanium is chosen for metal inserts to be used on important works,
not only for its excellent resistance to corrosion but also for its coefficient of
expansion approximately equal to that of stone and about half that of aus-
tenitic stainless steels. These are, however, employed for the consolidation of
historic buildings or for the scheduling of hangings to a building outer
surface.
Game of Triangles
The three vertices (A, B and C) of an equilateral triangle are marked on a
paper together with a fourth point denoted by P1 in the middle of the triangle.
Now, pull a random vertex among A, B and C. Let’s suppose that we select
A. We then connect the point P1 with A, and identify the midpoint of the
segment P1-A which we call P2. Let’s make another extraction. Suppose that
this time we select B. Draw then the point P2 with B and identify the mid-
point of the segment P2-B, which we call P3. Continuing with the extractions,
we identify the points P4, P5, P6, P7, P8, P9, P10, P11, P12…… Pn. Once
scored within the ABC triangle, there should be a sufficiently large number of
points and once the first 8 points P1 to P8 are deleted, the result is not a
chaotic set of points, as would be expected. Instead, we get the Sierpinsky
triangle, which is a fractal figure spotted by Sierpinsky in 1915 (Fig. 8.18).
And what does corrosion matter?
Curiously, a metallographic etching of the plane (1 1 1) of a monocrystal
of silver (Fig. 8.19) looks like the Sierpinsky fractal.
Fig. 8.18 Fractal Sierpinsky triangle
Fig. 8.19 Metallographic etching of the plane (1 1 1) of a monocrystal of silver
8:1 Since about 30 years, the exhaust of cars is made of stainless steel.
Previously, it was made of carbon steel and frequently suffered premature
perforation: for this reason, the material was changed. Make a corrosion
assessment, indicate the condition required for corrosion occurrence and try
to estimate the time-to-perforation.
8:2 The material selected for heat exchanger tubes in a food industry plant was
Ti. The choice was suggested on the idea to prevent food contamination by
metals. After six months of operating, tubes were perforated. Indicate pos-
sible causes for failure occurrence, if fluid process was slightly acidic.
8:3 To store concentrated sulphuric acid, carbon steel is used. Conversely,
transfer piping and pumps are made of stainless steel. Why? Estimate cor-
rosion rates.
8:4 Estimate the corrosion rate during an acidizing job carried out in an oil well
with a tubing made of low alloy steel if acidic solution is 20% HCl or 20%
formic acid at 50 °C. Compare the corrosion rates and suggest possible
strategies for such operating.
8:5 Suggest which metals can give working conditions represented in Fig. 8.14
by point ①, ② and ③ respectively.
8:6 Suggest which metals can give working conditions represented in Fig. 8.15
by point ①, ② and ③ respectively. Give a relationship with water velocity
for working conditions ①, ①′ and ①″.
8:7 Corrosion rate of steels in aerated waters depends on total dissolved solids,
TDS, although oxygen limiting current density does not. Give an explanation
and discuss how TDS affects corrosion rate.
8:8 Corrosion rate of cast iron in aerated waters is much lower than that for mild
steel. Give an explanation and explain by using Evans Diagrams.
8:9 A water-carrying pipe (100 mm in diameter) showed an average corrosion
rate of 0.2 mm/year. What is the expected corrosion rate in an extension
smaller pipe (50 mm in diameter) if exposed surfaces are clean (i.e., without
surface deposits) and cathodic reaction is oxygen reduction?
8:10 On the stay-vane in a water turbine drum the maximum corrosion rate was
found to occur at approximately 30 m/s. At even higher velocities the cor-
rosion rate was low. What is your interpretation?
8:11 A reinforced concrete structure is totally immersed in seawater. If rein-
forcements are active, calculate the corrosion rate due to oxygen reduction.
8:12 Comment and suggest the philosophy behind the techniques adopted for
preventing uniform corrosion listed below:
• Corrosion allowance, i.e., an extra thickness to be consumed within
design life, when expected/calculated corrosion rate is moderate
• Selection of appropriate metals (for example, stainless steel instead of
carbon steel for oxygenated low chloride containing waters)
• Environment conditioning by removing corrosive agents (for example by
de-oxygenation) or by injecting corrosion inhibitors
• Use of organic or metallic coatings or painting and/or cathodic protection
on structures exposed to soil and waters.
Bibliography 167
Bibliography
De Giovanni C (2017) Validation of a model Tafel-Piontelli for the calculation of corrosion rate of
metals in acidic solutions. Application to sweet corrosion of carbon steel. MS Thesis 2016–
2017, Politecnico di Milano
De Waard C, Lotz U, Milliams DE (1991) Predictive model for CO2 corrosion engineering in wet
natural gas pipelines. Corrosion 47(12):976
De Waard C, Lotz U, Dugstad A (1995) Influence of liquid flow velocity on CO2 corrosion: a
semi-empirical model, Corrosion, 95, paper n. 128, NACE, Houston, TX
De Waard C, Milliams DE (1975) Carbonic acid corrosion of steel. Corrosion 31(5):131
Lazzari L (2017) Engineering tools for corrosion. Design and diagnosis. European federation of
corrosion (EFC) Series, vol 68. Woodhead Publishing, London, UK
Kreysa G, Schütze M (eds) (2006) Carbonic acid, chlorine dioxide, seawater. In: DECHEMA
corrosion handbook, corrosive agents and their interaction with materials, vol 5. Wiley-VCH,
Weinheim
Kreysa G, Schütze M (eds) (2006) Chlorinated hydrocarbons. DECHEMA corrosion handbook,
corrosive agents and their interaction with materials, vol 8. Wiley-VCH, Weinheim
Kermani MB, Smith LM (eds) (1997) A working party report on CO2 corrosion control in oil and
gas production. Institute of Materials, London
Milano (in Italian)
Chapter 9
Macrocell Corrosion Mechanism
Rust in Peace… Polaris.

Megadeth
Abstract When a macrocell is formed in a corrosion process, an electrical field is

established in the environment because a net current flows from the anode to the
cathode, which are physically separated. This situation occurs in galvanic corrosion,
differential aeration, localized attacks such as pitting and crevice, and cathodic pro-
tection. Potential and current distributions are extremely important because they
determine the corrosion rate. Analytical solutions of electric fields exist only for very
simple geometry and simplified conditions. In the last two decades, the use of numerical
calculations based on Finite Element Methods (FEM) has overcome these difficulties.

https://doi.org/10.1007/978-3-319-97625-9_9
170 9 Macrocell Corrosion Mechanism
This Chapter gives an overview of macrocell electrical field and current distribution,
giving analytical solutions for both quantities in simple geometries, such as inside and
outside a pipe. In some of these geometries the throwing power is also evaluated.
9.1 Electrical Field in Uniform Corrosion
In uniform corrosion (Fig. 9.1), each point of the corroding metal surface is
simultaneously anode and cathode and, therefore, there is no net current flowing in
the environment. In other words, there are many minute microcells whose anodes
and cathodes are continuously and dynamically exchanging each other. The
working condition of the corroding system is represented by the Evans diagram as
the crossing point of anodic and cathodic curves. When measuring the potential,
there is one fixed value only, regardless the position of the reference electrode in the
electrolyte. In particular, as soon as the reference electrode is progressively moved
away from the surface, the potential does not change, as depicted schematically in
Fig. 9.2. According to this, an experimental confirmation for a uniform corrosion
condition is a constant and homogeneous potential mapping.
9.2 Electrical Field in a Macrocell
When a macrocell forms on a metal or bimetal surface, a potential distribution on

the exposed metal surface exists (the so-called potential mapping) and its influence
is extended within the electrolyte. Qualitatively measured, the potential changes as
a function of the increasing distance from the metal surface, as shown in Fig. 9.3.
Beyond a certain distance from the metal surface, the measured potential is constant
and it is called remote potential.
Uniform corrosion
Ecorr
Measured potential is constant

with distance from metal surface
Distance
Fig. 9.2 Potential trend with distance from a metal surface corroding uniformly
9.2 Electrical Field in a Macrocell 171
More generally, the electric field and all field-related problems are governed by
the Poisson-Laplace quasi-harmonic equation, which, for stationary phenomena
independent of time, assumes the general form1:
rðjrEÞ þ Q ¼ 0 ð9:1Þ
where E is potential function, Q is electric charge flux and j is conductivity. If j is

constant and independent of direction, Eq. 9.1 changes to:
jr2 E þ Q ¼ 0 ð9:2Þ
The derivative equation for an electrodic system becomes the current density:
i ¼ jrE ð9:3Þ
Based on Eq. 9.3, equipotential lines and current density lines are orthogonal to
each other.
9.2.1 Pure Ohmic Systems
In a purely ohmic conductor with resistivity q (q = 1/j), the term Q is nil and the
field equation is simplified to Laplace equation:
rðjrE Þ ¼ 0; or r2 E ¼ 0 ð9:4Þ
which gives Ohm’s law:
1 DE
i ¼ jrE ¼ rE ffi ð9:5Þ
q q
Boundary conditions are reduced to ∂E/∂n = 0, which means that insulated surfaces
do not exchange current.
1
Examples of field problems are: heat transmission (E = temperature, Q = heat, j = transport
coefficient), mass transport (E = pressure, Q = mass, j = transport coefficient) and the trans-
portation of current as in the case of cathodic protection, where E is electric potential, Q is
electrical charge and j is conductivity.
Ec
Macrocell corrosion
Eremote
Measured potential varies with

distance from metal surface
Ea
Distance
Fig. 9.3 Potential trend with distance from a metal surface where a macrocell works
9.2.2 Two-Electrode Macrocell
In a macrocell, there is an electrolyte and two or more electrode surfaces among

which the current is exchanged through electrode reactions, an oxidation reaction at
the anode and a reduction one at the cathode.
The system can schematically be divided into two distinct domains: the elec-
trolytic solution (the bulk) assumed to be a homogeneous ohmic conductor and the
double layer at the electrode surface. By assuming the double layer negligible, the
bulk is then governed by the Laplace equation, as an ohmic system:
r2 Ee ¼ 0 ð9:6Þ
where Ee is the electrolyte potential at the electrode–electrolyte interface given by:
Ee ¼ Em þ g ð9:7Þ
where Em is the potential of a metal surface, which is uniform and constant

(equipotential electrodes), and η is the overvoltage, which is positive for the anode
and negative for the cathode. Overvoltage η is function of current density, i, which
is exchanged with the electrolyte.
9.3 Current Distribution
Two types of current distribution are observed in electrochemistry: primary dis-

tribution, when the overvoltage is negligible and secondary distribution, when the
overvoltage applies.
9.3 Current Distribution 173
9.3.1 Primary Current Distribution
When overvoltage is negligible, Laplace equation solutions show that:

• Current distribution depends on geometry only, and not on electrolyte resistivity
• The ohmic drop is concentrated close to electrodes. As a rule of thumb, the
smaller the electrode, the higher the electrode ohmic drop contribution.
Current flows in the electrolyte from anode to cathode. The ohmic drop of a
general flux tube, nth, is given by:
Z Z
dL dL
Wohm;n ¼ In Rn ¼ In q ¼ in Sq ð9:8Þ
S S
n n
where Rn is electrical resistance, In is circulating current in flux tube nth of length

L and section S. Both in and S vary with L.
Table 9.1 reports Laplace equation solutions to calculate the primary current
distribution for simple geometry; for more details refer to Kasper (1940), Wagner
(1952) and Newman (1974).
By comparing two flux tubes, which have the same ohmic drop because over-
voltage is negligible, the current density ratio is a function of geometry, only:
Wohm;1 ¼ Wohm;2 ð9:9aÞ

R dL
i1
ffi R2 S ð9:9bÞ
i2 dL
1 S
Generally, with an increase in flux tube length, there is a decrease in current density
and therefore, the system is characterised by poor throwing power. Conditions of
uniform
R primary distribution are created only by particular geometries where the
term dL=S is constant for all current paths, that is, in practice, when electrode
systems are made of large parallel plates, concentric spheres or coaxial cylinders.
9.3.2 Secondary Current Distribution
When electrode polarisation is established, solution of Laplace equation has to take

into account boundary conditions between the overvoltage and the current density.
In general, the secondary current distribution can be expressed as a function of the
following type:
Table 9.1 Primary current distribution for simple macrocell geometry
174
Potential Current Resistance

Parallel plates Cathode Y Ez ¼ q I Sz Uniform R ¼ q SI
(large surface area) P(x,y) Ex;y ¼ const ia ¼ ic ¼ SI
X
d = distance from plates d Z
S = surface area of plates Anode
Cathode

Spheric 1 Uniform q 1
Er ¼ q4pI ra 1r I
R ¼ 4p ra r1c
(concentric spheres) ia ¼ 4pI r2 ic ¼
a 4p rc2
R ffi 4pqra if ra rc
ra; rc = radius of two spheres
r = distance from centre
Anode
Cylindrical Er ¼ 2pqIL ln rra Uniform R ¼ 2pq L ln rrca

(coaxial cylinders) I
ia ¼ 2p IL ra ic ¼ 2p L rc
L rc
h i
Infinite plate (cathode) qI z NOT uniform R ffi p2qd
Ez ¼¼ 2p d 2 z2
(small anode at distance d on Z axis) imax ¼ 2pId2
r = distance of point P (x, y) from anode 3
d
projection i ¼ imax pffiffiffiffiffiffiffiffiffiffi
2 2
d þr
þz
Infinite plate (cathode) Ez ¼ qp LI ln ddz NOT uniform RL ffi pqL
(linear anode at distance d on Z axis and infinite ðd þ zÞ2 þ x2
q I imax ¼ p1d LI if d anode
2
Ey;x ¼ 2p L ln ðdzÞ2 þ x2
length) ix ffi imax d2 dþ x2 diameter
r = distance of point P (x, y) from anode
projection
Flat disk Ed ffi 4pqId Approximately R ffi 4pqro

(cathode radius ro) with ro d uniform
qffiffiffiffiffiffiffi2ffi
Anode at infinite distance 1ro
d = distance from disk
i ffi 2pI r2
o r2 o
9 Macrocell Corrosion Mechanism
9.3 Current Distribution 175

i dg
¼ f C; q; ð9:10Þ
iav di
where iav is the average current density, C a geometric factor, dη/di the overvoltage
function and q the electrolyte resistivity.
Therefore, unlike primary distribution, the secondary distribution does not depend
on geometry only and is, in particular, electrolyte resistivity dependent. As a
general conclusion, secondary distribution is more uniform than primary, because
overvoltage effects that spread current distribution overlap geometric factors
determining the primary distribution.
When the cathodic reaction is hydrogen evolution, overvoltage is low (Tafel
slope is about 120 mV/decade) so that current distribution is closer to the primary
than the secondary distribution. Conversely, when the cathodic reaction is oxygen
reduction, overvoltage is much higher in the order of 1 V, so that secondary dis-
tribution prevails. This typically occurs in galvanic corrosion and cathodic pro-
tection in natural environments, especially in low resistivity solutions such as
seawater, where overvoltage largely exceeds ohmic drop.
9.4 Throwing Power
The term throwing power refers to the ability of the current to reach areas distant
from anodes. It is thus related to both primary and secondary current distributions.
A macrocell generally has poor throwing power, although for different reasons: in
high resistivity electrolytes because primary distribution applies and in low resis-
Rtivity electrolytes because of geometry (reduction of the term S in the integral
dL=S).
To calculate, or rather, to estimate the throwing power, ohmic drop, DV, settled
in the electrolyte must be considered assuming constant and uniform overvoltage
contributions: in other words, the driving voltage available for overwhelming the
ohmic drop in the electrolyte is considered known. Based on this assumption, the
ohmic drop can be written as follows:
Z
DV ¼ I R ¼ q in dL ð9:11Þ
n
where symbols are known. Throwing power, Lmax, as the maximum distance
between the two electrodes assuming a constant current density, i, within the
electrolyte, can be obtained from Eq. 9.11 and approximated to the following two
forms:
DV
Lmax ffi k ð9:12aÞ
qi
sffiffiffiffiffiffiffiffiffiffiffiffiffi
DV /k
Lmax ¼k ð9:12bÞ
qi
where /k is the characteristic dimension and k is an appropriate constant for each

geometry. Table 9.2 summarizes the empirical equations possibly used for the
calculation of throwing power for typical geometries.
9.5 Typical Geometries
Equations reported in Table 9.2 for simple typical geometries, such as inside a pipe,
on a plate or on external surface of a pipe, which deals with pitting, crevice,
differential aeration and galvanic corrosion, as well as galvanic anode cathodic
protection systems, are obtained in the following paragraphs, assuming a uniform
cathodic current density, ic.
9.5.1 Inside a Pipe
With reference to Fig. 9.4, the current supplied by the anode that crosses the pipe
section is a function of the distance from the anode, according to the following
expression:
Ix ¼ ip£ðLmax Lx Þ ð9:13Þ
Table 9.2 Throwing power Geometry Throwing power

for typical macrocell
geometry (from Lazzari 2017) Pitting on a plate like geometry Lmax ffi DV
q
2qi
ffiffiffiffiffiffiffiffiffiffiffiffiffi
2DV£pit
Lmax ffi qi
qffiffiffiffiffiffiffiffiffiffiffiffiffi
Inside a pipe DV£pipe
Lmax ffi 2qi
Outside a coated pipeline Lmax ffi DV

qffiffiffiffiffiffiffiffiffiffiffiffiffi
2qi
DV£pipe
Lmax ffi 10 qi
Lmax: Throwing power (m); /pit: diameter of the localised

corrosion attack (m); /pipe: diameter of the pipe (m); i: cathodic
current density (A/m2); q: resistivity (X m); DV: ohmic drop (V)
Applicable conditions: 1 < q (X m) < 103; 0.01 < i (A/m2) < 1
9.5 Typical Geometries 177
Pipe
Anode
Lx L max
Fig. 9.4 Throwing power inside a pipe
where Ix is current that crosses the tube section at distance Lx, i is uniform current
density over the pipe’s internal surface, / is internal diameter and Lmax is maximum
distance or throwing power, which can be derived taking into account that at a
distance Lx from the anode, the ohmic drop and resistance are given by:
@V ¼ Ix @R ð9:14aÞ
q
@R ¼ @L ð9:14bÞ
S
where q is electrolyte resistivity and S (=¼ p /2) is the section area. By substituting
I and ∂R, it changes to:
4qip£ðLmax Lx Þ 4qiðLmax Lx Þ
@V ¼ @L ¼ @L ð9:15Þ
p£2 £
Integrating the expression from 0 to DV (ohmic drop) with L between 0 and

Lmax, Eq. 9.15 becomes:
2qiL2max
DV ¼ ð9:16Þ
£
From Eq. 9.16 Lmax can be calculate:

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DV£pipe
Lmax ffi ð9:17Þ
2qi
where /pipe is the internal tube diameter or equivalent tube diameter in the case of
different cross section fluxes.
9.5.2 Outside a Pipeline
The throwing power can be estimated by assuming a spherical electrical field as

depicted in Fig. 9.5. Like in the Wenner method measurement, as illustrated in
Chap. 19, where the electrical field in considered hemispherical, the following
linear relationship applies:
DV ffi kqiLmax ð9:18Þ
where DV (mV) is the driving voltage totally consumed as ohmic drop in the
electrolyte, i (mA/m2) is cathodic current density (assumed constant), q (X m) is
electrolyte resistivity, Lmax (m) is throwing power and k (adimensional) is a
constant.
The throwing power, Lmax, is given by:
DV
Lmax ffi ð9:19Þ
2qi
The constant k is often taken as being equal to 2, as FEM simulations confirmed

for a pipeline in electrolytes with resistivity greater than 1 X m and cathodic current
density greater than 0.1 mA/m2.
A more general approach can start from Eq. 9.17, then introducing the pipeline
diameter, /pipe, as characteristic dimension. From FEM simulation, the equation
can be approximated to the following:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DV£pipe
Lmax ffi 10 ð9:20Þ
qi
This equation is applicable under the following conditions: pipeline diameter:

0.1 < /pipe (m) < 1; electrolyte resistivity: 1 < q (X m) < 1000; cathodic current
density: 0.01 < iC (A/m2) < 1.
Lx
Lmax
Cathode
Anode
Current flux diameter Current flux diameter
Fig. 9.5 Throwing power outside a tube

9.5 Typical Geometries 179
9.5.3 On a Plate
Two approaches can be adopted: (1) one based on the assumption that the electrical
field is hemispherical around the anode as in the case of pitting corrosion (as shown
in Fig. 9.6); (2) one based on the evaluation of the ohmic resistances on both sides,
anode and cathode.
Method # 1
Similar to a pipeline, throwing power can be estimated by assuming a spherical
electrical field around the anode (for instance a pit) as shown in Fig. 9.6; taking into
account FEM simulations, the following can be obtained:
DV
Lmax ffi ð9:21Þ
kqi
where DV (mV) is the driving voltage totally consumed as ohmic drop in the electrolyte,
i (mA/m2) is cathodic current density (assumed constant) and q (X m) is electrolyte
resistivity. The constant k is often taken as being equal to 2, as FEM simulations
confirmed for electrolytes with resistivity in the range 1 < q (X m) < 1000 and current
density iC in the range 0.01 < iC (A/m2) < 1.
Method # 2
By this second approach, let’s assume that the anode (e.g. a pit) is a flat disk with
diameter / fixed on a plate working as the cathode and the electrolyte has a large
domain. The macrocell current flows from the anode, a circle-shaped area, to the
cathode with the radius equal to the throwing power, Lmax, as shown in Fig. 9.6.
The ohmic drop, DV, already given in Eq. 9.16, is given by two terms physically
located at the electrodes (the smaller the electrode, the closer the ohmic drop to the
electrode).
The resistance of a disk-shaped anode can be approximated to the following:
q
Ra ffi ð9:22Þ
2p£
where q is electrolyte resistivity and / is anode diameter. The resistance of the

cathode can be expressed by a similar equation also because of a disk-shaped type
with a diameter of twice the throwing power. As / is generally much smaller than
Fig. 9.6 Throwing power on

a plate Cathodic area
Anodic area
the expected throwing power, Lmax, only the ohmic drop at the anode applies,
therefore:
q
DV ¼ IR ffi I ðRa þ Rc Þ ffi I ð9:23Þ
2p£pit
The current, I, can be easily calculated by assuming the cathodic current density
as constant:
I ffi ipL2max ð9:24Þ
and
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 DV£pit
Lmax ffi ð9:25Þ
qi
Accordingly, the throwing power depends on pit size, electrolytes resistivity and
cathodic current density (1 < q (X m) < 1000; 0.01 < iC (A/m2) < 1).
9.6 Maximum Surface Area Ratio
In a macrocell, throwing power inherently defines the surface area ratio. As

experience has proved, parameters determining the throwing power affect the sur-
face area ratio setting up the macrocell. Accordingly, a similar relationship used for
throwing power applies for maximum surface area ratio as follows:
sffiffiffiffiffiffiffiffiffiffi
Sc Sc DV
ffi 1þ ffik ð9:26Þ
Sa max Sa max q iC
where symbols are known. In near neutral-to-alkaline electrolytes the cathodic

process is oxygen reduction, accordingly the cathodic current density is the oxygen
limiting current density, iL (0.01 < iL (A/m2) < 1), and the constant k (m−1/2) is
about 20 when ohmic drop DV is expressed in V and resistivity q is X m
(1 < q < 1000).
9:1 Consider a macrocell mechanism on a metal surface with formation of anodic

and cathodic zones. How does the potential change by increasing the dis-
tance from the metal surface where the macrocell works?
9:2 What is the difference between primary and secondary current distribution?
9:3 Consider the statement: “when the cathodic reaction is hydrogen evolution,
current distribution is closer to the primary than secondary distribution.
Conversely, when the cathodic reaction is oxygen reduction, secondary
current distribution prevails”. Explain.
9:4 What is the throwing power? What is the effect of electrolyte resistivity and
current density on throwing power?
9:5 Evaluate the throwing power of a macrocell, which can setup in a heat
exchanger between the tube-plate made of cupronickel and the tubes made of
titanium. The fluid is aerated seawater. By painting internally the titanium
tubes, how does the throwing power change? Derive a relationship as
function of the coating efficiency.
9:6 Estimate the driving voltage of a galvanic corrosion macrocell for the fol-
lowing case studies in seawater:
• Carbon steel and copper
• Zinc and carbon steel
• Carbon steel and stainless steel.
For each case study, indicate the anode, the cathode and the pertinent
reactions.
9:7 Estimate the driving voltage of the corrosion macrocell established in the
crevice and pitting corrosion of stainless steel in seawater. Compare the value
with the driving voltage of a galvanic corrosion macrocell between carbon
steel and stainless steel in seawater (previous exercise).
9:8 A pipe system carrying aerated water consists of a section made of stainless
steel separated from a carbon steel section by a polymeric composite spool,
0.1 m long. Try to determine the throwing power on the macrocell on either
anodic side or cathodic side. (Note. Both section are connected to the
grounding system). What is the influence of the nature of the metals
involved? What would be the difference if metals are copper and aluminium?
9:9 Calculate the throwing power inside tubes of a heat exchanger, of ½ inch in
diameter, when the fluid is seawater (resistivity 0.2 X m) and fresh water
(resistivity 20 X m), considering two separated case studies: tubes made of
noble metal and made of a low nobility metal, then corroding.
9:10 Estimate the maximum surface area ratio, (Sc/Sa)max, for the macrocell
established by a galvanic coupling in soil between carbon steel and a copper
made grounding system. Assume a well-aerated soil.
Bibliography
Lazzari L, Pedeferri P (2006) Cathodic protection. Polipress, Milan, Italy

Lazzari L, Pedeferri P (1981) Protezione catodica. CLUP, Milano, Italy
Lazzari L (2017) Engineering tools for corrosion. Design and diagnosis. European federation of
corrosion (EFC) Series, vol 68. Woodhead Publishing, London
Kasper C (1940) The theory of the potential and the technical practice of electrodeposition. Trans
Electr Soc 77:365–384
Newman J (1974) Mass transport and potential distribution in the geometry of localised corrosion,
NACE-3, 45–61, Houston TX
Wagner C (1952) Contribution to the theory of cathodic protection. J Electr Soc 99:1
Chapter 10
Galvanic Corrosion
The world is holding back

The time has come to galvanize.
The Chemical Brothers
Abstract Galvanic corrosion occurs when two or more metals with different
practical nobility are electrically connected and immersed in the same environment:
the less noble metal experiences an increase in corrosion rate due to the presence of
the more noble one. The effects of this coupling on the less noble and the more noble
metal are discussed in this chapter and represented by Evans diagram. The main
factors influencing the extent of corrosion rate increase are analysed: availability of a

https://doi.org/10.1007/978-3-319-97625-9_10
184 10 Galvanic Corrosion
driving force for galvanic corrosion, its possible dissipation in cathodic overvoltage
and ohmic drop in the electrolyte, ratio between cathodic and anodic areas. Finally,
prevention of this localized corrosion phenomenon is briefly described.
10.1 Effects on Metal Corrosion
Galvanic corrosion, also called bimetallic corrosion, occurs when two metals
immersed in an electrolyte are in electrical contact and are characterized by a
different practical nobility, i.e., a different free corrosion potential. The less noble
metal, M, with more negative potential, works as anode and its corrosion rate is
accelerated by the coupling (Fig. 10.1). The noble metal, N, with more positive
potential, behaves as cathode, hence its corrosion rate decreases up to a halt. In
addition, materials with electronic conductivity can work as cathode, such as
magnetite that forms near welds, calamine in hot rolling, magnetite in boilers, and
also graphite and sulphides in industrial processes. A current, I, so-called galvanic
current or macrocouple current, circulates inside the electrolyte from less noble
metal to more noble and within metallic circuit in opposite direction (Fig. 10.2).
The first mention of the galvanic effect can be dated on 1799 by Giovanni
Fabbroni, who wrote on Journal de Physique: “[…] I have observed that the alloys
used for soldering roof copper plates of the Observatory of Florence have rapidly
transformed, altered to a white oxide, only at the junctions […]”. A few years later
on 1805, Davy suggested to prevent corrosion attack through a galvanic coupling,
by which cathodic protection was born.
Besides an acceleration of the corrosion rate of less noble metal, there may be
side effects such as:
• Possible passivation of less noble metal (titanium in reducing environments)
• Hydrogen evolution on more noble metal with possible hydrogen embrittlement
of susceptible metals (high strength steels, titanium)
• Reduction of oxides, sulphides or other chemical species present on cathode
surface.
By introducing the surface area of the anodic and cathodic metals, SM and SN
respectively, referring to Fig. 10.3, the macrocell current, I, is equal to the anodic
current exiting the less noble metal, IM, and to the cathodic current, Ic:
I ¼ IM ¼ Ia ¼ Ic ð10:1Þ
Fig. 10.2 Galvanic corrosion

I
of metal M (less noble) by
coupling with more noble
metal N
M N
10.1 Effects on Metal Corrosion 185
(a) (b) I a = Ic
M or N
C C
A A C
C C
(c) (d) 
I
1 2
N Ic Ia Ic Ia
M N
M
C C A A
A C C A C A
C C A A
Fig. 10.3 Scheme of galvanic current between metal M, less noble, and metal N, more noble
The anodic current exiting the metal M is:
Ia ¼ icorr SM ð10:2Þ
where icorr is the corrosion rate on the less noble metal M of exposed surface SM.
The cathodic current is the product of the cathodic current density, ic, by the total
surface where the cathodic process occurs:
Ic ¼ ic ðSM þ SN Þ ð10:3Þ
By inserting Eqs. 10.2 and 10.3 in Eq. 10.1, the corrosion rate on the less noble
metal M in a galvanic coupling is obtained:
icorr ¼ ic ð1 þ SN =SM Þ ð10:4Þ
Galvanic corrosion rate is proportional to the cathodic current density, ic, and to
the surface area ratio (SM + SN)/SM. When SN SM the ratio approximates to
SN/SM. To show the practical effect of surface area ratio, Evans proposed his
students to carry out the experiment illustrated in the following box.
Figures 10.4 and 10.5 show two examples of galvanic attack in industrial
applications caused by the coupling with more noble materials, as graphite used as a
gasket and magnetite that forms near welds.
Fig. 10.4 Galvanic corrosion of stainless steel, AISI 304 grade, coupled with graphite in aerated
flowing acid solution
Fig. 10.5 Galvanic corrosion of weld in the presence of a magnetite layer

10.1 Effects on Metal Corrosion 187
Evans’ Experience on Galvanic Corrosion

To give students a practical demonstration of the effect of surface area ratio in
galvanic corrosion, Evans invited them to carry out the following experiment.
Prepare a carbon steel plate of surface area 1 m2, one face coated, and dip
it in seawater in a harbour zone, practically in stagnant condition. The mass
loss after 1 year exposure is 780 g. Corrosion rate is then 100 lm/year
(the reader is asked to verify this calculation).
Now, prepare another twin carbon steel plate and apply a gold plating on
half of the bare surface, then dip it in same harbour zone. The mass loss after
1 year exposure is as before, 780 g. Root cause is because of same oxygen
availability on 1 m2 plate (no matter if the surface of the plate is half steel
and half gold). But, corrosion rate of steel is 200 lm/year.
Now, prepare a third carbon steel plate with ¾ of steel bare surface gold
plated and again dip it in the same harbour zone. The mass loss after 1 year
exposure is again 780 g. So the corrosion rate of exposed steel (1/4 of the
1 m2 surface area) is 400 lm/year.
And so on, by preparing other carbon steel plates, gold plated for 7/8 or 9/
10 of the bare surface, then obtaining a corrosion rate 8 times and 10
times higher, respectively. The influence of the surface area ratio was then
evident.
Silverware Cleaning
A curious household beneficial effect of galvanic coupling is the method used
to clean silverware which blackens by the presence of traces of H2S in the
atmosphere to form a thin film of brownish silver sulphide. The procedure
consists of putting silverware in a sodium bicarbonate solution in an alu-
minium pot; to speed up the process, near boiling water is suggested. After a
while, black spots disappear magically, even in recesses.
What happened?
Simply, the effect of the galvanic coupling between aluminium, the pot,
and silver, the more noble metal, on which the cathodic reaction (hydrogen
evolution) occurs then reducing silver sulphide to silver; on the anodic side a
slight surface corrosion of aluminium takes place. Instead of an aluminium
pot, which is now difficult to find in a kitchen, then an aluminium foil on the
bottom of any pot type can be used. To increase the cleaning effect, mag-
nesium can be used, if available, instead of aluminium: still it is a matter of
galvanic coupling.
E
Global
Eeq,H cathodic
2
2H + 2H +
+2 curve
e- +2
e-
H H
2 on 2 on
Zn Pt 3 2
Ecorr
4
1
E’corr 2+ +
-
2e
Zn
Eeq,Zn Zn
iH i’corr iH icorr log i

2,Zn 2,Pt
Fig. 10.6 Simplified Evans diagram for galvanic coupling of Zn and Pt in an acid solution
10.2 Galvanic Effects on Less Noble Metal
Let’s consider a galvanic coupling in acidic solution between an active metal, for
example zinc, and a more noble metal, for example platinum. On zinc, both anodic
and cathodic processes occur simultaneously, whilst on platinum only a cathodic
process takes place. A simplified E-logi plot, shown in Fig. 10.6, can conveniently
represent corrosion conditions, set before and after coupling, where current coin-
cides with current density and ohmic drop is disregarded.
Point ① represents free corrosion condition (i′corr and E′corr) of zinc before
coupling, point ② corrosion condition (icorr and Ecorr) of zinc after coupling. The
final condition is obtained by summing cathodic current density ③ on platinum
and the one of point ④ on zinc, which equals anodic current density on zinc
(condition of electro-neutrality). The dotted line represents the global equivalent
cathodic curve. It appears that, after coupling, corrosion rate of zinc increases from
i′corr to icorr and hydrogen evolution splits on platinum and zinc, where on the latter
it decreases (compare ① and ④).
Let’s consider now an active–passive metal as titanium coupled with platinum in
a de-aerated acidic solution. As for previous case study, Fig. 10.7 shows a sim-
plified E-logi plot of corrosion conditions before, point ①, and after coupling, point
②. Titanium in point ① is on active zone, showing a corrosion rate, i′corr; in point
② titanium is in the passivity zone and the corrosion rate, icorr, drops to passivity
current (at least, one order of magnitude lower). According to this result, in this case
the galvanic coupling produces a protection effect, quantified by the difference
i′corr − icorr. Point ③ and point ④ indicate hydrogen evolution on platinum and
titanium, respectively. Potential moves from E′corr to Ecorr.
In summary, by a galvanic coupling with a noble metal, corrosion rate of an
active less noble metal increases, conversely the one of an active–passive metal
may decrease.
10.2 Galvanic Effects on Less Noble Metal 189
Ti
Eeq,H
2
Ecorr 2
4 2 3
H+
+2
e-
H
2 on
Ti
1 2H +
E’corr +2
e-
H
Eeq,Ti 2 on
Pt
iH iH icorr i’corr log i

2,Ti 2,Pt
Fig. 10.7 Simplified Evans diagram for galvanic coupling of Ti–Pt in deaerated acid solution
10.3 Galvanic Effects on More Noble Metal
Let’s consider an opposite case study as seen above, where a metal, for example
iron (i.e., mild steel) is coupled with a less noble metal, for example zinc. On iron,
both anodic and cathodic processes occur simultaneously, while on zinc the anodic
process takes place, only.
Again, assuming that current coincides with current density, the simplified E-
logi plot of Fig. 10.8 refers to the galvanic coupling in an acid solution. Point ①
represents free corrosion condition (i′corr,Fe and E′corr) of iron before coupling, point
② corrosion condition (icorr and Ecorr) of iron after coupling. The final condition is
E
2H + 2H +
+2 +2
e- e- e
-
H 2+ +2
H Fe
2 on 2 on
Z Fe Fe -
E’
n 2+ + 2e
corr Zn
1 Zn
3 4 2
Ecorr
5
Eeq,Fe
Eeq,Zn
icorr,Fe i’corr,Fe icorr log i
Fig. 10.8 Simplified Evans diagram for galvanic coupling of Fe–Zn in an acid solution
obtained by summing anodic current density ③ on iron and the one of zinc, point
④, which equals cathodic current on iron (condition of electro-neutrality). The
dotted line represents the global equivalent anodic curve (of iron plus the one of
zinc). It results that, after coupling, corrosion rate of zinc increases and corrosion
rate of iron decreases (compare ① and ③).
In practice, by changing the anodic to cathodic area ratio, dotted line can cross
cathodic line in point ② at a potential below the equilibrium potential of iron: when
this condition sets up, the corrosion rate of iron zeros.
Figure 10.9 shows the iron-zinc galvanic coupling in oxygen-containing neutral
solution: the corrosion condition changes from ① (free corrosion of iron) to point
② that is close to free corrosion condition of zinc, so that corrosion of iron stops.
This is the so-called immunity condition that is achieved by applying cathodic
protection (see Chap. 19).
When the more noble metal is active–passive, again coupled with zinc and
operating in high oxidizing condition, as shown in Fig. 10.10, potential moves from
corroding point ① to point ③ within the passive range, established by the cor-
rosion potential of zinc (point ②). At point ③ corrosion rate, icorr,M, is the passivity
current density, hence negligible. This effect is named cathodic protection by
passivity (see Chap. 19); typical examples are the galvanic coupling of stainless
steel with zinc or also iron in seawater and galvanic coupling between passive steel
and zinc in concrete.
Figure 10.11 shows the hypothetical simplified E-logi plot when the active–
passive metal works in passive state (point ①) and is coupled with a less noble
metal as Zn. Operating condition of this galvanic coupling would be point ②, at
which cathodic process occurs on active–passive metal, and global anodic process
would be the sum of corrosion rate of zinc (point ③) and the one of noble metal in
E O2 + 2H
2O + 4e -
4OH -
-
2+ + 2e
Fe
Fe
E’corr 1
-
2+ + 2
e
Eeq,Fe Zn
Zn
Ecorr
2
Eeq,Zn
i’corr icorr log i
Fig. 10.9 Simplified Evans diagram for galvanic coupling of Fe–Zn in a neutral aerated solution
10.3 Galvanic Effects on More Noble Metal 191
E O2 + 2H
2O + 4e -
4OH -
1
E’corr
-
2+ + 2e
Zn
3 2 Zn
Ecorr
icorr,M i’corr icorr= icorr,Zn log i
Fig. 10.10 Principle of cathodic protection by passivity through a galvanic coupling with a less
noble material
1
E’corr O2 + 2
H2 O + -
4e
4OH -
True
behaviour
5 - 4
Ecorr e
M2 + 2
+
M - 3 2
2+ 2e
Zn Zn +
icorr,T i’corr icorr,M icorr log i
Fig. 10.11 Simplified Evans diagram for a galvanic coupling between passive metal and a less
noble metal
active condition (point ④). This representation is misleading since it implies

that the passive metal would become active and corrosion rate would increase from
i′corr to icorr,M, while the noble passive metal remains passive because the alkalinity
produced by the cathodic process (i.e., oxygen reduction) impedes the activation,
hence the corrosion condition moves to point ⑤, icorr,T. Accordingly, the dotted line
represents the true behaviour.
10.4 Galvanic Coupling Representation by Evans

Diagrams
Simplified Evans diagrams considered so far in this Chapter (Figs. 10.6, 10.7, 10.8,
10.9, 10.10 and 10.11) are used because they help understand the effects of a
galvanic coupling. However they are misleading. In fact, when measuring the
potentials of the metals involved in the coupling, either in laboratory or on field, the
operating conditions predicted by these representations, i.e. measured working
potential, do not fit. In fact in all environments, even in high conductive ones as
seawater, the potential of the two coupled metals is different and never given by the
crossing point of anodic and cathodic curves.
There is a twofold reason: first, anodic and cathodic current densities cannot be
considered equal because their ratio, ic/ia, is as a minimum 2. Second, and most
important, the macrocell current established by the galvanic coupling causes an
ohmic drop, IR, in the electrolyte; in other words, to have the macrocell current
circulation in the electrolyte, the potential of the cathode (positive pole of the
established cell) must be higher than the anode (negative pole). The set up of the
ohmic drop in the electrolyte determines the designation of the two following
parameters: the potential of the anodic metal, EAN, and the potential of the cathodic
metal, ECATH, after the galvanic coupling.
In the following graphs (Figs. 10.12, 10.13, 10.14, 10.15, 10.16 and 10.17) the
real working conditions are reported. In each graph, only involved anodic and
cathodic curves are reported. Highlighted points have the following meaning:
• Point 1: free corrosion potential of more noble metal
• Point 2: free corrosion potential of less noble metal
• Point 3: corrosion potential of more noble metal after coupling, ECATH
• Point 4: corrosion potential of less noble metal after coupling, EAN.
3
ECATH
IR
EAN
4
2
icorr,Zn iGC,Zn log i
Fig. 10.12 Simplified Evans diagram for galvanic coupling of Zn and Pt in an acidic solution
taking into account the ohmic drop
10.4 Galvanic Coupling Representation by Evans Diagrams 193
ECATH 3
IR
EAN 4
icorr,Ti iGC,Ti log i
Fig. 10.13 Simplified Evans diagram for galvanic coupling of Ti and Pt in de-aerated acidic
solution taking into account the ohmic drop
ECATH
3
IR
EAN 4
iGC,Fe iGC,Zn log i
Fig. 10.14 Simplified Evans diagram for galvanic coupling of Fe and Zn in an acidic solution
taking into account the ohmic drop
To calculate the potential difference between the two metals, which is also the
driving voltage, DV, of the cell, reference has to be made to Chap. 9. In short, the
following relationship applies:
2
Sc
DV ¼ ECATH EAN ¼ IR ffi ic q ð10:5Þ
k Sa
1
3
ECATH
4
IR
EAN
iGC,Fe iL iGC,Zn log i
Fig. 10.15 Simplified Evans diagram for galvanic coupling of Fe and Zn in a neutral aerated
solution taking into account the ohmic drop
E
1
3
ECATH
IR
EAN
4
2
ip = iGC,M iL iGC,Zn log i
Fig. 10.16 Principle of cathodic protection by passivity of an active–passive metal through a

galvanic coupling with a less noble metal
where symbols are known and k is a constant, about 20 m−0.5 for plate-like
geometry. It is important to note that when using this relationship, surface areas Sa
and Sc cannot be considered independent, as discussed in Paragraph 10.5.3.
10.4 Galvanic Coupling Representation by Evans Diagrams 195
3
ECATH
IR
4
EAN
ip iL log i
Fig. 10.17 Simplified Evans diagram for galvanic coupling of stainless steel and graphite
(example reported in Fig. 10.4) taking into account the ohmic drop
10.5 Four Main Factors
In summary, galvanic coupling depends on the following main four factors:

• Practical nobility which determines potential difference between coupled metals
• Overvoltage of cathodic reaction on more noble metal
• Surface area ratio
• Electrolyte conductivity.
10.5.1 Practical Nobility
The driving voltage set by the galvanic coupling is the difference between the two
free corrosion potentials in the environment, which depends on nature, composition
and structure of the metal, presence of oxide films or other compounds on metal
surface, composition, temperature and oxidizing power of the electrolyte. The rank
of practical nobility of metals depends on the environment to which the coupling is
exposed: aerated, stagnant or turbulence conditions. Table 10.1 shows the practical
nobility rank of metals in seawater. To illustrate how practical nobility varies in a
wide range as electrolyte condition changes, let’s consider a stainless steel
immersed in seawater:
• If seawater is aerated, stainless steel remains passive and free corrosion potential
is close to equilibrium potential of oxygen reduction process, then approaching
the equilibrium potential of copper; instead, as soon as corrosion starts, potential
drops to a more negative system, approaching the equilibrium potential of iron
Table 10.1 Ranking of metals in seawater based on practical nobility (from LaQue 1975)
More noble
Platinum Brass
Gold Hastelloy B (60 Ni, 32 Mo, 6 Fe, 1 Mn)
Graphite Nickel (active)
Titanium Tin
Silver Lead
Hastelloy C (62 Ni, 18 Cr, 18 Mo) Stainless steel (active)
Stainless steel (passive) Cast iron
Nickel (passive) Mild steel
Soldering alloy Cadmium
Monel (60 Cu, 40 Ni) Aluminium (commercially pure)
Copper nickel Zinc
Bronze Magnesium and alloys
Copper Less noble
• In seawater with low oxygen content or even deaerated, potential drops from a
noble value due to passive condition, then close to copper, to a value typically
close to active conditions, then close to iron, even if it is in passive state.
Mix-Ups
Metals may change position in the rank of practical nobility by changing
environmental conditions. In some cases, there may be a real reversal. There
are considerable potential variations from standard condition when anions
forming complexant or insoluble salts are present (thermodynamic issue, see
Chap. 3); also kinetics effects give similar changes. For example, in general,
zinc is less noble than iron and then protecting iron in a galvanic coupling
(i.e., by cathodic protection). However, at temperatures above 40 °C the
formation of an oxide with properties of a semiconductor makes zinc in
absence of chlorides more noble than iron, then causing corrosion rather than
protection of iron. Similarly, tin is generally cathodic against iron, instead in
presence of food substances which passivate iron and form complex with tin,
there is a reversal so that tin becomes anodic and iron cathodic. Similarly,
iron is less noble than copper, nevertheless in phosphate containing envi-
ronments iron passivates, then becoming more noble than copper.
Influence of Surface Condition
Sometimes, to predict galvanic corrosion, the practical nobility to be con-
sidered is not the one of initial surface condition, instead it is the stationary
one established by reactions occurring on early exposure stage. This is the
case of brass when dezincification takes place, so that surface composition
changes strongly, giving a thin copper-rich layer, with practical nobility as
10.5 Four Main Factors 197
copper. A similar behaviour occurs on grey cast iron in some electrolytes

where iron is selectively etched so that a graphite film forms on its surface.
The opposite occurs in case of local destruction of a surface film due to high
turbulence or abrasion effects, which brings active the initially passive metal,
hence changing practical nobility.
10.5.2 Cathodic Overvoltage on More Noble Metal
Catalytic properties that noble metals exert on the cathodic reaction influence the
corrosion rate in galvanic coupling. This is the reason why often passive metals
(which are covered with oxide films) are not very effective in accelerating the
galvanic attack of less noble metals because the most frequent cathodic process, i.e.,
oxygen reduction, takes place slowly. For example, let’s consider galvanic coupling
of commercial aluminium with copper or with stainless steel in seawater: although
copper and stainless steel show roughly same nobility (i.e., same free corrosion
potential), hence same driving voltage, the corrosion rate of aluminium is much
lower in stainless steel-aluminium coupling than in copper-aluminium one, for
about an order of magnitude. This different behaviour depends on different over-
voltage of oxygen reduction, which is much higher on stainless steel than copper;
instead, overvoltage on titanium is even higher than stainless steels and is much
lower on magnetite (iron oxide that forms a passive film on carbon steel).
10.5.3 Surface Area Ratio and Maximum Corrosion Rate
An important factor in defining corrosion rate in galvanic coupling is surface area

ratio, as Evans’ experience, reported in the box, clearly demonstrated. Accordingly,
the corrosion rate in the presence of a galvanic coupling, Crate,GC, is given by:
Sc þ Sa Sc
Crate;GC ¼ b ic ffi b ic ð10:6Þ
Sa Sa
where the conversion factor, b, in the case of iron is 1.2 (1 A/m2 = 1.17 mm/
year ≅ 1.2 mm/year); ic (A/m2) is the current density of the cathodic reaction, and
Sc and Sa are the cathodic and anodic surface areas, respectively.
However, unlike Evans’ experiment, surface area ratio is not always the one we
think or simply we measure, because it is determined by the electrical field setup by
the galvanic macrocell; in other words, it is determined by the throwing power,
Lmax, of the macrocell, as discussed in Chap. 9. It can be stated that the maximum
surface area ratio is given by Eq. 9.26 as follows (from Lazzari 2017):
sffiffiffiffiffiffiffiffiffiffi
Sc þ Sa Sc DV
ffi ffik ð10:7Þ
Sa max Sa max ic q
where DV (V) is ohmic drop or driving voltage (i.e., the practical nobility difference
of the two metals), q (X m) is electrolyte resistivity, ic (A/m2) is cathodic current
density and k is an experimental constant. By comparing Eqs. 10.6 and 10.7, it
results:
sffiffiffiffiffiffiffiffiffiffiffiffiffi
ic DV
Crate;GC ffik ð10:8Þ
q
Practical experiences and FEM simulations have shown that Eq. 10.8 is applicable
for the following intervals: 1 < q (X m) < 103 and 0.01 < ic (A/m2) < 1.
In summary, surface area ratio depends on:
• Driving voltage
• Cathodic current density which generally varies for oxygen limiting current
density in the range 0.01 < iL (A/m2) < 1
• Electrolyte resistivity (1 < q (X m) < 103)
• Geometry of the domain, through constant k, generally taken as 20 m−0.5.
10.5.4 Electrolyte Resistivity
As stated by Eq. 10.8 corrosion rate of a galvanic coupling depends strongly on

electrolyte resistivity; assuming the same driving voltage, corrosion rate decreases
as resistivity increases; for instance, in high resistivity electrolytes like fresh water
galvanic effects are often negligible, whilst in high conductivity ones like seawater
corrosion rate is at least two orders of magnitude greater.
Electrolyte resistivity determines also the throwing power, therefore the exten-
sion of the attack on the anodic (i.e., less noble) metal. As resistivity increases,
anodic and cathodic processes tend to localize close to the coupling boundary (low
throwing power) and the opposite occurs in high conductivity electrolytes (high
throwing power).
As a rule of thumb, resistivity influences galvanic coupling in an open domain as
follows:
• Distilled water (q 2000 X m or r 5 µS/cm): affected zones do not extend
beyond some tenths of a millimetre
• Fresh waters (q 20–50 X m or r 200–500 µS/cm): affected zones do not
extend beyond a few centimetres
• Seawater (q 0.2 X m or r 5 S/m): galvanic effect extends to distances of
the order of meters.
10.5 Four Main Factors 199
10.5.5 Geometry of the Domain
Besides electrolyte resistivity, domain geometry is another important factor

influencing galvanic corrosion: for example in small diameter tubes or thin film like
electrolyte, as it happens on atmospherically exposed surfaces, the extension of
affected (working) areas is greatly reduced; however, strong condensation in marine
atmospheres leads to a galvanic corrosion not negligible as it would be in less
aggressive atmospheres.
10.6 Prevention
With reference to Figs. 10.18, 10.19 and 10.20, prevention of galvanic corrosion is
achieved by:
• Avoiding dangerous couplings with a choice of metals close in scale of practical
nobility
• Separating coupled metals, for example, by insulating flanges
• Taking care that the anodic-to-cathodic area ratio is not unfavourable (Sa Sc)
• Applying paints on both surfaces or only on the cathodic one. Avoid painting of
anodic metal, only
• Applying cathodic protection.
Fig. 10.18 Example of More noble metal

galvanic corrosion control by Less noble metal
insertion of a sacrificial
replaceable unit
Replaceable unit
Fig. 10.19 Insulating flange

More noble metal
Insulating
Less noble metal
(a) (b) (c)

Less noble metal Less noble metal Less noble metal
Pitting
More noble metal More noble metal More noble metal
Fig. 10.20 Example of corrosion prevention by protective coatings: a correct; b correct;

c incorrect
Electrical insulation as prevention method for galvanic coupling is not always

easy to obtain in practice. For example, consider a pump and relevant piping. The
electrical contact takes place not only through the connecting flanges, but also
through the structural supports, other pipes and most likely through the grounding
system.
Painting may be used as prevention method, provided its application on cathodic
areas, i.e., more noble metal, or on whole coupling, i.e., both anodic and cathodic
areas. Painting of less noble metal only (as sometimes occurs in trying to protect the
zone that corrodes) is very dangerous because, in the presence of defects, surface
area ratio is largely unfavourable (Fig. 10.20c).
The Professor and Seadog

The writer heard this story from Professor Hoar during a lecture on galvanic
corrosion in Cambridge, UK, mid 1970s. As professor Hoar was a brilliant
actor, Pedeferri thought that the story could not be true, nonetheless very
instructive for students. In 1940 in Virginia, USA, in spite of echoes of war
coming from Europe, the owner of a wealthy tobacco farm decided to pur-
chase a 24-m long yacht, named Seadog, made of an exotic material for those
times: the monel, a nickel-copper alloy (about 65% Ni and 30% Cu). Indeed,
he could afford it.
Not to lose time while designing the boat, he started purchasing hull
sheets, meanwhile Pearl Harbor attack forced the U.S. to enter the war. Monel
became strategic material, so it was no longer possible to purchase rivets
made of monel and steel was then proposed and agreed. Since galvanic
corrosion was a concern, a professor of a nearby University was asked to
investigate the matter. The professor, scrupulously, connected a monel
sample with a rivet and measured the galvanic current once immersed in
seawater. Such current was small and then the professor concluded that
galvanic corrosion was acceptable and steel rivets would have solved the
problem for at least two decades. “It is enough” said the “tobacconist” and
the yacht construction began. The Seadog was built in record time, then
launched and after six weeks sank.
10.6 Prevention 201
Hoar concluded: “In front of the coast of Virginia, plates of monel of the
poor Seadog still lie”. What happened? The Professor perfectly measured the
current flowing between monel and steel, but the geometry or surface area
ratio was much different, so corrosion rate in seawater was some orders of
magnitude higher than what measured in laboratory. Truly, the story was
referred by Speller (1926) some years before with some small different details.
Draft Beer
This case study is taken from Fontana’s book (1986). In the 1950s in United
States, in beer brewery industry, although beer is not a particularly aggressive
solution, tanks were made of carbon steel, internally coated with phenolic
resin, to avoid contamination by corrosion products, which alter beer taste.
The protective coating served the purpose provided no mechanical damage
was present, especially on the bottom. To overcome this inconvenience, a
company decided to change the bottom only and not the wall of tanks, by
replacing phenolic resin coating with a stainless steel clad, AISI 304 grade.
After a few months of service, pinhole corrosion, never seen before, appeared
in a narrow band above the weld, near stainless steel, because of galvanic
corrosion through coating porosity and the bare stainless steel surface.
Galvanic Corrosion of Artefacts Exposed to the Atmosphere

In dry environment and in the absence of condensed water, as often happens
inside buildings, galvanic corrosion is not a concern for atmospherically
exposed artefacts. The iron crown kept in a reliquary in the Cathedral of
Monza, Italy, is an ideal example to prove it. The crown is a ninth century
artefact and, according to tradition, crowned the kings of Italy in the middle
age and Napoleon two hundred years ago. It consists of a circle of gold
studded with gems and diamonds, carrying inside a thin strip of iron, which,
according to tradition, was fashioned with one of the Holy Cross nails. (There
are many doubts about the nature of the metal because in 1985 it was found
that the nail is not magnetic, so it may not be iron but zinc or tin or silver;
nevertheless, we continue to believe in it). A perfect galvanic coupling, which
has never worked for a thousand and more years because exposed to dry
atmosphere: the iron strip is perfectly preserved so far.
Going from inside to outside the dome, things change. Figure 10.21 shows
a detail of a damage occurred on a monument dedicated to heroic soldiers
due to galvanic corrosion. In fact, to fix labels of soldier names, made of
bronze, carbon steel rivets were erroneously used. The rainwater film, made
acidic by pollution during ’60–’70 of XX century, produced a galvanic attack
of the rivet. The picture shows also the area that has worked as cathode.
Fig. 10.21 Example of galvanic coupling: a bronze plate fixed with carbon steel rivets
Particular and unique examples of galvanic corrosion of gilded bronze

artefacts exposed to the atmosphere are Marco Aurelio in Campidoglio,
Rome; the Grifo in Perugia; the doors of the Baptistery of Florence (two by
Ghiberti, one is named Paradise, and one by Pisano); the horses of Venice.
Indeed, these artefacts are batteries ready to work, although the driving force
is modest. Corrosion of bronze occurs at gold foil pinholes, but for almost
five centuries, no damage took place because corrosion products were
insoluble and protective by plugging the pinholes. Unfortunately, since ’50s
of 20th century, things have changed because due to acid rains corrosion
products became soluble. The writer in the mid-70s could see under the belly
of one of the horses of Venice, at that time still exposed in S. Marco Square,
blue corrosion products of copper sulphate, a clear sign of occurring corro-
sion. Although in the other mentioned cities the environment is less critical
than that of Venice, wisdom administrators decided to preserve such monu-
ments into a museum and copies were exposed.
Also the Statue of Liberty in New York suffered galvanic corrosion and a
repair was necessary in early 1990s. The copper sheets of the statue are
internally fixed to a carbon steel frame, which corroded due to the formation
of a layer of condensed water. Carbon steel was replaced with stainless steel,
then limiting the galvanic effect of the coupling.
10:1 What are the four main factors affecting galvanic corrosion?
10:2 Represent by means of Evans diagram the electrochemical free corrosion
condition of the following materials exposed to seawater, making a ranking
based on their practical nobility: copper, super-austenitic stainless steel,
AISI 304 stainless steel, titanium, zinc, and mild steel.
10:3 Discuss the effect of electrolyte resistivity on the maximum corrosion rate in
galvanic coupling.
10:4 Corrosion rate of commercial aluminium is higher when coupled with
copper rather than with stainless steel, although copper and stainless steel
show roughly same free corrosion potential. Why?
10:5 Discuss by means of Evans diagram the electrochemical behaviour of
stainless steel, Pt enriched on surface, to have stable passive behaviour.
10:6 Give an exhaustive comment of Fig. 10.16. Compare galvanic coupling
effects described in Figs. 10.15 and 10.16.
10:7 Write a testing procedure for measuring anode and cathode potential as well
as potential distribution on a galvanic coupling.
10:8 A carbon steel plate (1 m2 exposed surface area) and a zinc plate (16 cm2
exposed surface area) are coupled in stagnant seawater containing 10 mg/L
of oxygen.
• Which is the anodic material?
• How is current direction in seawater?
• Determine corrosion rate of the anodic material
• Determine the time for total consumption of the anodic material if initial
thickness is 10 mm.
10:9 A carbon steel plate, 5 mm thick, is coated with a copper layer, 0.1 mm
thick and is completely immersed in fresh water (q = 20 X m). A localised
defect of copper layer, 10 cm2 large, is present.
• Which corrosion form is possible?
• Which is the anodic area? And the cathodic area?
• Draw schematically corrosion current path
• If oxygen limiting current density is 20 mA/m2, when will the plate be
perforated?
10:10 A localised corrosion attack occurred on a stainless steel plate (square
shape, 1 m wide; 5 mm thick) immersed in seawater. The anodic area was
1 cm2. Draw corrosion current path and estimate corrosion rate. What
would have been the corrosion rate in fresh water assuming same oxygen
limiting current density of 50 mA/m2?
Giovanni Fabbroni
He was a prominent Florentine intellectual across XVIII–XIX centuries and
for many years deputy director of the Imperial Royal Museum of Physics and
Natural History in Florence. Vivid animator of Florentine cultural life, he
showed interest in many different fields, from economics to chemistry and
also agrarian and justice. In 1792 at the Academy of Georgofili, in Florence,
he presented a paper on the action of metals when coupled, which was
published only in 1799 in Journal de Physique (49, 348, 1799) with title:
“Sur l’action chimique des différent métaux entr’eux, à la température
commune de l’atmosphère; et sur l’explication de quelques phénomènes
galvaniques, (About the chemical action of different metals coupled at
atmospheric temperature; and on the explanation of some galvanic phe-
nomena). Piontelli wrote that with this work Fabbroni “founded the chemical
theory of galvanism and laid the foundations of galvanic corrosion theory ten
years before Volta’s invention.”
His paper is primarily the result of acute observations. For example, he
wrote: “I noticed that alloys used to solder copper plates on the mobile roof
of the Observatory of Florence had rapidly transformed, altered into white
oxide, right at contact with copper plates. I also knew that iron nails that
fasten copper sheets of ships hulls rusted so much that their stem expanded
even to exceed their head size.”
It is also the result of a series of ingenious experiences such as the fol-
lowing: “In a pot filled with water I put some golden foils, in another pot,
silver and in a third copper and then in others, tin, lead and so on. In other
pots I put the same metals two by two, separated by a small glass plate, one
more and the other less oxidizing.
Finally, in a third series of glasses the same couples of metals in contact
each other. The first two series showed no change, whereas in the third, the
more oxidizing metal became visibly oxidized immediately after being put in
contact with another metal and the oxide grew gradually. This phenomenon
began, albeit imperceptibly, as contact was made […] but after a month I
observed that different metals not only became oxidized but on their surface
were formed even small salt crystals of different shapes. It seemed, therefore,
that a chemical action [between metals] took place in a clear manner.” He
further stated: “I believe that from these and other observations we have to
recognize that metals in these cases exert a reciprocal action that is the cause
of phenomena that occur following their joining or when they come in
contact.”
In the past, scientists’ opinion on these statements has been contradictory.
Someone have acknowledged Fabbroni’s observations on corrosion of cou-
pled metals the embryo of the chemical theory of batteries; others have even
ignored that he certainly marked the beginning of the correlations between
corrosion and galvanic coupling. Today, nobody put in doubt that Fabbroni’s
paper has been one major scientific event.
P.S. The beautiful Museum of History of Science in Florence, heir to the

Museum where Fabbroni worked, which devotes an entire room to his former
deputy director, does not mention this important contribution. We hope there
will be a remedy.
Alessandro Volta, the Practical Potential Ranking and the Driving

Force
In 1792 the future inventor of the pile decided to classify the metals in
relation to the greater or lesser capacity of the bimetal arc formed by them to
excite stronger convulsions in the frog and to give acidic or rather basic
flavors on the tongue tip. With these two techniques, Volta was able to
evaluate the extent and direction of the electric current around the circuit
consisting of the bimetallic arc and the body of the frog, and then he decided
which of the two metals is more noble. Then, comparing all the metals two by
two, he built up the scale of the conductors of the first class, which possess a
different power to push the electric fluid and drive it forward in the wet
conductors, or second class: in practice a sort of scale or series of potentials,
indeed the prototype of the series of potentials that will come later. And so he
wrote: one can comfortably split the metals in three categories, placing tin
and lead in the lower one, iron, copper and brass in the middle, and gold,
silver and platinum in the upper one. So then it is more useful to oppose to
one of the lower rank, that is to lead or tin, one of the higher rank, gold or
silver and the latter maximum.
This is not yet the scale that Volta will establish the following year, which
concerns a greater number of metals and alloys and different “mines”,
including manganese dioxide and carbon. Volta rightly held a lot on this scale
and he claimed its priority. He wrote: “Practically I had already sketched it at
the beginning of 1793 […]. It differs little from the other scale or series that
Dr. Pfaff gave us in 1793.
One is admired by the work that, seven years before the invention of the
pile, Volta was able to accomplish, but also by the sharpness of his obser-
vations. For example, the scientist from Como notes the importance of the
nature, the composition, the structure of metals in defining the electro-
chemical behavior. He wrote: The small movements of the frog are obtained
even with an electrical arc apparently constituted by a single metal because
[…] even accidental small differences between the two ends of the metallic
arc (differences in alloy, in hardening, in tempering, in heat and perhaps
other modifications that we do not know) are enough to give movement to the
electric field. […] We can not even trust two similar coins, as there may be
some difference between them.
Volta introduced another important concept. I merely recall an investi-
gation by Varney and Fisher on the authorship of the concept of driving force
or electromotive force, or “driving virtue” to use Volta’s words: obviously it

is a concept of paramount importance in electrochemistry and even in cor-
rosion (above all in galvanic coupling). The two scientists wrote in an article
with a significant title: Electromotive Force: Volta’s Forgotten Concept: “We
have examined over a hundred references in which electromotive force is
mentioned. They include beginning as well as advanced texts, scientific
dictionary, encyclopedias and papers. None credits Volta with originating the
term”.
These (and other) oversights show that evidently the inventor of the pile,
“the apparatus that gave the physicists so much amazement”, has clouded the
scientist who, in the nine years preceding the invention and in the two that
follow it, has operated with success in experimental and theoretical electro-
chemistry, with very successful raids also in corrosion.
Pietro Pedeferri
Bibliography
Fabbroni G (1799) Sur l’action chimique des diff érents métaux entr’eux, à la temperature
commune de l’atmosphère; et sur l’explication de quelques phenomènes galvanique. Journal de
Physique 49:348
Fontana M (1986) Corrosion engineering, 3rd edn. McGraw-Hill, New York, NY
LaQue FL (1975) Marine corrosion, The Electrochemical Society monograph series. Wiley, New
York, NY
Speller FN (1926) Corrosion. Causes and prevention. McGraw-Hill, London, UK
Chapter 11
Pitting Corrosion
A thousand times better petting than pitting.

Peter Ironfoot
Abstract This chapter describes a localized corrosion attack called pitting, which
is typical of active-passive metals in oxidizing chloride-containing environments:
the passive film breaks locally, then corrosion proceeds at the damaged spot, few
millimetres wide or even less, creating a macrocell with the surrounding intact
passive metal. The influence of metal composition and environmental parameters
on corrosion, pitting and repassivation potential for stainless steel in chloride
containing environments is shown. Empirical parameters such as Pitting Resistance
Equivalent Number (PREN) are discussed and correlated to the likelihood of pitting
occurrence. The use of Pedeferri’s diagram, a potential vs chloride content diagram,
is also introduced, as a tool to assess corrosion conditions of an active passive metal
in chloride-containing environments.

https://doi.org/10.1007/978-3-319-97625-9_11
208 11 Pitting Corrosion
11.1 Pitting Morphology
Stainless steels, nickel-based alloys, copper and copper alloys, aluminium alloys,
titanium and titanium alloys, carbon steel in concrete and other metals can be
employed because a nanometre-scale oxide layer forms spontaneously on their
surface, the passive film, which greatly reduces corrosion rate. When passive film
breaks, localised corrosion of the underlying metal occurs, often accelerated
(Fig. 11.1).
Pitting is a severe localized corrosion which produces a deep penetrating attack,
the pit, with diameter less than a few millimetres, occurring most often isolated in a
number varying from a few to several hundred per squared meter. The term pitting
is often used to simply indicate a localized corrosion attack, however, it should be
used more properly for the typical localized attack occurred on active-passive
metals in oxidizing chloride containing environments. According to the ASTM G46
standard, a pit is defined extensive shallow or narrow deep or even elliptical,
transverse, sub-skin, vertical or horizontal, as depicted in Fig. 11.2. Some examples
of pitting attack are shown in Figs. 11.3, 11.4, 11.5 and 11.6.
The severity of pitting is twofold: once started, penetration rate is so high that it
affects the whole metal thickness in short time; on the other hand, the attack is
intrinsically of stochastic nature on either initiation time or localization; hence,
prediction is a matter of probabilistic approach.
Pitting propagation is the result of a macrocell mechanism: the anodic area is
inside the pit while the cathodic zone is the external surrounding passive area,
where oxygen reduction is the most common cathodic process. Penetration rate is
high because cathodic to anodic area ratio is as high as 100 in high conductivity
electrolytes and noble cathodic process.
Fig. 11.2 Typical forms of

pitting attack (from ASTM
G46)
11.1 Pitting Morphology 209
Fig. 11.3 Pitting corrosion

on a AISI 304 stainless steel
plate in the presence of
chlorides
Fig. 11.4 Pitting corrosion

on a AISI 304 stainless steel
plate of a heat exchanger due
to the presence of chlorides
The circulation of macrocell current gives rise to a series of reactions and

chemical modifications: inside the pit pH decreases and chloride content increases
to further stimulate the anodic attack, and on the external passive surface pH
increases, then helping strengthening passivity. Inside the pit, conditions necessary
to trigger stress corrosion cracking may establish (see Chap. 13).
11.2 Pitting Mechanism
Pitting corrosion follows two distinct stages: pit initiation and pit propagation
(Fig. 11.7).
Fig. 11.5 Cavernous pits on AISI 304 stainless steel in the presence of chlorides
Fig. 11.6 Pitting-like

corrosion on a carbon steel
pipe transporting formation
water
11.2.1 Pit Initiation
The initiation stage is the time required for the local breakdown of passive film,
which is produced by the action of specific chemical species present in the envi-
ronment, such as chloride ions (Cl−) and to a lesser extent halides F−, Br− and I−. It
is agreed that the necessary electrochemical condition required to locally break-
down the passive film is that the cathodic process has to be more noble than a
specific operational parameter, named pitting potential, which depends both on
metal and environment properties.
This step might last a few weeks up to several months, depending on metal and
operating conditions:
11.2 Pitting Mechanism 211
Thickness
loss
Pipe
thickness
ion
gat
opa
Pr Corrosion rate
Initiation
Perforation time
time
Fig. 11.7 Stages of pitting corrosion: initiation and propagation
• Strength of passive film, related to the metal chemical composition

• Inclusions
• Surface finishing
• Stagnant or turbulent fluid conditions
• Presence of biofilm and MIC
• Chloride (or halide) content
• Oxidizing species
• Continuous exposure time (wetting permanency)
• Horizontal versus vertical surfaces.
Typically, pits start where passive film is weaker or flawed (for example, near
welding because of depletion of some elements, or because oxide film is too thick
on work-hardened zones) or where the local environment is more aggressive due to
an increase in temperature or concentration of aggressive species.
Impurities and inclusions present on metal surface can perturb passive film
formation, which results weaker and thinner and also mechanically stressed, hence
favouring pitting initiation.
Surface finishing strongly influences pitting initiation: smooth surfaces are more
resistant or result into few, large pits, while rough surfaces experience easier ini-
tiation of numerous small pits.
In order to strengthen the passive layer, in industrial plants passivation treat-
ments are performed. A typical treatment consists of acid pickling followed by
immersion in a passivating solution, and a final rinsing in NaOH and water.
Stagnant condition favours pitting initiation, while agitation or turbulence help
inhibit it. For example, for AISI 304 stainless steel, chlorides content to trigger
pitting at 20 °C in agitated solutions is about 200 ppm and sometimes even more,
and drops to 100 ppm or even less in stagnant solutions.
Another important aspect related to pit initiation regards bacterial activity. In

1976 the first paper on the subject appeared by the Italian researchers Mollica and
Trevis (1976), and it is now well known that bacterial activity, caused by either iron
bacteria or sulphur-oxidizing ones, raises the potential of the cathodic process
occurring on stainless steels. This potential increase takes place after the formation
of oxidizing species, such as hydrogen peroxide, or in fresh water, when manganese
ions are present, due to the formation of a redox couple.
In addition, the presence of oxidizing species, which leads to a cathodic process
with a noble potential, such as the presence of free chlorine, promotes pitting
initiation. This experimental evidence is used in laboratory to enhance pitting ini-
tiation on stainless steels by using a solution of ferric chloride, which exhibits a
noble potential as high as about +0.4 V SCE due to the redox couple Fe3+/Fe2+ (see
also the Pourbaix diagram of iron).
Another practical important factor is the continuous exposure time (or wetting
permanency) as illustrated by a household example. Common cookware is made of
austenitic stainless steel (typically 18-8, or AISI 304 grade); although often in
contact with a chloride-containing environment, the cooking food, which is theo-
retically harmful for pitting initiation (even if the environment is bacteria free)
pitting does not start. This behaviour depends on the limited exposure time, i.e., few
minutes to few hours, which is not enough to locally destroy the passive film.
Furthermore, operations as washing and drying reset the initiation time countdown.
Same considerations apply to the behaviour of batch reactors made of stainless
steels in food and chemical industry, which work substantially in the same way as
cookware.
Finally, since inside pits the electrolyte concentrates, then increasing its density,
pits can grow only on horizontal surfaces; curiously, on vertical surfaces it can
initiate, then growing inside wall thickness proceeding downward vertically.
Pitting Initiation Theory

For materials that initially are typically passive, e.g. aluminium and stainless
steels, it is assumed that pitting is initiated by adsorption of halide ions that
penetrate the passive film at certain positions. This happens at weak points of
the oxide film, e.g. at irregularities in the oxide structure due to grain
boundaries or inclusions in the metal. Absorption of halide ions causes strong
increase in ionic conductivity in the oxide film so that metal ions can migrate
through the film. In this way, localized dissolution occurs, and intrusions are
subsequently formed in the metal surface.
Another theory is that the initial adsorption of aggressive anions at the
oxide surface enhances catalytically the transfer of metal cations from the
oxide to the electrolyte and thus causes successive local thinning of the oxide
film.
A third possibility is that the attacks start at fissures in the passive layer.
Which of the mechanisms is the most effective depends on both material
and environment.
from Bardal (2004)
Pitting Potential
A key parameter for pitting occurrence is pitting potential, Epit. It is an
empirical, operational parameter, i.e., not defined as the equilibrium potential or
the corrosion potential, instead is obtained through a laboratory measurement
procedure, now standardized (see ASTM G61), because its value is influenced
by how the measurement is carried out, for instance by potential scan rate.
Pitting potential, Epit, which is the upper limit of passivity range, lowers as
chloride concentration in the electrolyte increases as shown in Fig. 11.8.
Above Epit the protective film is perforated, making the corrosion process
possible. The pitting attack can therefore occur only if the free corrosion
potential, Ecorr, namely the potential of metal before pit initiation, is greater
than Epit; this happens when a passive metal is in contact with solutions of
sufficiently high oxidizing power. Conversely, if free corrosion potential,
Ecorr, is below pitting potential, Epit, (Ecorr < Epit) pitting does not start.
It is therefore evident that as pitting potential decreases pitting initiation
becomes possible also in gradually less oxidizing electrolytes. On the other
hand, as cathodic potential decrease because of reduced oxidizing power, the
number of metals that can withstand pitting widens.
E
Fig. 11.8 Potentiodynamic
curve for determination of
pitting potential and repassi- Epit
vation potential
Erp
Ecorr
log i
Pitting as Stochastic Event

Filed experience and laboratory testing confirmed that pitting initiation is
random in nature; moreover, pit in a very initial stage should be considered
unstable or metastable and can re-passivate or propagate on a stochastic or
probabilistic base. Figure 11.9 shows an example of metastable pits observed
during laboratory testing for pitting potential determination.
To determine pitting potential, which seems to follow a normal distribu-
tion, it can be assumed as the value at which the probability of pitting po-
tential is 0.5, after a total number, N, of measurements obtained from the
cumulative function:
n
P Epit ¼ ð11:aÞ
N þ1
where n is the number of samples that had pitted at a potential value, Epit,
under potentiostatic test condition.
The induction time at a given potential, E, is the measured time after the
application of potential, E, at which n samples have initiated pits. Survival
probability, P(t), is the cumulative function:
n
PðEÞ ðtÞ ¼ ð11:bÞ
N þ1
where n is number of samples that initiate pits by time t after application of

potential, E. The pit generation rate, k, given by:
d
kðtÞ ¼ ln PðEÞ ðtÞ ð11:cÞ
dt
Fig. 11.9 Potentiodynamic E

curve showing metastable pit
formation
Epit
Metastable
pit
Ecorr
log i
can also be used as a measure of susceptibility to pitting.

from Frankel (1998)
11.2.2 Propagation of Stable Pits
Once a stable pit initiates, a macrocell current starts flowing, as shown in

Fig. 11.10, between the anode (i.e., where passive film has broken down and metal
dissolves) and the surrounding passive zones acting as cathode. Inside pit, the
solution becomes gradually more aggressive as hydrolysis reaction of metal ions
proceeds, hence acidification increases and pH drops to values close to 3–4:
Mz þ þ zH2 O ! MðOHÞz þ zH þ ð11:4Þ
Conversely, on cathodic zones outside the pit, pH increases, then passive film
strengthens and other pits cannot initiate within.
As corrosion proceeds, metal cations migrate and diffuse towards the pit mouth,
then reacting with hydroxyl ions and precipitating as hydroxide: this configuration
is called occluded cell. Figure 11.11 depicts an example of occluded cell for copper
in hard water containing traces of chlorides, showing how hydroxide precipitates as
series of layers of different oxides and salts.
Another important consequence of macrocell current flow is that chloride con-
centration increases inside pit; in the case of stainless steels, chloride concentration
can increase more than one order of magnitude compared to bulk concentration.
According to this mechanism, called autocatalytic, pitting corrosion proceeds inside
the metal and does not spread on the surface.
Fig. 11.10 Schematic

representation of an occluded
cell O2 O2 O2
OH- OH- OH-
Cathode Metal ions Cathode
H+ Cl-
Anode
CuCO3 2 (green)
CuCl (white)
Cu2O (red) CuO (adherent)
Copper
Fig. 11.11 Schematization of operculum that may form on the pit of copper tubing in contact with
water (from Pourbaix 1973)
11.2.3 Corrosion Rate of Stable Pits
The corrosion rate of a pitting attack is given by the macrocell current, IMC, which
can be written as follows:
IMC ¼ Ia ¼ Ic ¼ icorr Sa ¼ ic ðSc þ Sa Þ ð11:5Þ
where meaning of symbols is known. Accordingly, corrosion rate, which is pitting

penetration rate, Crate-pit, is given by:
Cratepit ¼ icorr ¼ ic ðSc þ Sa Þ=Sa ð11:6Þ
where surface ratio is determined by the electric field established by the macrocell.
Rearranging above equation, as shown in Chap. 9, taking into account the throwing
power and oxygen reduction as cathodic process, pitting penetration rate, Crate-pit
(mm/y), has the following expression (Lazzari 2017):
sffiffiffiffiffiffiffiffiffiffiffi
iL DV
Crate;pit ffik ð11:7Þ
q
where q (X m) is electrolyte resistivity (1 < q < 103), iL (A/m2) is oxygen limiting

current density (0.01 < iL < 1), DV (V) is driving voltage and k is an experimental
constant. Driving voltage is in general given by:
DV ¼ ðEc Epit ÞIR ð11:8Þ
where Ec is potential of the cathodic process, Epit is pitting potential and IR is the
ohmic drop. The latter can be reduced to two main contributions: ohmic drop at
anode (because of its tiny size) and ohmic drop at cathode due to the oxide film
resistance. If the oxide film has good insulating properties, the macrocell is dras-
tically reduced: this is the case of aluminium in seawater, where pit growth is quite
slow because aluminium oxide is an insulator. In summary, driving voltage, DV, is

up to 1 V for stainless steels and 0.1 V in the case of aluminium.
11.3 Pitting on Stainless Steels in Chloride-Containing

Solutions
For stainless steels, pitting in chloride containing solutions is one of most threat-
ening localized corrosion attacks. To forecast, hence to prevent, pitting corrosion of
stainless steels, four parameters have to be considered:
• PREN index
• Free corrosion potential
• Pitting potential
• Repassivation potential.
11.3.1 PREN Index
In case of stainless steels and nickel alloys, experience and laboratory testing have
shown the influence of metal composition on pitting susceptibility. An index called
PREN (Pitting Resistance Equivalent Number) has been proposed and is currently
used. The main agreed definition of PREN is the following:
PREN ¼ ½%Cr þ 3:3 ½%Mo þ 16 ½%N ð11:9Þ
As rule of thumb, stainless steels with PREN lower than 18 (as 13 or 17% Cr, or
18-8, i.e. AISI 304 type) are recommended in the presence of low chloride content
or under special conditions as discontinuous operation, absence of oxygen and other
oxidants, cathodic protection or favourable galvanic coupling or at high pH, such as
in concrete.
Molybdenum containing stainless steels as AISI 316 type, with PREN 26, can be
used for non-acidic brackish waters with chloride content up to 1 g/L, at temper-
ature not exceeding 30–40 °C; conversely, in seawater they can suffer pitting.
Higher PREN stainless steels, such as 35–40 or higher, resist pitting attack in
seawater, provided there are no galvanic couplings with carbonaceous materials and
they are not anodically polarized and without chlorination treatment. For best
performance, even in presence of chlorine, the use of stainless steel with a PREN
greater than 45 is mandatory (such as superaustenitic steels or superduplex: for
example, alloys with 6% molybdenum, such as the alloy 254 SMO).
11.3.2 Free Corrosion Potential
The free corrosion potential, Ecorr, of a passive stainless steel, that is, before cor-
rosion initiation, mainly depends on the oxidizing power of the solution, and then
increases with the content of oxygen or other oxidizing species that may be present,
such as chlorine, ferric and cupric ions.
In the case of stainless steels in seawater at temperatures below 30–40 °C, the
presence of bacterial activity leads to the formation on the surface of a film con-
sisting of biological substances, the so-called biofilm, which catalyses the reduction
of oxygen and increases Ecorr by more than 300 mV.
Ecorr increases spontaneously in the presence of a galvanic coupling with more
noble metals or graphite, or by an anodic polarization due to a stray current
interference, and decreases under cathodic protection or cathodic polarization
conditions (for instance in contact with less noble metals such as zinc, aluminium or
carbon steel).
11.3.3 Pitting Potential
Pitting potential, Epit, depends on both stainless steel composition and environ-
mental conditions, namely, chloride content, pH and temperature. Figure 11.12
shows the qualitative influence of chloride content on pitting potential.
Figure 11.13 summarizes the anodic behavior of two austenitic steels in a solution
at a fixed Cl− content: the first (AISI 304, PREN 18) does not contain molybdenum,
the second (AISI 316, PREN 24–28) does, and shows the best behavior. Pitting
potential depends also on surface finishing and, in particular, on the conditions of
the passivating layer; for example, a significant reduction of pitting potential is
found in so-called colored zones (tinted zones) composed of mixed oxides that are
formed on heat-affected-zones of welds performed in non-controlled atmosphere or
during hot forming. The original passivity is regained by removing oxides by
pickling and by repassivation.
For an estimation of the pitting potential as function of stainless steel compo-
sition, chloride content, temperature, flowing conditions and electrolyte composi-
tion, reference can be made to Lazzari (2017).
11.3.4 Repassivation Potential
Once pitting has initiated, it proceeds even at lower potentials than Epit; however, if
potential is decreased below a value called repassivation potential, Erp, where
Erp < Epit, pits stop growing, as shown in Fig. 11.14 (Pourbaix 1973).
11.3 Pitting on Stainless Steels in Chloride-Containing Solutions 219
Fig. 11.12 Influence of E

chloride content on pitting
potential
Epit
Chlorides
log i
Fig. 11.13 Example E

of influence of stainless steel
composition on pitting
potential
Epit AISI 316
Epit AISI 304
log i
Fig. 11.14 Anodic curve of E

an active-passive material
Pitting
identifying pitting and
repassivation potentials Epit
Imperfect
passivity
Erp
Perfect
passivity
Eeq
Immunity
log i
Pitting potential, Epit, and repassivation potential, Erp, indicatively about 300 mV
lower, identify three potential ranges:
• E > Epit: the attack starts and proceeds
• E < Erp: perfect passivity, the attack cannot start and, if already started, stops
• Erp < E < Epit: imperfect passivity, the attack does not start and, if already
started, it proceeds.
11.3.5 Pedeferri’s Diagram
For each stainless steel, that is, for each PREN, pitting and repassivation potentials
depend on chloride content, as proved by laboratory testing and experience.
Pedeferri proposed a potential-chloride, E-[Cl−], diagram (Fig. 11.15) that has now
his name. Pedeferri proved the diagram for passive carbon steel in concrete and
forecasted its extension to stainless steels in chloride containing solutions.
Pedeferri’s diagram helps understand the cathodic prevention technique he invented
(Pedeferri 1995).
11.3.6 Pitting Induction Time
From experience, the time required for pitting initiation, which is the time required
to locally breakdown the passive film, once established the electrochemical con-
dition Ec > Epit, where Ec is potential of the cathodic process and Epit is pitting
potential, is considered by many authors as a stochastic variable.
Fig. 11.15 Pedeferri’s 0.4

diagram for carbon steel in
0.2 Corrosion
concrete
Pit can initiate and propagate
0
-0.2
E (V CSE)
Imperfect passivity
-0.4 Pit does not initiate but can propagate
-0.6
Perfect passivity
-0.8
Pit does not initiate and propagate
-1.0
Immunity
-1.2
0 0.5 1 1.5 2
Chloride content (% by cement mass)
11.3 Pitting on Stainless Steels in Chloride-Containing Solutions 221
Indeed, induction time for a specific stainless steel (in other words, for a fixed
PREN) depends on many factors, as:
• Chloride content
• pH
• Temperature
• Fluid velocity
• Potential of the cathodic process.
The key parameter is the driving voltage, DEpit, as difference between the potential
of cathodic reaction occurring on passive film, Ec, and pitting potential, Epit. The
driving voltage summarises all the influencing factors. The higher the driving
voltage available, the lower the pitting induction time.
An innovative approach is proposed in Lazzari (2017) where an estimation of the
pitting-induction-time, PIT (in h), is based on experimental data, which can be
summarized as follows:

PREN
2log½Cl ð1DEpit Þ
PIT ¼ k 10 ð11:10Þ
where k is an experimental constant close to 1 (in h) and other symbols are known.
As rule of thumb, if PIT exceeds about 104 h, pitting attack does not initiate if
operating conditions do not change. This behaviour is typical of phenomena which
are characterized by so-called infant mortality, i.e., should the passive film failure
occur, it occurs early after exposure or never.
It appears that the cathodic potential is of primary importance for the estimation
of the induction time. In general, the cathodic potential derives from the following
three conditions occurring in most industry related environments:
• Oxygen reduction in sterile electrolyte
• Oxygen reduction in the presence of biofilm
• Chlorine reduction.
In addition, the potential of ferric chloride solutions used in testing should be
considered.
The potential of oxygen reduction in a sterile electrolyte is simply the potential
obtained by Nernst equation, therefore function of pH and oxygen concentration.
An empirical equation is reported in Lazzari (2017) as follows:

50
EO2 ¼ 1:23 0:33 log 0:059 pH ð11:11Þ
½O2
where [O2] is oxygen concentration in ppm.

Potential of Stainless Steels in Seawater

Typical values of free corrosion potential, Ecorr, of stainless steel before
pitting initiation in seawater are as follows:
• Deaerated: about −0.5 V SSC (Silver/Silver Chloride reference electrode)
• Aerated, sterile seawater (no bacterial activity): around 0 V SSC
• Aerated, with biofilm (bacterial activity as natural seawater): up to +0.3 V
SSC
• Aerated with chlorine injection (about 0.5–1 ppm to reduce bacterial
activity): +0.6 V SSC
• Galvanic coupling with iron (or carbon steel): −0.4 V SSC
• Galvanic coupling with zinc or aluminium: from −0.8 to −1.0 V SSC
SCC has a potential +0.25 V SHE. If SCE (saturated calomel electrode) is
used, its potential is +0.24 V SHE.
In the presence of biofilm, such as in seawater, the potential of oxygen reduction

can be expressed simply by adding 0.3 V to the potential in absence of biofilm. This
300 mV increase was measured by Mollica and Trevis (1976) for the first time, and
then confirmed by other researchers, therefore:
EO2 =bio ¼ EO2 þ 0:3 V ð11:12Þ
In the presence of chlorine, such as in treated or sanitized waters, the potential of

cathodic reaction of chlorine reduction is more noble than oxygen reduction,
therefore pitting initiation can occur also in absence of oxygen. The potential of
chlorine reduction is obtained from Nernst equation as follows:
½Cl2
ECl2 ¼ 1:36 þ 0:6 log ð11:13Þ
36
where [Cl2] is chlorine concentration in ppm (>0.1).

Stainless steels in seawater can experience a pitting induction time varying from
a few days for AISI 304 grade to about a month for AISI 316 grade when biofilm
forms. As rule of thumb, because pitting is an infant-related phenomenon, in
practice induction time lasts less than a year. In other words, if pitting has not
started within a year from exposure time it will not occur anymore if operating
conditions remain unchanged.
11.4 Pitting Susceptibility 223
11.4 Pitting Susceptibility
To assess pitting susceptibility on stainless steels, parameters as pitting potential,

pitting critical temperature, critical chloride concentration and PREN are used.
11.4.1 Critical Pitting Temperature and Critical Pitting

Chloride Concentration
Critical Pitting Temperature, CPT, is the minimum temperature at which stainless

steel resists pitting attack, once fixed potential and environmental conditions.
Similarly, Critical Pitting Chloride Concentration, CPCC, is a threshold below
which pitting does not initiate.
Laboratory testing are performed based on international standard, such as ASTM
G48, ASTM G150 and ASTM F 746-04.
From testing results, CPT in a 6% ferric chloride solution, as often used for
comparison to rank stainless steels, is a function of PREN through the following
empirical relationship:

CPT C ffi 3:3 PREN 58 ð11:14Þ
For instance, CPT is 0 °CC for AISI 304, 20 °C for AISI 316, 75 °C for 254 SMO,
and 100 °C for 564 SMO.
Similarly, from laboratory testing results, CPCC is a function of stainless steel
composition, i.e., PREN, and operating conditions, namely pH and temperature, as
follows (Lazzari 2017):

PREN 7 pH T 25
log½CPCCcritical ffi ð11:15Þ
9 5 50
where parameters are known.

For reinforcing carbon steel in concrete structures exposed to the atmosphere,
CPCC ranges between 0.4 and 1% by cement weight; for galvanized steel it is about
1%, whereas for stainless steel AISI 304 or 316 is in the range 5–8%, which
decreases to only 3% on welded zones, covered with coloured oxide.
11.5 Pitting on Carbon Steel in Chloride-Contaminated

Concrete
Carbon steel reinforcements in sound concrete (pH > 13 and no chlorides) are
passive. Passivity breakdowns when chloride content at steel surface exceeds a
critical content. Pedeferri’s diagram helps understand the influence of potential and
chloride content. Three regions can be identified (Fig. 11.15):
• Corrosion condition (pit initiates and propagates)
• Imperfect passivity (pit does not initiate, instead it can propagate if started)
• Perfect passivity (pit does neither initiate nor propagate).
Pitting and repassivation potential curves depend on chloride content. At any
potential the critical chloride content is determined. It can be noted that as chloride
content increases, potential decreases. Reinforcement of concrete structures,
exposed to the atmosphere, shows a pitting potential usually around +0 V SCE then
critical chloride content is in the range 0.4–1% by cement weight. In the case of
structures immersed in water, where oxygen diffusion is impeded, and therefore
characterized by a corrosion potential lower than a few hundred mV, critical
chloride content is much higher. Repassivation potential, Erp, is approximately
300 mV more negative than pitting potential. For more details, refer to Bertolini
et al. (2013).
11.6 Pitting on Aluminium Alloys
Although aluminium passivates as stainless steel by forming an oxide layer on the

metal surface as soon as it is exposed to an electrolyte, pitting-like corrosion differs
strongly, mainly for propagation rate. As already mentioned, aluminium oxide is a
good insulator, therefore electrons are strongly impeded to flow from the metal to
the oxide-electrolyte interface.
Pitting initiation requires the presence of an anion able to locally breakdown the
passive film: typically, it is again chloride or more generally halogens. The most
important condition for pitting initiation is chloride concentration, which follows,
approximately, the same trend as stainless steels. One factor that strongly enhances
pitting initiation is the presence on the aluminium surface of metallic copper, as
small particles deposited from copper ions accidentally present in the solution: the
galvanic effect of copper on aluminium determines the passive film breakdown.
Because of the insulating properties of the oxide film, the macrocell set up by the
pit on aluminium alloys has a low throwing power, even in highly conductive
electrolytes as seawater: hence, many pits form, which is the opposite of what
happens on stainless steel, where only a few isolated pits forms.
The propagation rate of the numerous pits is much lower than that for stainless
steel because of the insulating properties of the oxide film. Instead of using the
11.6 Pitting on Aluminium Alloys 225
approach adopted for stainless steel, which could be used again, an empirical
equation is proposed as follows:
ypitdepthAl ffi k t0:33 ð11:16Þ
where the constant, k, is averagely 0.75 for pit depth in mm, considering time in
year. Accordingly, corrosion rate is given by:
0:25
CratepitAl ffi ð11:17Þ
t0:66
Crate is in mm/y and time, t, in year. The above equations are derived from labo-
ratory testing results, confirmed by field experiences (Godard 1967).
11.7 Pitting as Markovian Process or Prevention of Pitting
Copper is used in water circuits, with either freshwater or seawater. In rare cases, in
freshwater, copper suffers localized corrosion with a morphology and mechanism of
pitting. Copper and copper alloys resist corrosion in aerated waters because they
passivate, although the nature of passive film is coarse if compared with the passive
film of stainless steels. Therefore, in this case, it is more appropriate to call this
condition passivation instead of passivity. The passivation of copper is caused by
the formation of corrosion products, such as copper oxy-carbonate, Cu2(OH)2CO3.
Pitting initiation can follow two distinct mechanisms: by the first, initiation is
triggered by the presence of carbonaceous particles produced during drawing
manufacturing from the decomposition of lubricants and not removed by successive
proper chemical etching. The second one, discussed in literature, is somewhat
evanescent because there is no specific recognized condition for prediction of pit-
ting occurrence, unless again the presence of some noble particles.
Pitting propagation follows the macrocell mechanism and, therefore, general
equations apply, taking into account the following:
• The anodic process is copper dissolution, which occurs at quite noble potential.
Since oxygen reduction (i.e., cathodic process) occurs at potentials relatively
more noble than equilibrium copper potential, the driving voltage is much lower
than the one in case of pitting on stainless steels. For calculations, driving
voltage in practice is not exceeding 0.2 V
• The cathodic current density in the activation overvoltage interval is about one
order of magnitude lower than oxygen limiting current density. For calculations,
current density should not exceed 50 mA/m2.
In practice, the maximum corrosion rate is about 1 mm/year (oxygen current
density 50 mA/m2, driving voltage 0.2 V and water resistivity 20 X m).
Pitting Initiation for Stainless Steel as a Markovian Process

Pitting occurrence is stochastic in nature. Almost a century ago, Mears and
Evans introduced the concept of “probability of corrosion” and emphasized
the practical importance of a statistical assessment of localized corrosion
(Mears 1935), and starting from late 1970s probabilistic models to predict
pitting initiation were proposed. An interesting probabilistic approach is
based on Markov chain theory (Provan and Rodriguez 1989), valid for
memoryless processes. Indeed, pitting on stainless steel can be considered a
memoryless process, since if it happens, this is when critical conditions are
present, regardless any previous ones.
A Markov chain is a memoryless stochastic process that undergoes tran-
sitions from one state to another through a finite number of possible states,
until it stops at the so-called absorbing state. Each transition is characterized
by a transition probability given by the Markov transition matrix. The model,
described in Brenna et al. (2018), starts from a metastable state where
metapits form, then evolving toward stable pit (pitting occurrence) or passive
condition through a repassivation process. Figure 11.16 shows how the
model works based on five states. From a metastable condition, two com-
petitive processes can be recognized: (a) the breakdown of the passive film
with the formation of a stable occluded cell and (b) the formation of a passive
layer on the metal surface and death of metastable pits. Transition proba-
bilities are indicated as m, p and r, respectively from metastable to meta-
passive, metapitting to pitting and metapassive to passive. There are two
absorbing states: stable pitting, characterized by the formation of a macrocell,
and stable passive state.
From the initial metastable condition, the system transforms necessarily to
one absorbing state after a finite (countable) number of transitions. To
determine the final probability toward which absorbing state the system
evolves (i.e., pitting or passive state) probability p and r are the output of the
matrix calculation, once known the initial probability. The higher the final
probability r, the higher the resistance to pitting corrosion of the metal.
Initial probabilities are determined by the actual conditions, as depicted in
Fig. 11.17. In practice, to input the initial transition probabilities, m, p and r,
are calculated from parameters indicated in figure, namely: PREN, pH,
r 1-r 1-p p
1 Passive Metapassive Metastable Metapitting Pitting 1
m 1-m
Fig. 11.16 Five model states for pitting corrosion

11.7 Pitting as Markovian Process or Prevention of Pitting 227
1 2 3 4 5
1 Passive Metapassive Metastable Metapitting Pitting 1
r m 1-m p
Solution chloride Eprot

content
Critical chloride
PREN
content
Fluidodynamic PREN pH Temperature Crevice E
Fig. 11.17 Factors influencing the transition probabilities
temperature, chloride content, cathodic process or redox potential and fluid

velocity, then final probabilities, r and p, are obtained. When the final
probability, p, exceeds 50%, it could be concluded that susceptibility of metal
to pitting corrosion is too high for applications.
11.8 Prevention of Pitting Corrosion
To prevent pitting on susceptible metals, two strategies are followed based on the
evidence that it is difficult to stop a pit once started, if deeply penetrated: in the
latter case, a drastic grinding action is necessary, often almost impossible to put into
practice. Only shallow pits, less than 0.3 mm deep, can be recovered by washing
with alkaline, chloride-free solutions (for example sodium carbonate).
These two strategies are:
• Selection of resistant metals (for stainless steels, PREN is used as guide for
proper and safe choice)
• Application of cathodic protection.
Material selection in design phase has to take into account expected operating
condition for the entire design life (for instance, chloride content, oxidizing power,
acidity, bacterial activity, surface condition).
The second strategy is the application of CP which is effective both to prevent

pitting initiation (in this case, Pedeferri named it cathodic prevention, CPrev), and
to stop pitting propagation. In CPrev, it is sufficient to lower the potential below the
pitting potential, Epit, in the second, it is necessary to drop the potential below the
repassivation potential, Erp.
11.9 Applicable Standards
• ASTM G 46—Standard Guide for Examination and Evaluation of Pitting

Corrosion, West Conshohocken, Pa.: American Society for testing of Materials
• ASTM G 48—Standard Test Methods for Pitting and Crevice Corrosion
Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride
Solution, West Conshohocken, Pa.: American Society for testing of Materials
• ASTM G 61—Standard Test Method for Conducting Cyclic Potentiodynamic
Polarization Measurements for Localized Corrosion Susceptibility of Iron-,
Nickel-, or Cobalt-Based Alloys, West Conshohocken, Pa.: American Society
for testing of Materials
• ASTM G 150—Standard Test Method for Electrochemical Critical Pitting
Temperature Testing of Stainless Steels, West Conshohocken, Pa.: American
Society for testing of Materials
• ASTM F 746—Standard Test Method for Pitting or Crevice Corrosion of
Metallic Surgical Implant Materials, West Conshohocken, Pa.: American
Society for testing of Materials
• ISO 8993—Anodizing of aluminium and its alloys—Rating system for the
evaluation of pitting corrosion. Chart method, International Standard
Organization, Geneva, Switzerland
• ISO 8994—Anodizing of aluminium and its alloys - Rating system for the
evaluation of pitting corrosion. Grid method, International Standard
Organization, Geneva, Switzerland
• ISO 11463—Corrosion of Metals and Alloys—Evaluation of Pitting Corrosion,
International Standard Organization, Geneva, Switzerland
• ISO 15158—Corrosion of Metals and Alloys—Method of measuring the pitting
potential for stainless steels by potentiodynamic control in sodium chloride
solution, International Standard Organization, Geneva, Switzerland
• ISO 17864—Corrosion of Metals and Alloys—Determination of the critical
pitting temperature under potentiostatic control, International Standard
Organization, Geneva, Switzerland.
11:1 Pitting potential of stainless steel AISI 304 and AISI 316 in seawater at 20 °C
is −0.1 V SCE and +0.2 V SCE, respectively. Establish which material
suffers pitting in deaerated, natural aerated, chlorine containing and sterile
seawater. Can pitting corrosion initiate when stainless steel is coupled with
iron, zinc, or aluminium?
11:2 A tank designed to store natural, i.e. not treated, seawater was made of
stainless steel, 18-8 grade (AISI 304) with 4 mm thick bottom plate. Can
you predict perforation time if plant is in Norway, Italy and Persian Gulf?
What would you expect if waters were sterilized? Suggest remedial actions.
11:3 In a heat exchanger tube, seawater flows at a velocity of 1 m/s. Predict
pitting occurrence if tube is made of: (a) AISI 304 stainless steel; (b) AISI
316 stainless steel; (c) high-alloy austenitic stainless steel with 6% Mo. As
second choice, consider water velocity of 2 m/s and shutdown time (for
maintenance) of 2 weeks.
11:4 A plate made of stainless steel, grade AISI 304 (18-8 Cr–Ni), was immersed
in the water of a swimming pool. Pitting corrosion occurs on the plate
corresponding to some welds. Find most likely root cause for pitting cor-
rosion. Estimate pitting initiation time and pitting propagation rate. Suggest
practical solution, either in new design or for intervention.
11:5 In a case of pitting corrosion on an aluminium sheet in seawater, the largest
pit depth is 200 lm after 2 months. What will be the maximum depth
expected after 1 year? After 10 years?
11:6 In a piping system, cold seawater flows slowly, i.e. water velocity is lower
than 1 m/s. Which stainless steel would you recommend?
Conventional AISI 304 stainless steel or AISI 316 or high-alloy austenitic
stainless steel with 6% Mo?
11:7 Laboratory testing demonstrated that addition of sulphate ions (for instance
as Na2SO4) to a NaCl solution increases pitting resistance as follows: 18-8
steel (AISI 304, PREN 18) behaves like AISI 316 (PREN 25) in absence of
sulphate. Suggest an interpretation.
11:8 A localized corrosion attack occurred in the centre of a stainless steel plate
grade AISI 304 L (PREN 18). The anodic area (the pit) can be estimated in
1 cm2. The oxygen limiting current density is 50 mA/m2. How the current
will flow in the electrolyte? Evaluate the corrosion penetration rate in the
following conditions: fresh water (resistivity 20 X m), brackish water (re-
sistivity 5 X m). Refer to Chap.9 for the equation that defines the throwing
power on a plate geometry.
11:9 Cold seawater is flowing slowly through a pipe with a joint between
stainless steel and carbon steel pipes. Discuss if corrosion of the stainless
steel pipe can occur in the three following condition: (a) use of stainless
steel AISI 304; (b) use of stainless steel AISI 316; (c) use of high-alloy
austenitic stainless steel with 6% Mo.
11:10 For the following common stainless steels (AISI 304, AISI 316, AISI 430,
AISI 904, duplex 2205, duplex 2507) calculate the induction time in the
following working condition: seawater, lake water, drinking water (assume
proper values for the affecting parameters). Comment on the results.
Bibliography
Bardal E (2004) Corrosion and protection. Springer, London, UK

Bertolini L, Elsener B, Pedeferri P, Redaelli E, Polder P (2013) Corrosion of steel in concrete:
prevention, diagnosis, repair. 2nd edn. Wiley-VCH, Weinheim
Brenna A, Bolzoni F, Lazzari L, Ormellese M (2018) Predicting the risk of pitting corrosion
initiation of stainless steels using a Markov chain model. Mater Corros 69:348–357
Frankel GS (1998) Pitting corrosion of metals. A review of the critical factors. JES 145:2186–2198
Godard HP (1967) The corrosion of light metals. Wiley, New York, NY
Mears RB, Evans UR (1935) The “probability” of corrosion. Trans Faraday Soc 31:527–542
Mollica A, Trevis A (1976) The influence of the microbiological film on stainless steels in natural
seawater. In: Proceedings of the 4th International Congress on Marine Corrosion and Fouling,
paper n. 351, Juan-les Pins, France
Pedeferri P (1995) Cathodic protection and cathodic prevention. Constr Build Mater 20:12–20
Pourbaix M (1973) Lectures on electrochemical corrosion. Plenum Press, New York-London, UK
Provan JW, Rodriguez ES III (1989) Part I: development of a Markov description of pitting
corrosion. Corrosion 45:178–192
Chapter 12
Crevice Corrosion
Rust never sleeps.

Neel Young
Abstract Crevice corrosion is a form of localized corrosion related to the presence

of sub-millimetric interstices (gaps, screens, deposits) on the surface of a metal. The
mechanism involves the consumption of oxygen in the gap and the impossibility to
restore it, with consequent setup of a differential aeration macrocell. This chapter
presents the main aspects of metal and environment composition affecting the onset
of crevice corrosion and—like in the previous chapter—proposes empirical
parameters, as Critical Crevice Gap Size (CCGS), which help predict it.

https://doi.org/10.1007/978-3-319-97625-9_12
232 12 Crevice Corrosion
12.1 Definition
The presence of cracks, gaps, screens or deposits on a metal surface can give rise to
a localized corrosion form, called crevice corrosion or interstitial corrosion and
corrosion under deposit (Fig. 12.1). Crevice corrosion is a concern in many
environments for active-passive alloys as stainless steels, nickel alloys and titanium.
Typically, stainless steels suffer from crevice corrosion in seawater or in
chloride-containing solutions, present in most of industrial plants as in chemical,
petrochemical, pharmaceutical, food processing, as well as in biomedical, nuclear
and civil engineering.
Crevice corrosion produces local thinning or even perforation, with risk of out of
service of equipment and pollution of fluids; in some situations, the corroded area
can create conditions for stress corrosion cracking occurrence (see Chap. 13).
12.2 Crevice Critical Gap Size (CCGS)
The key parameter of crevice corrosion is the critical crevice gap size (or critical
interstice size), defined as the minimum that allows the aggressive environment to
enter the interstice but impedes the diffusion of oxygen. Critical gap size is between
0.1 µm and 0.1 mm, depending on metal composition. From literature data, in
particular from Oldfield and Sutton (1978), the critical crevice gap size for stainless
steels, assuming a crevice depth of 5 mm, can be estimated by the following
equation:
2
17
CCGS ffi ð12:1Þ
PREN
where CCGS is in lm and PREN is pitting resistance equivalent number, which is

calculated from stainless steel composition (see Chap. 11). Crevice corrosion
occurs when gap size is smaller than the critical one. In general, the narrower and
deeper the gap the higher the risk of crevice occurrence.
Figure 12.2 illustrates typical conditions that give rise to crevice corrosion as
follows:
• Cracks in the metal, typically due to lack of penetration in welds
• Surface overlapping as in joints and threaded connections. If metals are dif-
ferent, galvanic effects have to be evaluated
• Interstices between metal and non-metallic materials (plastic, rubber, glass or
wood) as typically in flanges and sealing gaskets
• Presence of deposits or scales or corrosion products or fouling.
12.2 Crevice Critical Gap Size (CCGS) 233
(a) (b) (c) (d) (e)
Fig. 12.2 Types of crevices due to: a Incomplete weld penetration; b and c joints; d seals;
e presence of a probe (from Shreir et al. 1994)
Fig. 12.3 Crevice corrosion

on AISI 321 stainless steel
after a few months in seawater
For example, in a heat exchanger, critical situations are: interstices between

plates, tubesheet and tube, tube and diaphragm, welding defects, supports, spacers,
joints (bolted or riveted or forced), under gas bubbles (gas-liquid-metal three-phase
contact), under deposits and porous coatings.
Severe crevice occurs in conditions of high heat flux as, for example, in gaps that
form between tubes and tubesheet in boilers; this situation worsens by the formation
of deposits and the increase in concentration of aggressive species.
Figures 12.3 and 12.4 show examples of crevice corrosion of stainless steel in
seawater.
12.3 Mechanism of Crevice Corrosion
The mechanism of crevice corrosion of stainless steels in chloride-containing

solutions follows three stages.

on AISI 316 stainless steel in
seawater
12.3.1 First Stage
It is also called incubation or oxygen depletion stage, during which oxygen inside
the gap is consumed through the corrosion reactions occurring on passive stainless
steel, namely, oxygen reduction and passive film growth, as follows:
O2 þ 2H2 O þ 4e ! 4OH ð12:2Þ
xM þ yH2 O ! Mx Oy þ 2yH þ þ 2ye ð12:3Þ
The rate of reactions equals the slowest one, which is the passivity current density
of the metal, ip (mA/m2).
How long this stage takes depends on two parameters: passivity current density,
ip, and crevice volume, i.e., maximum available oxygen mass inside crevice. It
appears evident that the most influencing and decisive parameter is the passivity
current density, which in turn is function of composition of stainless steel—in short,
of PREN, pH and temperature (see Chap. 5, Fig. 5.21).
It has to be considered that when passivity current density is very low, in spite of
the tiny gap, some oxygen diffusion, i.e., oxygen renewal, becomes possible,
therefore the incubation has never an end: accordingly, crevice can never start.
For an estimation of the duration of this stage reference can be made to Oldfield
and Sutton (1978a, b) and to Oldfield (1987).
12.3.2 Second Stage
The second stage starts once oxygen is completely depleted in the crevice. The
elimination of oxygen inside the crevice brings stainless steel in active condition, as
schematically shown in Fig. 12.5.
12.3 Mechanism of Crevice Corrosion 235
Fig. 12.5 Potential change E

inside crevice during first
stage: conditions inside
(IN) and outside (OUT) the OUT
interstice
IN
log i
During this stage, two important processes take place: inside the crevice, metal
ions concentration can exceed 1 M, so hydrolysis reactions take place:
M ! Mx þ þ xe ð12:4Þ
yMx þ þ xH2 O ! My ðOHÞx þ yxH þ ð12:5Þ
and pH drops to very low values, such as below 2 (mainly for the contribution of
chromium), hence impeding repassivation; outside crevice, oxygen reduction
increases alkalinity, therefore strengthening passivity.
12.3.3 Third Stage
Third stage is when macrocell current becomes stationary. Macrocell current can be
calculated as reported in Lazzari (2017) as seen for pitting in Chap. 11. It is
important to emphasize that for crevice corrosion the driving voltage is expected to
be lower than that of pitting due to the higher ohmic drop contribution through the
narrow gap. As rule of thumb, it could be considered about a half of that adopted for
pitting corrosion; hence, a value as low as 0.2 V. In aerated seawater, crevice
corrosion rate varies between 1 and 5 mm/year regardless the stainless steel grade.
For several aspects, crevice corrosion can be compared to pitting and some
authors consider crevice a particularly severe form of pitting or a pitting just ini-
tiated; others consider pitting a particular form of crevice corrosion, arguing that the
main difference is a matter of size (crevice corrosion in something macroscopic
whilst pitting is microscopic). In any case, experience tells that environmental
conditions, which cause pitting, cause also crevice corrosion, instead the opposite is
not always true.
12.4 Metal Composition
Crevice occurrence depends on many factors, primarily on those related to nature,

composition and structure of metal. In the case of stainless steels, the increase in
chromium content and even more the presence of molybdenum and nitrogen is
beneficial in promoting a stable passive film.
The resistance to crevice corrosion of stainless steels and other passive metals is
determined by the passivity current density, therefore it depends on PREN (see
Chap. 11). For example, in seawater stainless steels with PREN in the range 35–40
are not subject to pitting (at least for temperatures below 30 °C and no biofilm
formation), instead they can suffer crevice.
Even the type of crevice has an important influence. For piping systems used in
oil & gas industry operating at temperatures above 60 °C, superaustenitic steels
with 6% Mo (type 254 SMO—PREN 43) are suitable for flanges with O-ring seal
type, but not for threaded joints. For the latter, a superaustenitic steel with more
than 7% Mo (type 654 SMO—PREN > 50) has to be used.
Other parameters, in analogy to those used for pitting to determine whether
metals resist, are the critical crevice temperature (i.e., maximum temperature
without crevice attack for each gap size) and the critical potential. Both are smaller
than those for pitting and depend on crevice size; for example, crevice critical
temperature is about 15 °C lower than pitting critical temperature.
12.5 Environmental Factors
Factors favouring crevice are chloride content, acidity, temperature, potential and
bacterial activity: as each of these factors increase, crevice likelihood increases. For
example, incubation time for stainless steel AISI 316 grade is a few weeks in
seawater (pH around 8, chloride content 20 g/L) and increases to several months in
industrial waters (same pH and chloride content below 1 g/L). However, with same
chloride content, if pH drops from 8 to 5 or if the solution is contaminated by
bacteria, incubation time decreases by one order of magnitude.
The influence of potential is summarized by comparing Figs. 12.6 and 12.7,
which show the different crevice attack on two stainless steel plates in a test
performed with the multiple crevice assembly, which consists of a Teflon seg-
mented washer having a number of grooves and plateaus pressed on the metal
surface. An AISI 316 stainless steel plate freely exposed in seawater, showing a
potential between +0.2 and +0.4 V SCE, was compared with a plate of the same
material welded to carbon steel, hence operating at a more negative potential by
some hundreds mV. After an exposure of six months, the first specimen showed
crevice attacks as deep as 0.5 mm, while the second one showed no corrosion and
the formation of some calcareous deposit as consequence of the galvanic coupling
with carbon steel.
12.5 Environmental Factors 237
Fig. 12.6 Results of crevice

attack obtained with multiple
crevice assembly on an AISI
316 plate
Fig. 12.7 Results of crevice

attack obtained with multiple
crevice assembly on an AISI
316 plate welded to carbon
steel
12.6 Prevention of Crevice Corrosion
The prevention of crevice corrosion has to be carried out, primarily, in design and
construction phases in order to avoid crevices as cracks, gaps and deposits.
Sometimes, it is sufficient to change design through just a simple trick, as in the
case of heat exchangers, by choosing the aggressive fluid, for example sea water, to
pass inside tubes where crevice conditions are absent, unlike the shell side where
crevices are inevitably present (between tubes and tubesheet and tube and
diaphragms).
When crevice conditions are inevitable, its prevention follows two ways:
selection of resisting material or by cathodic protection (in the case of stainless
steels, iron anodes are often used). The conditioning of the electrolyte, as the use of
corrosion inhibitors or by removal of oxygen, is not recommended because risky: if
a crevice attack starts during the accidental suspension of the treatment, it cannot be
halted by the treatment restart.
12.7 Crevice-Like Corrosion of Active Metals
The presence of interstices is always an aggravating corrosion factor also for active
metals. The incubation mechanism is different, instead propagation follows again a
macrocell mechanism. Typical cases are accumulation or entrapment of aggressive
liquids in gaps, temperature increase in screened zones, non-homogeneous zones.
Differential aeration is a typical case of localized corrosion for carbon and low
alloy steels as active metals: the anode is inside a recess or interstice or beneath a
deposit where oxygen supply is reduced or even hampered and the cathodic zone is
where oxygen is available. Corrosion rate is ohmic drop controlled and determined
by the oxygen limiting current density; the anodic surface area is the gap or the
screened surface area and the effective cathodic surface area is determined by
throwing power (see Chap. 9). Some crevice-like attacks on active metals occur on
atmospherically exposed structures in absence of electrolyte outside the crevice, as
discussed in the following.
12.7.1 Corrosion Under Insulation
Under insulated surfaces of equipment operating in marine atmosphere there is

often a high chloride concentration, carried by percolating rainwater which has
washed polluted surfaces; beneath the insulation, high temperatures facilitate the
evaporation of water, then leading to high chloride concentrations. Similarly, in
chemical plants, the leakage of saline solutions favours contamination under
insulation.
12.7.2 Automotive Related Corrosion
Some hidden parts of cars chassis, made of steel sheets, present interstices, espe-
cially where sheets overlap, as well as in joints made by spot welding or by stapling
or sheet folding. Corrosion of these hidden parts is called in-out corrosion.
Junctions are located mostly inside boxed parts, as for example doors or bonnet,
which are made with two stapled sheets, one internal and the other external: inside
12.7 Crevice-like Corrosion of Active Metals 239
these boxes the environment is different from the external one. In these areas,
almost inaccessible for painting protection, corrosion proceeds invisibly until
interesting full plate thickness, then degrading aesthetics and jeopardizing structural
strength. Since about two decades, this corrosion has been neutralized by improving
design, simplifying and reducing the number of traps and overall by adopting
galvanized steel sheets.
12.7.3 Riveted Structures
Riveting or bolting of plates forms interstices, which retain moisture or electrolytes

of different origin, with risk of corrosion beneath because any prevention measure is
difficult. Corrosion products, which occupy a much larger volume than the corroded
metal (iron), provoke a significant distortion on coupled plates.
12.7.4 Stored Plates
A crevice-like corrosion takes place on galvanized or aluminium sheets used in civil

and furniture structures when stacked in high humidity storage environment.
Moisture condenses between overlapped surfaces and generates aesthetically unac-
ceptable surface alterations. For galvanized sheets, this phenomenon is known as
white corrosion for the whitish colour of the corrosion products. Best practice for
storage of these artefacts is dry condition or packaging in sealed polyethylene sheaths.
12.8 Filiform Corrosion
A particular type of crevice corrosion, called filiform corrosion, occurs beneath

paints or lacquers on a coated metal surface. Corrosion attack starts from coating
defects and grows as thin-looking grooves or wires, a few tenth of a millimetre
wide, which affect only superficially the metal surface, for example a few tenth of a
micron deep. Corrosion products, having a volume larger than that of the corroded
metal, cause local coating disbonding and formation of clearly visible linear bulges,
with the curious trend described in Fig. 12.8 and shown in Fig. 12.9 after a labo-
ratory testing. Each “wire” propagates in a straight line until it crosses another one
already developed; at this point, the wire proceeds in a mirrored or a parallel
direction, depending on the incidence angle, greater or lower than a critical value (if
greater there is reflection, if lower there is parallelism or merging), producing a
labyrinth-type array. Metals typically showing this attack are steel, aluminium and
magnesium when covered by coatings that are permeable to moisture, placed in an
atmosphere with relative humidity above 70%.
Fig. 12.8 Scheme of filiform corrosion
Fig. 12.9 Filiform corrosion

obtained during testing
The mechanism of this corrosion attack was studied through a transparent lac-
quer: in case of steel, the wire head became green because of ferrous ions while the
body became red because ferric ions formed by oxidation of previous ferrous ones.
Therefore, the anodic process is located in the head, where there is a lack of oxygen
and acidity by hydrolysis is maintained, and the cathodic areas, where oxygen is
more easily available, are localized behind (see sketch in Fig. 12.10). The alka-
linisation of the cathodic area explains the formation of the array: the acidic head of
a new wire is neutralized when crossing an old one, therefore it deviates.
Filiform corrosion stops as humidity decreases or coatings imperviousness
increases.
• ASTM G 48—Standard Test Methods for Pitting and Crevice Corrosion

Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride
Solution, West Conshohocken, Pa.: American Society for testing of Materials.
12.9 Applicable Standards 241
O2 H 2O
Head H2 O O2
Thin coating
Hydrolysis O2
Low pH - Low O2 Fe(OH)3
Steel substrate
Fig. 12.10 Filiform corrosion mechanism
• ASTM G 78—Crevice Corrosion Testing of Iron-Base and Nickel-Base

Stainless Alloys in Seawater and Other Chloride-Containing Aqueous
Environments, West Conshohocken, Pa.: American Society for testing of
Materials.
• ASTM G 192—Standard Test Method for Determining the Crevice
Repassivation Potential of Corrosion-Resistant Alloys Using a
Potentiodynamic-Galvanostatic-Potentiostatic Technique, West Conshohocken,
Pa.: American Society for testing of Materials.
• ASTM F 746—Standard Test Method for Pitting or Crevice Corrosion of
Metallic Surgical Implant Materials, West Conshohocken, Pa.: American
Society for testing of Materials.
• ISO 18070—Corrosion of metals and alloys—Crevice corrosion formers with
disc springs for flat specimens or tubes made from stainless steel, International
Standard Organization, Geneva, Switzerland.
• ISO 18089—Corrosion of metals and alloys—Determination of the critical
crevice temperature (CCT) for stainless steels under potentiostatic control,
International Standard Organization, Geneva, Switzerland.
12:1 Can a galvanic coupling influence the crevice initiation? Explain what
would be the expectation in case of coupling with a less noble metal or
instead a more noble one. Make an example.
12:2 A stainless steel is exposed to seawater with the presence of interstices (for
example, a plate-tube assembly without welding sealing). In design phase,
the coupling with titanium is analysed. What is your opinion about this
choice? Would you approve such a choice? Explain.
12:3 To prevent crevice of stainless steels, cathodic protection can be adopted.

Can you suggest protection conditions, as protection potential and protec-
tion current?
12:4 Crevice corrosion does not occur on aluminium alloys although their active-
passive behaviour. Suggest an interpretation.
12:5 Crevice corrosion on titanium alloys takes place in acidic chloride con-
taining solution at temperature above 70 °C. Try to investigate the mech-
anism involved through two phases: initiation and propagation.
12:6 In the case of stainless steels in seawater, crevice corrosion rate does not
depend on stainless steel grade or composition. Give an extensive
explanation.
12:7 Consider the previous exercise. What is the effect of a galvanic coupling
with titanium on crevice corrosion rate?
12:8 List the affecting parameters of crevice corrosion. Rank by your opinion
such a list from the most important to the lesser one and give a justification.
12:9 Crevice corrosion of stainless steels in seawater is influenced by the pres-
ence of biofilm. Because biofilm cannot grow inside the interstice, how do
you explain such influence? Can a treatment with chlorine, which avoids the
formation of biofilm, reduce the risk of crevice?
12:10 Once crevice corrosion of stainless steels in seawater has started, someone
suggests cleaning and neutralizing treatments to stop the corrosion propa-
gation. Discuss critically such recommendation, indicating the associated
risks, if any.
Bibliography
Oldfield JW (1987) Test techniques for pitting and crevice corrosion resistance of stainless steels
and nickel alloys in chloride containing environments. Int Mater Rev 32:153–170
Oldfield JW, Sutton WH (1978a) Crevice corrosion of stainless steels: I. A mathematical model. II.
Brit Corros J 13:13–22
Oldfield JW, Sutton WH (1978b) Crevice corrosion of stainless steels: II. Experimental studies.
Brit Corros J 13:104–111
Chapter 13
Stress Corrosion Cracking
and Corrosion-Fatigue
Stress corrosion and hydrogen-induced cracking resemble the

fable of the blind men and the elephant. Investigators have
tended to perceive only single aspects of the problem and to
design experiments in which important variables were either
not appreciated, not controlled, or not measured.
R. A. Oriani
Abstract When a susceptible metal is in contact with a specific environment, in

presence of a tensile stress exceeding a threshold, the corrosion-enhanced formation
of cracks and catastrophic failure is called stress corrosion cracking (SCC).
Although infrequent, consequences are so dangerous that it deserves to be described
in details: in this chapter, after the introduction of the SCC mechanism, mechanical,
metallurgical and environmental factors at its basis are explained, and specific
preventative measurements are suggested. Another form of degradation that links
mechanical stress and corrosion, i.e., corrosion-fatigue, is also described.
Fig. 13.1 Case study at the PoliLaPP corrosion Museum of Politecnico di Milano

https://doi.org/10.1007/978-3-319-97625-9_13
244 13 Stress Corrosion Cracking and Corrosion-Fatigue
13.1 Definitions
Stress Corrosion Cracking (SCC) together with Corrosion-Fatigue and Hydrogen

Embrittlement belongs to so-called Environmentally Induced Cracking or
Environment Sensitive Cracking. This chapter refers exclusively to SCC of metals
taking place through the anodic dissolution process (Fig. 13.1), whilst hydrogen
embrittlement is discussed in Chap. 14. In the past, SCC was known with different
names depending on metals and environments involved, for instance: caustic
embrittlement of carbon steel, seasonal cracking of brass, nitrate cracking, liquid
metal embrittlement and many others. To have SCC, a secific combinations
metal-environment-tensile stress as depicted by a Venn diagram (Fig. 13.2), that
result into the formation of cracks, is necessary. This condition is intrinsically rare
as the three factors are in an AND logic relationship (i.e., there is the need for the
simultaneous presence of all three conditions: a susceptible metal, a specific
environment and a tensile stress regime exceeding a threshold). Nevertheless, when
it happens, the resulting cracking has catastrophic consequences. For this reason it
has to be avoided.
Typical case studies of SCC reported in literature deals with:
• Carbon steel and low alloy steel in boilers, chemical equipment, piping, in the
presence of nitrate or alkaline solutions or hydrogen sulphide as in oil & gas
facilities
• High strength ferritic steels in aqueous environments
• Stainless steels in chloride containing solutions (Figs. 13.3 and 13.4) and high
pH solutions in chemical and petrochemical plants or in nuclear reactors
exposed to pure water at elevated temperatures (above 290 °C)
• Copper alloys in presence of ammonia
• Aluminium in chloride containing solutions.
Fig. 13.2 Representation of

required conditions for SCC
occurrence by means of a
Venn diagram
Stress Environment
SCC
Material
13.1 Definitions 245
Fig. 13.3 Example of SCC-related failure of a carbon steel pipeline
Fig. 13.4 SCC of high strength low-alloy steel tool joint in an oil and gas well
As said, SCC is produced only for specific metal-environment combinations. For

example:
• Austenitic stainless steels suffer SCC in chloride containing solution or in hot
alkaline solutions and not in ammonia as copper alloys or nitrate solutions as
carbon steel
• Carbon steel in nitric acid or hot alkaline solutions but not in solutions with
chlorides or ammonia
• Copper alloys in ammonia containing solutions and not in solutions with
chlorides
• High strength steels can crack simply in water. In this case, the specificity of the
environment is less significant.
SCC occurs in electrolytes, organic liquids, molten salts, liquid metals, gaseous
atmospheres, under scales. For example, titanium can crack in methanol, under
sodium chloride scale in hot or gaseous nitrogen tetroxide, N2O4. Even
non-metallic materials suffer cracking in specific environments; for instance,
polyethylene or natural and synthetic rubbers crack when mechanically stressed in
environments in which they are not soluble.
13.2 SCC Mechanisms
Several hypotheses of SCC mechanism have been proposed. Following a simplified

approach, there are two basic mechanisms, as described in Fontana (1986): one as
anodic and another one as cathodic. Accordingly, the growth of cracks takes place
according to one of the following mechanisms:
• Crack tip dissolution (called slip-dissolution) is based on the anodic dissolution
of the metal
• Crack tip rupture caused by atomic hydrogen, produced by the cathodic process,
which enters the metal and accumulates at crack tip (called Hydrogen
Embrittlement, HE).
The first mechanism claims a continuous crack growth by anodic dissolution of
the crack tip, which is active, while crack wall surface and surface outside the crack
remain passive, then a macrocell sets up (Fig. 13.5a). The reason why the crack tip
is active is that the stress field around it, representing a sharp defect, produces a slip
exposing new bare metal surface, which does not passivate. To match this critical
(a) (b)
σ σ σ σ
H+ + e- = H
H H
M2+M2+ H H
M2+ HH H
H
a) b)
Fig. 13.5 Simplified representation of SCC mechanisms: a slip dissolution; b hydrogen

embrittlement (HE). Adapted from Fontana (1986)
13.2 SCC Mechanisms 247
condition, it is required that the rate of formation of new bare metal surface by slip
deformation at crack tip (which equals strain rate caused by the tensile load) is of
the same order of magnitude of the passivation rate, which depends on electro-
chemical conditions.
When the mechanism is HE, as discussed in Chap. 14, crack grows by suc-
cessive mechanical ruptures at crack tip due to a decrease of metallic bond strength
that is caused by the accumulation of the atomic hydrogen originated by the
cathodic process (Fig. 13.5b). Steps of the mechanism are: the cathodic process
produces atomic hydrogen, which enters the metal and diffuses to the dislocations at
the crack tip, then provoking interatomic de-cohesion and crack growth; at the new
crack tip, new dislocations form and new atomic hydrogen arrives and so on cycling
in a discontinuous manner.
Several experiments support the two mentioned mechanisms. The most impor-
tant one is the influence of potential: a cathodic polarization decreases corrosion
rate and increases hydrogen evolution, therefore crack growth rate reduces when the
first mechanism applies, while it increases if it fits the second one; the opposite
happens when potential varies toward the anodic direction.
However, the two mechanisms do not explain the morphology of cracks either in
the case of slip-dissolution or HE when, in the latter, cracks are surprisingly
intergranular; furthermore, they do not predict when it may or may not be produced,
also taking into account that similar failure occurs in non-metallic materials. For
these reasons, other theories have been proposed to try and to put in one frame all
environment assisted cracking phenomena, corrosion-fatigue included.
13.3 Morphology and Conditions of Occurrence
SCC related failures often appear without plastic deformation, then at first sight it
could be mistaken for a fracture of brittle material; instead, metals suffering SCC
are normally ductile. Cracks form and grow in perpendicular direction to maximum
tensile stress and do not show visible corrosion products. Figure 13.6 depicts the
morphology of cracks which depends on metal, environment and entity and
(a) (b) (c)

σ σ σ σ σ σ
Fig. 13.6 Depict of the appearance of cracking propagation in SCC: a intergranular; b trans-
granular; c delta river transgranular
Fig. 13.7 a Transgranular cracks due to SCC observed on an AISI 316 stainless steel exposed to
seawater at 70 °C; b intergranular cracks from SCC on AISI 304 stainless steel in caustic soda,
200 °C
distribution of stresses, cracks are mainly inter-crystalline (intergranular) or

trans-crystalline (transgranular) and are more or less branched. Figure 13.7 shows
some examples of cracking morphology for different metals.
SCC follows three steps:
• Initiation, or incubation
• Propagation
• Final mechanical failure.
13.3.1 Crack Initiation
Starting from a smooth surface, a certain time is needed before the first micro-crack
can be detected, this time period, called incubation time for crack initiation varies
from a few minutes to several years, depending on mechanism of crack nucleation,
metal structure and environment properties such as salinity, pH and oxygen content
or other oxidizing species, open circuit potential, temperature, static or variable
applied stress. For example, austenitic stainless steels in boiling magnesium chlo-
ride solution show cracks after only a few hours of exposure; instead, nickel
super-alloys, used in nuclear reactors in contact with pure water at high temperature
(290–320 °C), show cracking after several years. In any case, crack nucleation is a
stochastic phenomenon and consequently incubation time is characterized by a high
scattering also influenced by the fluctuation of affecting factors.
The presence of notches as welding defects or mechanical grooves favours crack
initiation. However, SCC also occurs on smooth surfaces, free from macroscopic
defects. As often happens, the exposure environment is, per se, SCC safe, but as
13.3 Morphology and Conditions of Occurrence 249
Fig. 13.8 SCC starting at the

bottom of a pit
a consequence of local change, it may become harmful. This typically occurs inside
pits and crevices or under scales, because of concentration processes, as, for
example, in distillation columns of crude oil. Figure 13.8 shows cracks originated
from a pit bottom. In other situations, aggressiveness increases because temperature
increases, as in heat exchangers; to reduce this risk in household boilers made of
austenitic stainless steel, where SCC may occur beneath the calcareous deposit that
precipitates in high hardness waters, cathodic protection is adopted.
13.3.2 Crack Propagation
Once a crack has initiated, its propagation takes place by the combined action of a
corrosion mechanism and the applied tensile stress, at a crack growth rate, which
varies in a wide range between 10−6 m/s (≅31 m/y) and 10−11 m/s (≅0.3 mm/y),
the latter being close to laboratory measurement limit. This crack growth stage is
called subcritical or stable propagation stage. For example, SCC growth rate is
close to the upper limit for:
• Austenitic stainless steels in chloride containing solutions
• Copper alloys in ammonia
• Carbon steels in nitrate solutions.
Conversely, crack growth rate is close to the lower limit for example for:
• High nickel alloys, as alloy 600 used in nuclear plants in contact with pure water
at 290 °C
• welded carbon steel in liquid ammonia with traces of water.
Eventually, as crack size comes across a critical value in accordance with fracture
mechanics, as discussed later, crack propagates at a very fast rate under the action
Corrosion
penetration
Thickness
metal A B
Unstable
propagation Stress corrosion
dcrB cracking
Pitting
dcrA
ti trA trB Time
A: low toughness metal

B: high toughness metal
Fig. 13.9 SCC time to failure for two metals, A and B, with different fracture toughness with
crack initiation from a pit (trA and trB service life of A and B, respectively; dcr is critical defect
size). Adapted from Brown (1968)
of purely mechanical stress to the final rupture, that can be brittle or ductile. This
behaviour is called instable crack propagation stage.
Time-to-failure of SCC is the sum of crack initiation time and crack growth
time. Figure 13.9 shows schematically the behaviour of two metals, A and B, with
different fracture toughness, both suffering SCC from an initial pitting attack. It is
possible to observe the pitting initiation time, ti, and the SCC propagation time,
whose sum gives the time needed to reach unstable propagation, i.e. the end of
service life for material A, trA, and B, trB. Fracture toughness of metal A is lower
than the one of metal B, so that critical crack size for A, dA, is smaller than the one
for B, dB, and accordingly, time-to-failure for A is lower than the one for B.
13.4 Mechanical Aspects
The conventional approach for studying SCC is, once identified the
metal-environment coupling susceptible to SCC, the experimental determination of
the time-to-failure obtained on smooth specimens by varying the applied nominal
stress, r, as affecting mechanical parameter. Although the nominal stress does not
reflect the real stress at crack tip (because of the intensity factor), by this approach a
threshold stress, rth, is obtained, below which SCC does not take place. This
parameter, which is regarded as a metal characteristic, is affected by a high scat-
tering because measured on smooth specimens. For this reason, it cannot be used
for design purposes; instead, it is useful to carry out a ranking of candidate metals
through tailored laboratory tests.
13.4 Mechanical Aspects 251
Since mid-1970s, SCC studies adopted concepts, parameters and methods of

fracture mechanics, assuming that sharp defects were, cautionary, always present in
metals, then enabling to trigger crack initiation; this, indeed, is realistic because
defects are always present in raw metals or generated in construction and also
during operating.
13.4.1 Stress Intensity Factor, KI, and Fracture Toughness,

KIC
The stress at the tip of a sharp notch increases as tip radius lowers. It is demon-
strated that in elastic behavior and without plasticization at the notch tip, the stress
field at the tip is represented by a parameter called stress intensity factor, KI,
expressed by the following relation:
pffiffiffiffiffiffi
KI ¼ br pa ð13:1Þ
where b is dimensionless geometry correction factor, whose value depends on

geometry of component and defect (typically in the range 1–2), r is a characteristic
stress and a is a characteristic crack size.
From a purely mechanical point of view, the stress intensity factor, KI, allows to
specify the condition for unstable fracture propagation in low ductility metals,
which takes place when KI reaches a critical value, KIC, called fracture toughness.
Fracture toughness, KIC, is an inherent material property. Since SCC occurs for an
applied tensile stress below the yield strength (i.e., in the elastic range), KI, among
various parameters of fracture mechanics, resulted as the most appropriate.
13.4.2 Crack Growth and KISCC
Experience has shown that there is a finite crack propagation rate of SCC, for which
the term subcritical growth is used, when KI has values between the limits given by
two parameters:
• A threshold value, called KISCC that indicates the value of the stress intensity
factor below which cracks cannot grow by an SCC mechanism
• KIC, the fracture toughness.
As crack grows, nominal stress r as well as KI varies, either increasing or
decreasing. When increasing, that is under constant load condition, subcritical crack
growth proceeds until KI equals KIC with final sudden rupture; in the second case,
which occurs under constant strain condition, crack propagation stops as KI
decreases to KISCC.
While KIC is an intrinsic parameter of materials, similarly KISCC is an intrinsic

parameter of metal-environment coupling and, in principle, can be used as design
parameter. In practice, this approach is not followed because of a twofold reason:
the scattering of results in laboratory testing and its variability even with little
variations of either metal or environmental characteristics, for instance, impurities
in metal composition and changing of environmental parameters.
13.4.3 Crack Growth Rate and KI
Relationship between crack growth rate, da/dt, and stress intensity factor, KI, is
shown in a semi-logarithm plot in Fig. 13.10. In the range KISCC to KIC, three
intervals can be found:
• Interval I: crack growth rate depends strongly on KI, whereby a small increase
of KI produces orders of magnitude increase of crack growth rate
• Interval II: two possible behaviours
– Curve (A) for slip-dissolution mechanism: crack growth rate is roughly
independent on KI and generally coincides with the corrosion rate at crack
tip. Accordingly, rather than mechanical, controlling factors are those
associated with the corrosion process as driving voltage, current density of
cathodic process and environment resistivity
– Curve (B) for hydrogen embrittlement mechanism, where mechanical factors
generally govern the crack growth.
• Interval III: crack growth rate increases rapidly as KI approaches fracture
toughness, KIC.
log (da/dt)
I II III
KISCC KIC KI
Fig. 13.10 Schematic trend of crack growth rate with stress intensity factor
13.4.4 Crack Growth and Strain Rate
At the beginning of 1970s, Parkins showed that SCC does not depend only on
stress level, instead on strain rate and it seems erroneous to assume that there is a
critical stress threshold, rth. Parkins showed precisely that SCC occurs only when
strain rate falls within a critical interval that depends on metal/environment cou-
pling and applied potential. As shown later, this behavior is typical for metals
following the slip-dissolution mechanism, where crack grows by the dissolution of
the active crack tip, while other surfaces are passive. In short, the mechanism claims
that as first step crack tip becomes active due to the formation of new bare surface
caused by the strain, followed by a second step by which the corrosion attack takes
place during the repassivation time. This cycle film rupture-corrosion -repassivation
starts again and so continuing. Figure 13.11 shows examples of SCC behaviour for
different strain rates in various environment compositions and applied potentials;
Fig. 13.12 illustrates also how strain rate influences stress-strain curves. Eventually,
Fig. 13.13 shows that small, slow fluctuations of applied load, unable to sustain
fatigue or corrosion-fatigue phenomenon may be sufficient to widen the range of
conditions for crack to grow.
13.4.5 Test Methods—SSRT
When testing SCC susceptibility, an important parameter is the strain rate range that
must be specified. Parkins developed and suggested a test method at constant strain
rate, called as Slow Strain Rate Test, SSRT, consisting of the application on either
Fig. 13.11 Effect of strain

rate on SCC occurrence on 1100
Mg–Al alloys in a 20 g/L
chromate containing solution
1000
with different amounts of g/L Cl
Maximum load (N)
chlorides (from Parkins 1973)

2,5
900 5
35
800
700
600
10-3 10-4 10-5 10-6

Strain rate (s-1)
σ
(MPa) In CP: E = -1000 mV SCE
600
550
.
ε = -10-6 s-1
.
ε = -10-5 s-1
300
250
Free corrosion .
ε = -10-6 s-1
0 3.8 11 33 ε (%)
Fig. 13.12 Stress-strain curves of an austenitic stainless steel containing nitrogen for different
strain rates in free corrosion and under cathodic protection in magnesium chloride boiling solution
(from Magnin 1996)
Fig. 13.13 Effect of small

fluctuations of tensile load on σ
th
intergranular SCC occurrence (MPa)
on C-Mn steels in carbonate/ Static
bicarbonate solutions at 82 °C
and −0.65 V SCE (from 400
Parkins 1972)
300
72% Y
200
100
-7 -6 -5 -4 -3
10 10 10 10 10
Frequency (Hz)
pre-cracked or smooth specimens of a constant strain rate, in the interval 10−6 to

10−4 s−1, which determines a time to failure ranging from a few minutes to a few
weeks. The selected strain rate depends on environment aggressiveness and pas-
sivation tendency of the metal. In the SSRT the stress-strain curve obtained in the
environment under examination is compared with the one obtained on the same
material in an inert environment, e.g., vacuum, dry air or oil, when the material is
susceptible to SCC, the maximum applied load is lower than that required in the
inert environment at same testing conditions. SCC occurrence is also evaluated by

metallographic observations of fracture surface in combination with the ductility
decreasing measured as reduction of fracture surface area and percentage elongation
on failed specimen.
13.5 Environment-Related Parameters
Table 13.1 shows a partial list of combinations of metal-environment that give

SCC; the list has grown with time making clear the concept of specific environment
for a metal. Based on that, corrosion engineers have become aware that only precise
environments can promote SCC on a metal.
As SCC starts, there is the need, at least for the anodic mechanism, that the
reaction occurring at the crack tip is faster than repassivation, otherwise either a
general attack or pitting would take place. Accordingly, an environment is specific
when it enables to ensure the passivity of exposed surfaces and crack wall surfaces,
and at the same time makes the crack tip active.
In most cases, the environment should exhibit the combined presence of factors
that act in opposite directions: one favours passivation and the other does not. For
Table 13.1 Metal/environment combinations susceptible of SCC

Metal Environment (solutions) Temperature
(°C)
Carbon steel Caustic >80
Carbonate-bicarbonate 50/60
Nitrate 50/60
Phosphate 50/60
Liquid ammonia with traces of Tamb
water All
CO/CO2/H2O
Austenitic stainless steel Neutral aerated containing >80/100
chloride
Acid containing chloride Tamb
H2S containing chloride Tamb
Caustic 80/120
Oxygen containing pure water 100
Nickel alloys Caustic >100/200
Nickel alloys (Cr < 30%) Water with dissolved H2 >250/280
Sensitized stainless steel and nickel Polythionates and thio-sulphates Tamb
alloy
Copper alloy Ammonia containing Tamb
Aluminium alloy Chloride containing Tamb
Titanium alloy Alcoholic containing chloride Tamb
example, magnesium alloys suffer SCC in chromates-chlorides mixtures, that is, in

the presence of a passivating agent (i.e., chromates) and a depassivating one (i.e.,
chlorides), but not when only one of these species is present.
In general, it is observed that metals highly resistant to corrosion because pro-
tected by a passive film such as titanium, aluminium, nickel, chromium and
stainless steels, suffer SCC when a chemical species, for example chlorides, that
enables to breakdown the passive film is present.
Conversely, metals easily corroding, for example magnesium alloys and carbon
steels, suffer SCC only if a passivating chemical species is present, such as
hydroxides, carbonates and nitrates.
For the above reasons, SCC occurs only in narrow ranges of potential, across the
active/passive boundary or the passive/transpassive one (Figs. 13.14 and 13.15):
therefore, the cathodic process is important, as well as the presence of galvanic
couplings that determine the working potential. Accordingly, oxygen content or the
presence of oxidizing species can move the working potential inside or outside the
critical range. For examples: austenitic stainless steels suffer SCC in pure water
containing traces of chlorides at temperature above 200 °C only if oxygen is pre-
sent; conversely, in carbonates and bicarbonates solutions the presence of oxygen
keeps carbon steel potential outside hazardous conditions.
An important variable is temperature: as it increases, SCC occurrence increases
(except for HE, see Chap. 14). There is often a temperature threshold (Fig. 13.16).
As temperature changes, environment composition may change, making SCC
possible; for example austenitic stainless steels suffer SCC at temperatures around
60 °C with a few tens of ppm of chlorides, while at temperatures close to 300 °C,
typical of nuclear plants, critical chloride concentration drops below 1 ppm;
eventually, below 50 °C, SCC does not occur at any chloride content, at least in
neutral and alkaline solutions.
Fig. 13.14 Potential E

intervals for SCC occurrence.
Adapted from Staehle (1977)
log i
13.5 Environment-Related Parameters 257
1000
Potential (mV SHE)

Potential (mV SCE)
1000
500 Liquid
Nitrates Hydroxides ammonia 500
0
0
Chlorides
-500
Carbonates
-500
Hydroxides
-1000
Fig. 13.15 Potential intervals for SCC occurrence with slip-dissolution mechanism of carbon
steel in different electrolytes (after Parkins)
Temperature
(°C)
SCC SCC SCC SCC SCC
80 P P P SCC
60 P SCC P
40 O O P S P
20 O O S S S
102 103 104 105

Cl- concentration (ppm)
Fig. 13.16 Temperature and chloride content mapping for AISI 304 stainless steel: SCC, pitting
(P), rouging (S), no corrosion (O) (Sedriks 1996)
13.6 Metallurgical Factors
13.6.1 Composition
Composition and structure of the metal, in combination with environmental con-

ditions, influence the occurrence of SCC. For example, the addition of nickel to
steel improves SCC resistance in alkaline environment, while it does not in nitrate
1.000
Time-to-failure (h)
100
10
0 10 20 30
Nickel content (%)
Fig. 13.17 SCC resistance of Ni containing ferrous alloys in MgCl2 boiling solutions (Copson
1959)
containing solutions, and decreases in presence of chlorides. Similarly, the addition

of molybdenum to ferritic steels is beneficial in carbonates/bicarbonates containing
environments but has an opposite effect in alkaline solutions. Nevertheless, a
general trend exists for predicting SCC.
Pure metals (99.99% grade or above) have a very high resistance to SCC;
however, just a small level of impurities such as in commercially pure metals (for
example 99.5%) is sufficient to decrease the resistance to SCC. An interpretation is
that selective corrosion attack, caused by the impurities as inclusions or inter-
metallic phases, triggers SCC initiation.
The addition of an element to an alloy as solid solution changes SCC resistance:
sometimes as content increases, resistance decreases to a minimum and then
growing again. For instance, stainless steels exhibits the minimum resistance to
chloride-induced SCC when nickel content is about 10% (Fig. 13.17) which mat-
ches the one of most used austenitic stainless steels, as AISI 304 and 316 stainless
steel. These grades suffer SCC in chloride containing solutions, even at low stress
level (100–150 MPa), when temperature exceeds 50–60 °C.
Stainless steels with low to zero nickel content, such as duplex type (with
austenitic–ferritic structure) with about 4–7% Ni and ferritic type, which contain no
nickel, resist much better to SCC. Furthermore, SCC resistance increases when
nickel content exceeds 20% (so-called alloys 20 and superaustenitic stainless steels)
or even better when it exceeds 40% (nickel based alloys) as depicted in Fig. 13.18.
13.6 Metallurgical Factors 259
Temperature
(°C)
Superaustenitic
250
stainless steel
150
Austenitic-ferritic
stainless steel
50
AISI 304-316
1 102 104
Cl-concentration (ppm)
Fig. 13.18 Chloride induced SCC in neutral solution (above lines) for austenitic, superaustenitic
and duplex steels. Adapted from Denhard (1960)
KI
(MPam)
100
80
KIC
60
40
KISCC
20
0
700 1.000 1.300 1.600
σY (MPa)
Fig. 13.19 KIC and KISCC of AISI 4340 low alloy steel as function of yield strength (Brown
1968)
13.6.2 Mechanical Strength
The mechanical strength of a metal, regardless how it is obtained, influences SCC

susceptibility through KISCC. Figure 13.19 shows for a low alloy steel how the yield
strength, rY (obtained at different tempering temperatures) influences KIC and
KISCC which both decrease as yield strength increases; KISCC, i.e., SCC suscepti-
bility, is more strongly influenced.
13.6.3 Sensitization
Sensitization plays a very important role in SCC susceptibility. Let's consider two
case studies regarding austenitic stainless steels, which sensitize in the temperature
range 500–850 °C, see Chap. 15.
The first case study, which caused in the past major problems in petrochemical
industry, deals with the exposure of sensitized austenitic stainless steels to sul-
phurous acid, thiosulphates or polythionic acids (these latter form by action of
moisture and oxygen on sulphide scales) causing SCC also at room temperature.
Stainless steel components may suffer SCC after a shutdown when production
restarts because of two occurrences: first they sensitize during operating if exposed
to the critical temperature interval and secondly polythionic acids form from sul-
phides during shutdown. This phenomenon was reproduced in laboratory.
The second case study deals with caustic soda solutions. The use of conventional
austenitic stainless steels for treating high purity soda up to concentrations of 50%
is an optimal choice from a technical-economical perspective, if temperature is
never higher than 60–70 °C: this strong limitation depends on the fact that at higher
temperatures a slight sensitization, possibly present near welds, is sufficient to cause
SCC.
Other factors affecting SCC occurrence are the presence of precipitates, their
distribution and orientation after a plastic deformation process as shown by the
anisotropic resistance to SCC of aluminium alloys after lamination, which is greater
when the applied stress is parallel to the rolling direction.
13.7 SCC Prevention
There are two general approaches for SCC prevention: the so-called safe-life and
fail-safe. The first one, which is adopted in the vast majority of applications, checks
that candidate material, environment composition, operating conditions (tempera-
ture, potential, tensile stress level) do not match the requirements for crack growth.
Only in rare cases the fail-safe philosophy is adopted: that is, when crack growth
rate is very low (for example cracks on welds in liquid ammonia containing tanks)
and monitoring is possible and reliable.
In practice, the prevention of SCC is obtained through:
• Reduction of either mechanical tensile stresses, in particular residual stresses, or
defect size so that the stress intensity factor, KI, is always lower than the
threshold value, KISCC
• Control of metallurgical, environmental and electrochemical (i.e., potential)
influencing factors.
13.7 SCC Prevention 261
13.7.1 Reduction of Stress and Defect Size
Stress level that triggers SCC is the sum of operating stresses due to internal
pressure and external loads, residual stresses as consequence of manufacturing
process, cold working, heat treatment, welding, construction stresses due to the
matching of the different parts to be joined during plant construction when com-
ponents do not perfectly fit; thermal stress for thermal expansion during operating.
Accordingly, the elimination or reduction of these stresses is different; in manu-
facturing it consists of stress relieving heat treatments, for example one hour at
300 °C for copper alloys, or one hour at 500 °C for stainless steels, in construction
by improving design and welding procedure control, in operating by avoiding
thermal inhomogeneity.
When high-strength alloys are employed because of the need to stand high loads,
SCC prevention must be based on fracture mechanics, by calculating the maximum
defect size tolerable at the nominal stress applied using the stress intensity factor,
KISCC, so that SCC cannot propagate. If critical defect size is detectable by a
non-destructive method, prevention is based on routine inspection; if not, design
must be changed by selecting another material or different heat treatment or by
changing environmental conditions or reducing stress level. Finally, as general
warning, it is necessary to bear in mind that SCC susceptibility increases as
mechanical strength increases, regardless how it is obtained.
13.7.2 Control of Environment, Metallurgy and Polarization
Environment control for SCC prevention consists of eliminating or reducing the

content of chemical species that trigger SCC initiation, either in bulk or locally as in
interstices or under deposits.
A polarization can bring the potential outside critical intervals, for instance by
the application of cathodic protection, as in the case of AISI 321 stainless steel
heating elements in household boiler by magnesium anodes.
Most often, to avoid risk of SCC, a resistant material is chosen. For example, in
the presence of chlorides at temperatures above 60 °C, the use of austenitic stainless
steels has to be discarded, and it is necessary to switch to highest grade such as
nickel-based alloys, or, conversely, to less expensive metals, such as carbon steels,
which suffer generalized corrosion but not SCC in these environments.
13.8 Corrosion-Fatigue
Metals subjected to a cycling variable tensile load can suffer a phenomenon of crack
formation and propagation, called fatigue, which may lead to rupture although the
applied load is lower than tensile strength. Figure 13.20 shows a typical mechanical
fatigue fracture surface, where beach marks (striations), as typical fingerprint of
fatigue, are easily recognized. The presence of an aggressive environment may
accelerate fatigue crack propagation so the phenomenon is called corrosion-fatigue
(C-F). The cracks are usually numerous, although branching typical of SCC do not
appear, and are predominantly transcrystalline on surfaces which are perpendicular
to the tensile stress direction.
Before reviewing the corrosion-fatigue, it is worth refreshing the pure
mechanical fatigue.
13.8.1 Mechanical Fatigue
The classical approach for studying fatigue is through r–log N diagrams (called
S-N diagrams or Wöhler diagrams), illustrated schematically in Fig. 13.21. The
number of cycles to failure increases as the oscillation amplitude of applied load,
Dr decreases. For carbon and low alloy steels a stress threshold exists, called
fatigue limit, rf, below which cracks do not grow.
S-N curves are affected by a high statistical dispersion as cycle number to failure
for a given value of r includes both crack initiation and propagation phases.
Fig. 13.20 Typical mechanical fatigue failure (case study at the PoliLaPP corrosion Museum of
Politecnico di Milano)
13.8 Corrosion-Fatigue 263
σ
(MPa)
Ferrous materials
σf
Non
ferr
ous
mat
eria
ls
101 102 103 104 105 106 107 108

Cycles to failure (N)
Fig. 13.21 r-log N diagram for fatigue
Typically, a crack starts from notches, surface micro defects as non-metallic

inclusions and dislocation slips. To study more accurately the crack propagation
phase, a fracture mechanics approach has to be used. Then, crack growth rate is
plotted against load amplitude, DKI, defined as difference between maximum and
minimum stress intensity factor during a load cycle:
DKI ¼ KI;max KI;min ¼ b ðrmax rmin Þ ðp aÞ0:5 ¼ b Dr ðp aÞ0:5 ð13:2Þ
where b is a geometry factor, Dr is the difference between maximum stress, rmax,

and minimum stress, rmin, and a is crack size. Figure 13.22 shows the plot of
da/dN
(mm/cycle) Subcritical crack propagation
according to Paris law
10-4
Unstable
10-5 fracture
No crack
propagation
10-6 da
= CKIm
dN
KI,max= KIC
10-7
KI,th KIC(1-R) KI
Fig. 13.22 Crack growth rate as function of DKI

fatigue crack growth rate per cycle (da/dN) as a function of DKI in inert environ-
ments. Crack growth proceeds according to the following equation:
da
¼ C DKIm ð13:3Þ
dN
called Paris law, where C and m are two constants of the metal and DKI, (Eq. 13.2)
can also be written as KImax (1 − R) where R is KImin/KImax. Relevant parameters
are:
• DKI,th, or threshold value, below which a crack, even pre-existing, for example
in welds or wrought, does not propagate
• DKIC, as maximum value reached: when KI,max = KIC, the crack becomes
unstable and propagates at high velocity
• Module, m, of Paris law which gives the slope of the fatigue crack growth rate
as a function of DKI in the interval DKI,th − DKIC.
13.8.2 Influencing Factors
An aggressive environment can enhance fatigue damage rate by reducing the ini-
tiation time e.g. by pitting, and accelerating crack propagation rate, this phe-
nomenon is called corrosion-fatigue. Figure 13.23 shows a case study of C-F in
seawater.
Variables involved are many and interrelated, including metal and environment
properties as well as the mechanical stress level. It is important to note that on one
side fatigue is a damage phenomenon controlled by the number of cycles
Fig. 13.23 C-F failure of a

carbon steel chain in seawater
(case study at the PoliLaPP
corrosion Museum of
Politecnico di Milano)
(a) (b) (c)

Stress Stress Stress
Reference curve Aggressive Decreasing frequency
(usually air) species
increased
Aggressive
environment
Number of cycles to failure, N Number of cycles to failure, N Number of cycles to failure, N
Fig. 13.24 S-N curves for steel: a influence of aggressive environment; b influence of
aggressiveness; c influence of load frequency
independently of the frequency or of the cycle period, on the other side corrosion is
a time dependent phenomenon. Figure 13.24 shows by means of r-log N diagrams
how the presence of an aggressive environment and frequency of load variation
influence general behaviour of corrosion-fatigue. It appears that the fatigue limit
vanishes in presence of an aggressive environment and the higher the frequency, the
lower the environment influence; hence, accelerated testing of corrosion-fatigue is
not possible.
13.8.3 Corrosion-Fatigue and Fracture Mechanics
da/dN − DKI curves depend on whether the metal is susceptible or not to SCC in
the considered environment. When the metal is not susceptible to SCC, fatigue
behaviour is called True Corrosion Fatigue (TCF) and, conversely, when it is
susceptible, Stress Corrosion Fatigue (SCF).
13.8.4 True Corrosion Fatigue
Figure 13.25 shows an example of TCF on a platform node near a weld. When TCF
applies, da/dN − DKI plot in semi-logarithmic scale is the one shown in Fig. 13.26.
In the presence of an aggressive environment, DKIth reduces, DKI range widens,
crack growth rate, da/dN, increases in the entire DKI range and da/dN − DKI
relationship does not change, therefore Paris law applies again:
da
¼ C DKIm ð13:4Þ
dN
Fig. 13.25 Example of cracking near a weld on a platform node due to true corrosion-
fatigue (case study at the PoliLaPP corrosion Museum of Politecnico di Milano)
da/dN
True corrosion-fatigue
Fatigue
KI,max= KIC
KI,th KI = KIC(1-R) KI
Fig. 13.26 Comparison of fatigue and TCF
where constants, C* and m*, no longer depend on metal only, instead also on
environment and load variation frequency. In particular, C* decreases as frequency
increases until it reaches, at highest frequencies (above 10 Hz), the same value
C governing fatigue in air. Figure 13.27 shows for a carbon manganese steel that as
frequency increases, crack propagation rate in seawater and in air tends to coincide.
The waveform has no influence on crack growth rate for fatigue in air, instead it
does influence for corrosion-fatigue, because the effect of environment is produced,
at least for most metal–environment couplings, only during the tensile load phase,
i.e., while plastic deformation occurs at crack tip.
The most important and studied case is corrosion-fatigue on submerged nodes of
offshore platforms, not cathodically protected, in harsh environments such as North
10
vcrackseawater
4
vcrackair
1
log
10-2 10-1 1 10
Frequency (Hz)
Fig. 13.27 Influence of frequency on TCF of carbon-manganese steel in seawater, expressed as

ratio between crack propagation rate in seawater and in air
Sea and Alaska, where sea also provides high cyclic stress/load variations espe-
cially during the frequent and persistent winter storms. In these cases, the cracks
propagate from weld beads of nodes or tubular joints.
13.8.5 Stress Corrosion Fatigue
When metal–environment coupling is susceptible to SCC, crack growth rate

increases remarkably as KI,max exceeds KISCC. This type of attack is called Stress
Corrosion Fatigue to indicate that cracking follows an SCC mechanism although
stress is variable with time. Figure 13.28 shows schematically how crack growth
rate increases as DKI varies: generally, DKISCC is higher than DKI,th so that TCF
occurs first, then once KI,max equals KISCC there is a sharp increase in crack growth
rate because SCC prevails, then the typical plateau appears when the
slip-dissolution mechanism applies.
Which Potential?
Since the 1970s, when offshore structures operating in North Sea experienced
several failures studies on fatigue behavior in seawater of carbon–manganese
steels with ferritic–pearlitic structure proliferated. In particular, the behavior
of welded joints of platforms, from which cracks originated, was studied in
free corrosion and cathodic protection (CP) conditions, at different potentials.
The set of data collected shows the complexity of this phenomenon. Let's
consider, for example, only the influence of potential.
For low values of DKI, the potential condition that makes the crack growth
rate minimum, several times smaller than that measured in free corrosion and
log (da/dN)
SCF
Fatigue in air
TCF
KI,max= KIC
KI,max= KISCC
KI,th KISCC(1-R) KIC(1-R) KI
Fig. 13.28 Crack growth rate versus DKI for SCF
nearly the one measured in air, is −0.8 V SCE. Instead, crack growth rate
increases hugely at potential more negative than −1.3 V SCE (overprotection
condition).
For high values of DKI, crack growth rate is minimum at −0.7 V SCE, i.e.,
near free corrosion condition, probably because a minimum of corrosion
favours the blunting of crack tip. At recommended CP conditions, i.e., po-
tential of −0.8 V SCE, crack growth rate increases slightly and remains stable
up to −1.1 V SCE, then increases again.
So, which protection potential has to be adopted? Working condition
consists for a small percentage of the structure life of high DKI, which pro-
duces very deep cracks, and for most of the time low DKI. By applying the
Miner’s law (hypothesis of effect addition) corrosion-fatigue at low DKI
weighs much more than that at high DKI. Therefore, for cathodically pro-
tected offshore structures the best value of protection potential to limit
damages caused by corrosion-fatigue seems to be the same one recommended
to prevent general corrosion (−0.8 V SCE), provided that overprotection
condition is carefully avoided.
13.8.6 Prevention of Corrosion-Fatigue
The strategy for C-F prevention depends on mechanism: TCF, SCF by

slip-dissolution (anodic) and SCF by HE (cathodic).
For TCF, the strategy is based on the increase in DKI,th for instance by means of
surface treatments, such as rolling, hammering or peening, which generate a
compressive stress surface layer, 50–75 lm thick.
For SCF by slip-dissolution (anodic), two interventions help increase SCC
resistance: an increase of DKI,th as above and the reduction of crack tip corrosion
rate (given by the plateau) by injecting inhibitors or by applying cathodic protec-
tion, for instance with the application of anodic metallic coatings (for example, zinc
on steel). Conversely, cathodic coatings (for example, nickel on steel) are dan-
gerous since the presence of porosity or defects enhances fatigue on the base metal.
For SCF by HE (cathodic), the strategy is based on the increase in DKI,th only.
Attention should be paid on cathodic protection because helpless and even dan-
gerous as soon as potential lowers from the standard protection
level (overprotection).
Sea Gem and Alexander Kielland Platforms

Before oil production booming in North Sea, most of offshore platforms of
the world (about a thousand in 1960) were in the Gulf of Mexico. Many
structural failures, which occurred in that area during the 1950s on platforms
weakened by corrosion, were attributed to temporary overloads caused by
tornados, so, accordingly, a new platform design was adopted to withstand
maximum loads generated by so-called 100-year storm, associated with
mandatory CP.
This design philosophy, validated in tropical seas where storms are an
exception, was extended to North Sea in the early 1960s, which, instead, is a
calm sea only exceptionally. Because of this, failure mechanism becomes
fatigue or corrosion-fatigue rather than overloads. Furthermore, CP design
philosophy didn’t change because it was ignored that passing from a warm
and calm tropical sea to a stormy, cold sea, as North Sea is, the protection
current at least doubles (higher oxygen limiting current density) and seawater
resistivity increased, too. So, severe corrosion-fatigue soon appeared although
same structures had long operated without problems in the Gulf of Mexico.
The Sea Gem platform sank on Dec. 27th 1965 with 13 workers dead, and
many other failures occurred without so dramatic consequences. The last
disaster was in 1980, when the Alexander Kielland platform wrecked causing
123 deaths.
During the 1970s, design philosophy changed again, taking into account
corrosion-fatigue and introducing a redundant design to avoid that a com-
ponent failure would jeopardize the security of the structure. In parallel, based
on what learned from experience, CP design and CP criteria for offshore
structures were upgraded; in other words, CP in seawater advanced from an
empirical practice to a rational engineering.
13.9 Some Conclusions
As conclusion of this chapter on environmental assisted cracking of metals, it could

be useful to summarize, in a unified framework, conditions for crack propagation
due to purely mechanical or jointly mechanical and environmental actions.
Critical parameter used for the classical approach to failure analysis is the
nominal stress measured on a smooth specimen for the following conditions:
• rR for mechanical failure under static load
• rth for crack initiation and propagation under SCC
• rCF for fatigue on corrosion-fatigue
When linear elastic fracture mechanics approach is adopted, the following three
critical parameters are referred to:
• KIC for mechanical failure
• KISCC for SCC
• Kth for fatigue or corrosion-fatigue.
These six parameters (rR, rth, rCF, KIC, KISCC and Kth) can be represented on a two
axes diagram in double logarithmic scale, nominal stress, r, and crack length,
a (Fig. 13.29).
The three conditions of classical approach are three straight lines parallel to the
abscissa, while critical conditions expressed in terms offracture mechanics through the
parameter KI, are straight lines with slope −1/2, according to equation: KI = b r (a)½.
To represent on this diagram also conditions of initiation and propagation of
fatigue cracks in terms of K, it has to consider that:
DK ¼ KImax ð1 RÞ ð13:5Þ
log σ
D
(a)
(a) σσR
(b) σσth
(c) σσCF
(b) C
(1) σKIC β∙a-1/2
(2) σKISCC β∙a-1/2
(3) σKth β∙a-1/2
B
(c)
(1)
(2)
A (3)
log a
Fig. 13.29 Schematic representation of critical conditions for crack propagation. Adapted from
Sinigaglia et al. (1979)
13.9 Some Conclusions 271
where R is KImin/KImax ratio. If R = 0, KImin is 0, then DK = KImax.

In practice, it is not possible to determine rigorously critical parameters because
data on geometry, stress level and environment are scattered; accordingly, on the
plot a band rather than a line is reported. Each point of the diagram represents a
structure or a part of it, subjected to a nominal stress, r, and containing defects
smaller than a maximum value amax, which is defined as minimum defect size
determined by applicable non-destructive testing. Four zones are identified:
• Zone A: it is a safe condition (life structure is unlimited, no subcritical prop-
agation of defects is possible)
• Zone B: defects can propagate through fatigue or corrosion-fatigue to reach size
to trigger SCC
• Zone C: defects propagate through SCC under static or variable load, then
leading to final mechanical fracture
• Zone D: structure is mechanically unstable.
• ASTM G 30, Making and using U-bend stress-corrosion test specimens,

American Society for testing of Materials, west Conshohocken, PA.
• ASTM G 36, Standard practice for evaluating stress-corrosion-cracking resis-
tance of metals and alloys in a boiling magnesium chloride solution, American
Society for testing of Materials, west Conshohocken, PA.
• ASTM G 37, Standard practice for use of Mattsson’s solutionof pH 7.2 to
evaluate the stress-corrosion cracking susceptibility of copper-zinc alloys,
• ASTM G 38, Standard practice for making and using C-ring stress-corrosion test
specimens, American Society for testing of Materials, west Conshohocken, PA.
• ASTM G 49, Standard practice for preparation and use of direct tension stress-
corrosion test specimens, American Society for testing of Materials, west
Conshohocken, PA.
• ASTM G 58, Standard practice for preparation of stress-corrosion test speci-
mens for weldments, American Society for testing of Materials, west
Conshohocken, PA.
• ASTM G 129, Standard practice for slow strain rate testing to evaluate the
susceptibility of metallic materials to environmentally assisted cracking,
• ISO 6957, Copper alloys. Ammonia test for stress corrosion resistance,
• ISO 7539, Corrosionof metals and alloys. Stress corrosion testing, International
• NACE TM 0177, Laboratory testing of metals for resistance to sulfide stress

cracking and stress corrosion cracking in H2S environments, NACE
International, Houston, TX.
13:1 Describe the crack growth mechanism by tip dissolution. Provide an

example.
13:2 In your opinion, what is the effect of metal microstructure on hydrogen
embrittlement susceptibility?
13:3 What is the effect of a cathodic polarization on stress corrosion cracking?
13:4 Consider this statement: “in general, it is observed that metals highly
resistant to corrosion because protected by a passive film such as titanium,
aluminium, nickel, chromium and stainless steels, suffer SCC when a
chemical species, for example chlorides, that enables to breakdown the
passive film is present”. Justify this sentence according to SCC mechanism.
13:5 What is the effect of nickel content on SCC of stainless steel in hot chloride
containing solution? Which stainless steels do you suggest for such
applications?
13:6 What is the difference between KIC and KISCC? Do these parameters depend
on the environment?
13:7 An AISI 316 stainless steel pipe (18% Cr, 8% Ni, 2% Mo) transports a
chloride-containing solution at 80 °C. The pipe (wall thickness 30 mm),
due to the internal pressure, suffers a tensile stress. By non-destructive
testing, a crack-like defect (length 1 mm), transversally oriented with
respect to the applied stress, has been detected on the metal surface.
Calculate: a) the maximum tensile stress without leading to stress corrosion
sub-critical crack propagation; b) the maximum crack length before critical
crack propagation if a tensile stress of 700 MPa is applied.
13:8 Discuss the effect of the frequency on the applied tensile load on SCC.
13:9 Discuss the effect of sensitization of austenitic stainless steels on SCC.
13:10 In a hypothetical metal-environment combination, KISCC < KIth. Suggest a
possible da/dN − DKI plot and comment the expected behaviour. Suggest a
possible practical example.
Dany Sinigaglia - Dany Sinigaglia (1936-83) graduated from Politecnico di
Milano (Milan, Italy) in 1962 receiving the gold metal for the best thesis. He started
research activities at the Politecnico, where he was nominated lecturer in
Metallurgy in 1969 and associated professor in 1982. He was a very good and
tireless researcher. Since the mid-sixties he started the study of localized corrosion
with methodologies and techniques absolutely innovative for that time. He was one
of the first to propose theoretical models of corrosion interpretation in occluded
cells, to develop calculation methodologies to highlight the influence of
electrochemical, geometrical and environmental factors in the onset and develop-

ment of localized attacks. Later, he was involved in fracture mechanics approach of
stress corrosion cracking. Who worked with Dany could appreciate his qualities as
a researcher and a teacher (he held the metallurgy course) but unfortunately, a
premature death prevented him from fully showing what temper he was done,
because he certainly would have become an important reference in the field of
corrosion and metallurgy. He published books on metallurgy, fracture mechanics
and environmental assisted cracking, together with about 100 publications on
journal and congress proceedings.
Bibliography
Brown BF (1968) The application of fracture mechanics to stress corrosion cracking. Met Rev
156:55
Brown BF (1971) The theory of SCC in alloys. Im: Scully JC (ed) NATO Scientific Affairs
Division, Brussels
Brown BF (1977) SCC control measures. NBS Monograph 156, National Bureau of Standard,
Washington DC
Copson HR (1959) Physical metallurgy of stress corrosion fracture. Interscience, New York,
p. 247
Denhard EE (1960) Effect of composition and heat treatment on the stress corrosion cracking of
austenitic stainless steels. Corrosion 16(7):359t–370t
Fontana M (1986) Corrosion engineering, 3rd edn. McGraw-Hill, New York. ISBN
0-07-100360-6
Henthorne M (2016) The slow strain rate stress corrosion cracking test—a 50 year retrospective.
Corrosion 12(72):1458–1518
Magnin T, Chambreuil A, Bayle B (1996) The corrosion-enhanced plasticity model for stress
corrosion cracking in ductile FCC alloys. Acta Mater 44(4):1457–1470
Parkins RN, Fessler RR, Boyd WK (1972) Stress corrosion cracking of carbon steel in carbonate
solutions. Corrosion 28(8):313–320
Parkins RN, Wearmouth WR, Dean GP (1973) Role of stress in the stress corrosion cracking of a
Mg-Al Alloy. Corrosion 29(6):251–260
Sedriks AJ (1996) Corrosion of stainless steels, 2nd edn. Wiley, New York
Sinigaglia D, Re G, Pedeferri P (1979) Cedimento per fatica e ambientale dei materiali metallici.
CLUP, Milano, Italy (in italian)
Staehle RW (1977) Predictions and experimental verification of the slip dissolution model for
stress corrosion cracking of low strength alloys. In: Staehle RW, Hochmann J, McCright RD,
Slater JE (eds) NACE-5 Stress corrosion cracking and hydrogen embrittlement of iron base
alloys. NACE International, Houston
Chapter 14
Hydrogen-Induced Damage
If a hydrogen atom is as small as a golf ball, a hydrogen

molecule is as big as a basketball.
Abstract Hydrogen induced damage (HID) can occur at high temperature

(HT-HID) and at low temperature, (LT-HID). Hydrogen attack, affects steels
operating at temperatures typically above 400 °C in high pressure hydrogen at-
mosphere. The interaction of atomic hydrogen and metals at low temperature occurs
in different way. Atomic hydrogen is produced during electroplating processes (as
chrome plating, galvanizing and phosphating), chemical and electrochemical
pickling treatments, in welding if the humidity of consumables is too high, or by the
cathodic process in corrosive fluids: in this last case, so called cathodic poisons, as
H2S, inhibit molecular hydrogen formation and promote atomic hydrogen diffusion
into the metal. Once entered the metal, atomic hydrogen interacts with the metal
structure and may produce a “damage” of various forms, such as delayed fracture,
HIC (hydrogen induced cracking) and blistering, hydrogen embrittlement (HE). All
of these forms of damage are discussed in this chapter.

https://doi.org/10.1007/978-3-319-97625-9_14
276 14 Hydrogen-Induced Damage
14.1 Hydrogen Induced Damage
Hydrogen-metal interactions can occur at high temperature, indicated as HT-HID

(High Temperature Hydrogen-Induced Damage) and at low temperature, LT-HID
(Low Temperature Hydrogen-Induced Damage), whether temperature is above or
below 200 °C. An example of hydrogen embrittlement (Lt-HID) is reported in
Fig. 14.1.
There are other damage mechanisms induced by hydrogen in metals, when hydrogen
reacts with hydride-forming metals or with carbon to form hydrides or methane,
respectively. Typical hydride-forming metals are titanium and zirconium. In this case,
hydrides cause the brittle fracture of the metal along the hydride-matrix interface.
On carbon steels, hydrogen reacts at high temperature (T > 200 °C) with carbon
to give methane. This phenomenon occurs mainly at the surface of carbon steels,
causing decarburization; if it occurs internally, methane is trapped like hydrogen in
hydrogen induced cracking (HIC, see in the following), then creating internal
cracks and blisters, reducing fracture toughness, fatigue and creep resistance. This
type of damage is often called hydrogen attack. A scheme with classification of
HID is reported in Fig. 14.2.
14.1.1 Adsorption, Dissolution and Trapping
Atomic hydrogen is the smallest atomic element, because composed by a proton

and an electron, only. Accordingly, its size is so small that it can dissolve and
diffuse in metals: both phenomena depend on the crystalline structure of metal
lattice, and precisely on lattice structure and cell size.
Atomic hydrogen interacts with metals as schematically shown in Fig. 14.3.
First of all, hydrogen atoms adsorb easily on the metal surface reaching very high
Hydrogen-Induced
Damage (HID)
HT-HID
LH-HID
(hydrogen attack)
Blistering Delayed
Decarburization HE HIC Blistering
(methane) fracture
SSC SCC SCC

(hydrogen sulphide) (acidic solutions) (formation of hydrides)
Fig. 14.2 Classification of hydrogen-induced damage (HID)

14.1 Hydrogen Induced Damage 277
surface adsorption
void
dislocation
grain boundary
Fig. 14.3 Schematic representation of interaction of hydrogen atoms with metal lattice. Adapted
from Pundt and Kircheim (2006)
concentration on the surface, in practice one hydrogen atom for each cell, i.e., one
hydrogen atom for about 4 atoms of the metal. For example, for iron such con-
centration is about 4500 ppm (106/224).
In bcc structures (atomic packing factor 0.68) hydrogen atoms can occupy
octahedral and tetrahedral sites as shown in Fig. 14.4, then producing a cell dis-
tortion. Therefore, maximum solubility would be 1 atom per cell (i.e., one hydrogen
for two atoms of iron, which corresponds to about 900 ppm); this concentration
cannot be obtained because lattice should deform strongly, so the practical maxi-
mum hydrogen content in steel is about thousand times lower, around 1 ppm
(higher content up to 20 ppm can be measured when hydrogen is forced in and
screened, for instance by plating the surface with coatings made of fcc or hcp
metals, Cu, Ni, Cd and Zn).
Although compact structures, as fcc and hcp, have a packing efficiency 0.74,
exhibit an atomic hydrogen solubility of about one order of magnitude higher than
bcc, because fcc lattice has a large single octahedral interstitial site plus two small
Fig. 14.4 Interstitial sites in Tetrahedral interstitial

bcc structure where atomic
hydrogen can store
Octahedral interstitial
Fig. 14.5 Example of

hydrogen storage at edge
dislocations where lattice is
distorted
tetrahedral interstitial sites per cell. This is favourable to accommodate hydrogen

without any excess energy requirement.
In bcc structures, in addition to interstitial sites, there are hydrogen traps inside
crystals and grains, where hydrogen atoms store. To make it simple, hydrogen traps
can be classified by two types: reversible traps and irreversible or permanent traps.
Figure 14.3 shows most common reversible traps, precisely: dislocations, grain
boundaries, vacancies. These traps are called reversible because hydrogen easily
penetrates steel, when forced in, and easily leaves it by stopping hydrogen pro-
duction and by heating. Figure 14.5 shows how dislocations can host hydrogen
atom where the lattice is distorted.
Irreversible traps are coarse micro-voids, consisting of interfaces at inclusions,
especially manganese sulphide, MnS (Mn(II)), as shown in Fig. 14.6. To remove
this hydrogen, it is necessary to heat steel above 400 °C. As reported below, if trap
size is big, hydrogen atoms form a hydrogen molecule, then making it impossible to
recover, causing HIC and blistering (Fig. 14.7).
For iron and steels, Table 14.1 reports the types of traps for atomic hydrogen and
the associated binding energy and the degassing temperature, which are strongly
interrelated, to give an idea of the strength of such traps. For example, the hydrogen
entrapped in the matrix or adsorbed on the metal surface is easily stripped out at low
temperature when exposed to an atmosphere not containing hydrogen (in practice to
the open air). As a further example, atomic hydrogen stored at grain boundaries is
less bound than that at dislocations hence more easily depleted.
14.1.2 Diffusion
As said, atomic hydrogen has a different solubility which depends on crystalline

structure. Once it is dissolved in the surface layer of a metal, hydrogen can diffuse
Fig. 14.6 Elongated MnS inclusions in carbon steel
H+ H+
Electrolyte
H H2 H
H H
e- e- H
H
H H
H H H
2
H H2 H Void
Air
Fig. 14.7 Schematic mechanism of blistering and HIC formation on MnS inclusion traps
Table 14.1 Properties of reversible traps existing in iron and steel (average values from various
literature data)
Metals Traps Binding energy (kJ/mol) Degassing temperature (°C)
Fe Matrix 7 25
Grain boundaries 17 110
Dislocations 20–26 200–215
Microvoids 35–48 305
Carbides interfaces 97 725
Carbon steel Microvoids 35–48 480
(0.47% C)
AISI 4340 Dislocations 20–26 270
Microvoids 35–48 340
MnS inclusions 72 495
Table 14.2 Diffusion coefficient of hydrogen in different materials at room temperature (average
values from various references)
Material D (m2/s) Notes
Iron (carbon steel) 2.5 10−10 Hydrogen solubility in the lattice is about 1 ppm
Ferritic stainless steel 10−11
Austenitic stainless steel 2.15 10−16 Hydrogen solubility in the lattice is about 20 ppm
Martensitic stainless steel 2 10−13
Duplex stainless steel 10−13 to 10−14 Depending on the ferrite/austenite ratio
into the inner volume flowing from the zones at higher concentration to the ones at
lower concentration. Also the diffusivity within the lattice depends of the crystalline
structure. It is worth noting that solubility and diffusion are in opposition. Diffusion
is the prevailing mechanism which drives the interaction between hydrogen and
metals and explains the HID occurrence. Table 14.2 reports the diffusion coefficient
of atomic hydrogen in metals used in industry.
14.1.3 Atomic Hydrogen Produced by a Cathodic Process
During electroplating processes (as chrome plating or electrogalvanizing), phos-

phating, chemical and electrochemical pickling treatments, cathodic protection or in
case of corrosion in acidic solutions, on metal surface the process of hydrogen ions
reduction can take place; based on a simplified mechanism, this process follows two
stages through the intermediate formation of atomic hydrogen:
2H þ þ 2e ! 2H ð14:1aÞ
2H ! H2 ð14:1bÞ
Since each stage occurs with its own rate, generally different from each other, two
situations apply, whether the second step is faster or slower than the first one:
• Faster second step. As soon as atomic hydrogen is produced, molecular
hydrogen forms and evolves into solution, therefore, atomic hydrogen has no
time to enter the metal; to give a rough idea, 99% of produced atomic hydrogen
combines to give molecular hydrogen and less than 1% is available for entering
the metal
• Slower second step. This happens when some chemical species, called cathodic
poisons, which inhibit molecular hydrogen formation, are present. Cathodic
poisons include: sulphur, arsenic, antimony in the metallic phase, and cyanides,
sulphides and organic substances containing sulphur in the electrolyte. It follows
that only some of atomic hydrogen recombines forming molecular hydrogen,
Table 14.3 Percentage of hydrogen entering the steel in the presence of different sulphide content
in solution
[S2−] in solution (ppm) pH2 S in the gas in equilibrium with % of atomic hydrogen
the solution (bar) penetrating the steel
0.0035 1
0.035 16
0.35 0.0001 (=0.0014 psi) 33
1 0.0003 (=0.004 psi) 40
13 0.0036 (=0.05 psi) 60
100 0.028 (=0.39 psi) 75
1000 0.28 (=3.9 psi) 90
10,000 2.8 (=39 psi) 100
Extrapolated equation: Hab% ≅ 40 + 16 log (H2S, ppm)
Adapted from Hudson et al. (1968)
while atomic hydrogen concentrates at metal surface so that it can enter the
metal. For instance, again to give an estimate, only 10% of produced atomic
hydrogen combines, while the remaining enters the metal. Table 14.3 reports the
percentage of hydrogen entering the steel in the presence of different sulphide
content in solution.
Oxide films formed on the metallic surface are barriers for H absorption and are
hindering the hydrogen passage through the interface. When a cathodic poison is
present, hydrogen flow rate inside the metal increases and can reach a maximum
when cathodic overvoltage meets a critical value of approximately 100 mV.
This condition is encountered when sulphides and cyanides are present and cor-
responds to maximum hydrogen solubility in metals (for instance, of the order of
10−1 mol/dm3 for iron, about 12 ppm, at 25 °C).
Measurement of Hydrogen Diffusion in Metals

Figure 14.8 shows an experimental apparatus to measure diffusion rate of
atomic hydrogen in metals (Devanathan 1962). A thin strip separates two
compartments: the first one (I) contains hydrochloric acid and the second one
(II) contains an alkaline sodium sulphate solution, which passivates the steel
surface. The strip surface of compartment (I) works as cathode by means of
an auxiliary anode, in order to produce atomic hydrogen on the metal surface:
some atomic hydrogen enters the metal and diffuses in it, some others
combine to give molecular hydrogen, which escapes through the solution.
Simultaneously, in compartment (II) the strip surface works as anode by
means of an auxiliary cathode. By keeping with a potentiostat the anodic
potential below oxygen evolution potential, the anodic reaction possibly
occurring is oxidation of atomic hydrogen that reached the metal surface by
Fig. 14.8 Experimental Reference +

electrode Potentiostat
apparatus for atomic hydro-
gen diffusion evaluation +
A A
I II
H H H+
H2 Cathode
H H H+
H2 H H H+
Anode
H H H+
HCl Na2SO4 +
H H H+ inhibitor
Iron plate
diffusion. Therefore, the anodic current measures directly the diffusion rate of
hydrogen in the metal, which is governed by Fick’s law:
i C1 C2
¼J¼D ð14:aÞ
F s
where J is hydrogen flow (mol/m2s), i is circulating current density (A/m2),

D is diffusion coefficient (m2/s), C1 and C2 are hydrogen concentrations on
strip surfaces for compartment I and II respectively, s is strip thickness
(m) and F is Faraday constant (96,485 C). After an initial transient, a steady
state is reached when C2 = 0, i.e., all hydrogen that diffuses through the strip
is immediately oxidized, then relationship (14.a) becomes:
i C1
¼D ð14:bÞ
F s
which allows the calculation of the diffusion coefficient, D, by the mea-

surement of current density, i.
The diffusion coefficient of hydrogen in iron (bcc structure) has same order
of magnitude of the one of ions in aqueous solutions (D = 6.25 10−9 m2/s
at 25 °C); in other metals, for example austenitic steels (fcc structure), dif-
fusion occurs more slowly and diffusion coefficient is three orders of mag-
nitude lower.
Testing has shown that hydrogen diffusion occurs through interstitial
crossing in crystal lattice, therefore the diffusion coefficient depends on
temperature only. Accordingly, it increases with temperature, while is prac-
tically independent from either imperfections on grain boundaries or struc-
ture, whether poly or monocrystalline. In the presence of tensile stresses,
hydrogen diffusion significantly increases, while it decreases if compressive

stresses apply: this behaviour is due to changes of hydrogen solubility and not
changes in diffusion coefficient.
14.1.4 Decomposition and Solubility of Hydrogen at High

Temperature
In the presence of hydrogen containing gas at high pressure and at temperature

above 200 °C, iron catalyses the split of molecular hydrogen, H2 ! 2H, with
atomic hydrogen dissolution in iron lattice. Atomic hydrogen solubility varies with
temperature: maximum solubility is in molten iron, about 30 ppm, then decreasing
below 0.1 ppm at ambient temperature. According to Sievert’s law, the solubility of
atomic hydrogen in bcc iron can be expressed as follows:
1 1418
ln½Hbcc ¼ 1:628 þ lnðpH2 Þ ð14:2Þ
2 T
where [H]bcc is atomic hydrogen concentration in ppm, pH2 is hydrogen partial

pressure in bar and T is absolute temperature.
Atomic hydrogen can derive also from the thermal decomposition of water
coming from e.g., air humidity in contact with melted iron during steel production
or the humidity possibly contained in weld flux or welding electrode coating.
14.2 HT-HID or Hydrogen Attack
High temperature hydrogen-induced damage, also called hydrogen attack, affects

steels operating at elevated temperatures (typically above 400 °C) in high pressure
hydrogen atmosphere, as in refineries, petrochemical, ammonia production plants
and other chemical facilities and, possibly, high pressure steam boilers. Hydrogen
attack is one of the major problems in refineries, where hydrogen and hydrocarbon
streams are handled at up to 20 MPa and approximately 250 °C.
It is the result of reaction between dissolved atomic hydrogen and carbon of
carbides present in steel to form methane (C + 4H ! CH4). This reaction can
occur either on the steel surface or inside steel: the former leads to skin decar-
burisation, then to a decrease in hardness and an increase in ductility near the
surface, the latter forms blisters containing methane, at grain boundaries and/or at
precipitate interfaces, with reduction of local carbon content and strength resistance
as well as formation of fissures and cracks. Internal decarburisation, and in
Fig. 14.9 Micrographs of carbon steel C-1095 (0.95% C, 0.40% Mn). a original, b after 500 °C;
1000 bar; 1 h exposure (from Thygeson 1964)
particular the formation of methane and consequent development of voids, can lead
to substantial deterioration of mechanical properties of steels due to loss of carbides
and formation of voids (Fig. 14.9).
Main factors influencing HT-HID are hydrogen partial pressure, temperature,
exposure time and steel composition. The presence of elements forming stable
carbides such as Cr, Mo and V is very important: steels with chromium more than
5%, and austenitic stainless steels, do not suffer this attack. Cr, Mo, W, V, Ti and
Nb—i.e., carbide forming elements—are used in steels to improve resistance.
Industry experience indicates that post-weld heat treatment of Cr-Mo steel is
beneficial in resisting hydrogen attack in so-called hydrogen service.
In 1949, Nelson gathered and rationalised a number of experimental observa-
tions on different steels. Since that, API 941 Nelson curves (Fig. 14.10) are a
universally used guidance for carbon and low alloy steel selection and has been
updated a number of times. Nevertheless, today’s trend is the combination of
Nelson curves and risk-based inspection approach, as recommended by American
Petroleum Institute.
Hydrogen Sources
Hydrogen is adsorbed as atom. Most typical occurrence is during steelmaking
(production of forged steel), pickling/etching treatments, electrochemical
plating, and primarily in acidic corrosion. During steel forging, hydrogen
14.2 HT-HID or Hydrogen Attack 285
Internal
Surface
700
600
Temperature (°C)
1Cr-0.5Mo 6Cr-0.5Mo
500
2.25Cr-1.0Mo
400
1Cr-0.5Mo 2Cr-0.5Mo
300
0.5Mo
200
Carbon steel
50 100
H2 partial pressure (bar)
Fig. 14.10 Nelson curves for different grade of carbon and low alloy steels
comes from atmospheric moisture by water splitting and dissolves at high

temperature in fcc austenitic phase (c-iron). After cooling, as hydrogen sol-
ubility in bcc (a-iron) decreases by one order of magnitude, hydrogen atoms
remain trapped in inclusions, micropores and lattice interstitial sites, often
causing embrittling airline cracks (flakes). Similarly, atomic hydrogen is
produced in welding operation with humid consumable welding rods.
In pickling, electrochemical plating and acidic-related corrosion processes,
hydrogen atoms can also be directly absorbed by cathodic charging, which is
enhanced by substances, called cathodic poisons, such as arsenic, antimony,
sulphur, selenium, tellurium, and cyanide ions. These poisons stop hydrogen
atoms from forming molecular hydrogen, H2, then in atomic form it readily
diffuses into the metal. The most common cathodic poison is hydrogen sul-
phide, which is often present in the petroleum industry, during drilling,
completion and production of oil and gas wells.
14.3 LT-HID
The interaction of atomic hydrogen and metals at low temperature is different from
the one at high temperature in all ways: mechanism, occurrence time and type of
damage. It should be added that consequences of LT-HID are generally more severe
and uncontrolled than hydrogen attack at high temperature.
14.3.1 Delayed Fracture
Ferritic steels suffer hydrogen-induced damage, when hydrogen content exceeds a

critical value, through a drastic reduction of plasticity, while elasticity (i.e., Young
modulus or elastic modulus) remains unchanged. For high strength steels with a
tensile strength, rR, exceeding 1500 MPa, the critical hydrogen content is 1 ppm or
less, while it is about 5–10 ppm for steels with lower strength, in the range 500–
1000 MPa. The effect of dissolved hydrogen may appear mysterious, since the loss
of ductility cannot be observed through neither impact test nor tensile test on
smooth specimens even at low temperature; instead, it occurs in tests at low
deformation rate and with a pre-existing notch or crack. This behaviour is therefore
the opposite of the conventional one, where high strain rates and low temperatures
favour ductile-to-brittle transition. This is due to hydrogen diffusion as controlling
factor: hydrogen diffuses slowly towards micro-voids that form also slowly as steel
deforms above ambient temperature. In the presence of notches, hydrogen accu-
mulates at notch tip, where plasticization occurs, then mechanical strength
decreases. This is called delayed fracture or static fatigue that leads to a fracture
after times as longer as applied stress and hydrogen content are lower (Fig. 14.11).
Figure 14.12 shows the influence of hydrogen content on delayed fracture of a
high yield strength steel: time-to-failure, at constant applied stress (or the opposite,
applied stress at constant time-to-failure), increases as hydrogen content in steel
decreases. Fracture does not take place below a stress threshold, which depends on
hydrogen concentration, yield strength (i.e., microstructure), degree of deformation
and temperature.
Fig. 14.11 Hydrogen delayed fracture caused by acid pickling before galvanizing
14.3 LT-HID 287

(MPa)
2100
Without
hydrogen
1750
24 h
18 h
1400
12 h
1050
7h
700 3h
0.5 h
350
0.01 0.1 1 10 100 1000
t (h)
Fig. 14.12 Delayed fracture curves for ferritic low alloy steel, AISI 4340 grade, with different
hydrogen concentrations obtained by heating hydrogen saturated steel at 150 °C for various times
(from Barth 1969)
14.3.2 HIC and Blistering
When atomic hydrogen, while diffusing within the steel lattice, crosses a micro-void
it is trapped; as soon as another hydrogen atom arrives, the two combine to
molecular hydrogen with an extraordinary increase in pressure (two golf balls to
give a basketball size: about 600 times!). Local pressure increases so highly that
steel cannot withstand it, so cracking or deformation occurs. It has been estimated
that molecular hydrogen in blisters can reach a pressure as high as 104 bar,
therefore, if a hydrogen bubble forms around an elongated MnS inclusion that has a
crack-like shape, the very high internal pressure causes at the inclusion tip an
increase of stress in the metallic matrix that easily overtakes the tensile strength of
the material causing its failure by ductile tearing.
Applying a very simplified approach, considering Mariotte equation:
P/
r¼ ð14:3Þ
4s
where r is the stress generated by the hydrogen pressure, P, created in a blister, / is

void diameter and s layer thickness, the tensile stress produced in a layer 0.001 m
thick around a spherical void of 1 mm in diameter is about 250 MPa, which is a
value higher than the yield strength of bcc iron, i.e., of mild steel.
When cracking occurs, the phenomenon is called hydrogen-induced cracking,
HIC, when blisters form, the phenomenon is called blistering. Examples of
blistering are shown in Fig. 14.13. When atomic hydrogen forms molecular
hydrogen inside the metal in a microvoid, there is an equilibrium between:
• Concentration of hydrogen adsorbed on the metal surface, i.e., its degree of
coverage, hH
• Concentration of dissolved hydrogen in the metal CH,S, which is proportional to
hH
• Pressure of molecular hydrogen inside microvoid, PH2.
The above parameters depend on the overvoltage, ηH, of the hydrogen evolution
process which takes place on metal surface. When the slowest stage is the com-
bination of atomic hydrogen to give the molecule, the following relation holds:
2FgH
2
PH2 ¼ P0H2 e RT ð14:4Þ
where P0H2 is the external pressure of hydrogen, often taken as 0.1 MPa, PH2 is the
pressure of molecular hydrogen inside the microvoid and the other parameters have
the usual meaning. As cathodic overvoltage increases, similarly internal pressure
increases. For instance, with a cathodic polarization of 0.1 V, internal pressure
increases of about 30 times or 1000 times if polarization would be about 0.2 V.
For carbon steel plates used for pressure vessels and pipelines, the most affecting
inclusions are manganese sulphide, MnS, type II, because their form is flat as
obtained during hot rolling and are parallel to the rolling direction, hence providing
an easy trap with a crack-like shape for diffusing atomic hydrogen. Trapped
hydrogen forms small cracks, parallel to the plate. This phenomenon, called
Fig. 14.13 Example of blisters

14.3 LT-HID 289
Fig. 14.14 Stepwise cracking (HIC attack) in carbon steel
Hydrogen Induced Cracking (HIC), depends on the amount of hydrogen available

for diffusion into the steel and on time. For example, for a design life of 20 years,
the H2S partial pressure to produce an atomic hydrogen flow sufficient for HIC
occurrence on susceptible steels is 0.1 bar (corresponding to a concentration in the
aqueous phase of about 400 ppm). Higher partial pressures reduce the time more
than proportionally (for instance, at 1 bar the same steel shows evidence of HIC in
about hundreds of hours and blisters in a couple of years).
Figure 14.14 shows typical step-wise-cracking (SWC) occurring in a carbon
steel plate manufactured by austempering heat treatment, consisting of lamination at
temperature around 850 °C where the steel structure is austenitic.
14.3.3 HE Mechanism
As said, HE occurs if the following conditions are met:

• Sufficient atomic hydrogen in the metal
• Presence of a tensile stress
• Susceptible steel
• Temperature range that supports hydrogen transport (−50 to 150 °C) in steel.
In non-hydride forming elements, three mechanisms have been considered (Lynch
2007):
• HELP, Hydrogen-Enhanced Localized Plasticity
• HEDE, Hydrogen-Enhanced De-Cohesion
• AIDE, Adsorption-Induced Dislocation Emission.
It is worth noting that while cracking mechanisms are similar, the rate controlling
processes are very different. A combination of these three mechanisms occurs in
most cases. The most dominant mechanism will be dependent upon variables such
as strength, microstructure, slip-mode, stress intensity factor, and temperature, thus
affecting the fracture path and fracture surface appearance.
Furthermore, as practical evidence which has not yet a complete explanation, for
a given hydrogen content, steels appear in general more susceptible as strength
resistance increases and the tendency to embrittlement increases as strain rate
decreases. HE susceptibility decreases as temperature increases; this behaviour
prevails at room temperature, and disappears almost entirely in steels above 200 °C,
as dissolved hydrogen escapes out of steel.
Hydrogen-Enhanced Localized Plasticity (HELP) . This mechanism is based on
the presence of solute hydrogen ahead of cracks, specifically in hydrogen atmo-
spheres around both mobile dislocations and obstacles to dislocation movements.
By this mechanism, the hydrogen atmospheres distort when mobile dislocations
approach obstacles, meaning that the repulsion by obstacles is decreased. Since
hydrogen accumulation is localized near crack-tips, deformation is localized and
facilitated near crack-tips, resulting in an overall lower strain for fracture.
Hydrogen-Enhanced De-cohesion (HEDE) . This mechanism is based on the
weakening of iron-iron intermetallic bonds at or near crack tips due to a decrease in
the electronic charge density due to the presence of hydrogen in the crystal lattice in
interstitial sites, then favouring an easy tensile separation of the atoms. Fracture
surfaces should appear basically featureless with a few cleavage steps and tear
ridges separating de-cohered regions.
Adsorption Induced Dislocation Emission (AIDE) . This mechanism is based on
hydrogen-induced weakening of interatomic bonds, but with crack growth occurring
by localized slip. It has been proposed that adsorbed hydrogen weakens substrate
interatomic bonds and thereby facilitates the emission of dislocations from the crack
tips. There is also substantial dislocation emission ahead of the crack tip, resulting in
the formation of voids around particles or at slip band intersections. This behaviour
means that crack propagation occurs due to dislocation emission from crack tips also
with a contribution from the void formation ahead of the crack tip.
14.3.4 Failure Mode
The failure mode caused by HE, unlike SCC does not branch and varies from brittle
cleavage or quasi-cleavage fracture (i.e., with very little plastic deformation) to
intergranular, as shown in Fig. 14.15. To explain this behaviour, Beachem (1972)
(a) (b) (c)
Fig. 14.15 Simplified schemes of HE fracture morphology. Adapted from Beachem (1972)
14.3 LT-HID 291
proposed that cracks can develop by both transgranular and intergranular paths as
function of the stress intensity factor, KI:
• High KI (greater than 100 MPa√m) generates microvoids coalescence
(Fig. 14.15a)
• Intermediate KI leads to transgranular fracture by a quasi-cleavage mechanism
(Fig. 14.15b)
• Low KI (lower than 20 MPa√m) generates intergranular fracture (Fig. 14.15c);
this is typical for high strengh steels, with KIC much lower than 50 MPa√m.
14.3.5 HE by Hydrides
There are other damage mechanisms induced by hydrogen in metals, when

hydrogen reacts with hydride-forming metals as titanium and zirconium. In this
case, hydrides cause brittle fracture of the metal along the hydride-matrix interface.
It is worth illustrating the case of Ti. Titanium oxide is an excellent barrier to
hydrogen intrusion. However, when hydrogen is produced by cathodic processes in
galvanic coupling (typically with Al or Zn galvanic anodes or by impressed current
CP or in strong acids), hydrogen atoms can enter titanium through its oxide. At
temperature below 80 °C hydrogen diffusion is very slow, so hydrogen remains
practically on the surface at a concentration of several thousand ppm, causing a
surface hydriding that has little effect on mechanical properties.
Hydrogen solubility in a-Ti is 20–150 ppm at ambient temperature; hydrogen in
excess forms titanium hydrides, TiH/TiH2, which precipitate close to the metal
surface and embrittle the metal, causing crack propagation by repeated formation
and rupture of sub-surface hydrides. Ti hydrides appear as dark, acicular,
needle-like shaped. Thermodynamic conditions necessary for hydrogen evolution
depend, primarily, on pH and potential. For example, in seawater at 25 °C,
hydrogen starts evolving below −0.7 V SCE, but experience has shown that TiH2
formation requires potentials below −1.0 V SCE. An acceptable limit in cathodic
protection design, considered sufficiently conservative to avoid Ti embrittlement, is
−0.75 V SCE.
In a-b and in b-Ti, hydrogen solubility and diffusivity are much greater, due to
the more favourable bcc lattice of the b-phase. At low hydrogen pressures, b-Ti
grades are generally not susceptible to HE, due to the possibility of accommodating
larger quantities of hydrogen; yet, at high temperature they may experience an
increase in the ductile-to-brittle transition temperature, thus switching to brittle
behaviour even above room temperature. Conversely, a-b Ti alloys are particularly
prone to HE damaging by hydride formation, as hydrogen diffuses in the metal bulk
through b grains until it reaches the a lattice, causing the precipitation of hydrides at
a-b grain boundaries.
14.3.6 Sulphide Stress Cracking (SSC)
In the presence of hydrogen sulphide, H2S, which is a strong poison for atomic
hydrogen combination to give molecular hydrogen, in acidic oxygen-free solutions,
HE is called Sulphide Stress Cracking (SSC) and the occurrence condition is called
sour condition, as typical nowadays in oil and gas activities. To establish if sour
condition applies, the standard NACE MR0175-ISO 15156 “Petroleum and natural
gas industries—Materials for use in H2S-containing environments in oil and gas
production” is used worldwide. Based on that, sour conditions are determined by
H2S partial pressure, in situ pH and temperature. See Chap. 24 for more details.
As far as temperature is concerned, SSC is not an issue above 65 °C; as said
above, more severe condition for HE and therefore for SSC is at room temperature.
Atomic hydrogen is produced from the cathodic process in acidic oxygen-free
solution, therefore the lower the pH the more atomic hydrogen is produced. For
pH > 6.5 production of atomic hydrogen stops, so SSC does not take place. If
actual pH is not known (i.e., not measured in separated brine), it can be estimated
from CO2 partial pressure (for instance, Eq. 8.7) or by using specific nomograms
reported in the mentioned standard.
14.4 Prevention of LT-HID
The primary method to prevent LT-HID in all forms is to avoid the formation of
atomic hydrogen at the surface of metals. When produced in a corrosion process,
prevention or limitation of hydrogen production is achieved by removing or
excluding the presence of cathodic poisons. For example, in acidic pickling both
measures are adopted: the use of inhibitors to reduce corrosion rate, hence hydrogen
production, and the elimination of poisons, as sulphides and cyanides. Similarly, in
galvanic processes atomic hydrogen production is reduced by regulating the
operating conditions, in particular the current density. In welding processes, HE
prevention is done by adopting consumables or fillers free from moisture, which
would be the hydrogen source. Another way is the use of screens to hydrogen
diffusion, like impermeable coatings with fcc structure, as austenitic steels and
nickel, or even thick rubber.
When hydrogen production cannot be avoided, resisting metals must be selected.
In general, HE susceptibility increases significantly as mechanical strength
increases, hence proper heat treatments have to be considered.
In many cases, reversible hydrogen is eliminated by heating steel above 150 °C
for a time (in h) proportional to the square of thickness (in cm) (as rule of thumb,
2 h per ½ inch at temperatures between 150 and 200 °C). Treating time increases
when zinc and cadmium plating, with little permeability to hydrogen, is present.
A positive complimentary effect is the mechanical properties recovery.
14.4 Prevention of LT-HID 293
When selecting ferritic steels, in principle highly susceptible to HE, the addition
of nickel and molybdenum is beneficial while addition of chromium and molyb-
denum is detrimental.
14.4.1 Prevention of HIC and Blistering
As soon as H2S partial pressure in separated gas exceeds 0.03 bar (about ten times
the threshold used to classify sour conditions for risk of SSC), the prevention of
HIC follows two strategies:
• Reduction of hydrogen production rate by the use of corrosion inhibitors (in
practice, time increases proportionally with inhibitor efficiency, for instance
90% efficiency increases time-to-failure by ten times)
• Use of HIC resistant steels, by reducing or preventing the formation of man-
ganese sulphide either by the addition of elements more reactive with sulphur
than manganese, such as calcium and caesium (so-called rare earth treated
steels) that form hard sulphides, which do not deform during hot rolling, or by
lowering the sulphur content in steel below 20 ppm.
14.4.2 Materials for Sour Service
Metals susceptible to HE and specifically to SSC are characterized by a bcc crys-

talline structure, which is a susceptible microstructure. In general, fcc lattice metals
do not suffer HE. There are case studies showing SCC behaviour of austenitic
alloys at temperature exceeding 150 °C in the presence of high chloride content and
high H2S partial pressure; most likely, the cracking mechanism is primarily a
chloride-induced SCC with a mixed anodic and cathodic embrittlement mechanism.
Based on experience, gathered since early 1950s by NACE International, ferritic
steels resist SSC if the microstructure obtained by proper heat treatment shows a
hardness, HRC scale, lower than 22 (equivalent to HV 248). This limit is increased
for Ni, Mo containing low alloy steels up to HRC 26. As general rule of thumb,
with same tensile strength, the most resistant ferritic steels are quenched and
tempered, followed by bainitic and then normalized ones (ferrite and pearlite
microstructure); conversely, cold drawing steels are the most susceptible.
Both NACE MR0175 and ISO 15156 list classes and proprietary alloys suitable
for SSC service, i.e., resisting HE in sour service conditions. For more details, refer
to Chap. 24.
• API 941 Steels for Hydrogen Service at Elevated Temperatures and Pressures,
American Petroleum Institute, Dallas, TX.
• ISO 2626, Copper, Hydrogen embrittlement test, International Standard
• ISO 7539, Part 11—Stress corrosion cracking. Part 11: Guidelines for testing
the resistance of metals and alloys to hydrogen embrittlement and
hydrogen-assisted cracking, International Standard Organization, Geneva,
Switzerland.
• ISO 15156, Petroleum, petrochemical and natural gas industries—Materials for
use in H2S-containing environments in oil and gas production. Part 1: General
principles for selection of cracking-resistant materials; Part 2: Cracking-resistant
carbon and low alloy steels, and the use of cast irons; Part 3: Cracking-resistant
CRAs (corrosion-resistant alloys) and other alloys, International Standard
• ISO 17081, Method of measurement of hydrogen permeation and determination
of hydrogen uptake and transport in metals by an electrochemical technique,
• NACE MR 0175, Sulphide stress cracking metallic material for oil field
equipment, NACE International, Houston, TX.
• NACE TM 0284, Evaluation of Pipeline and Pressure Vessel Steels for
Resistance to Hydrogen-Induced Cracking, NACE international, Houston, TX.
14:1 Design the cell and specify operating conditions for the measurement of the
diffusion coefficient of hydrogen in metals.
14:2 Demonstrate that the maximum hydrogen solubility in iron at 25 °C, which
is of the order of 10−1 mol/dm3, corresponds to about 12 ppm.
14:3 List the hydrogen traps existing in iron and steel and classify them in
reversible and irreversible. Is there a relationship between the trend of the
binding energy and degassing temperature? Why?
14:4 Explain the trend of the values of the hydrogen diffusion coefficient reported
in the Table 14.2 on the basis of crystal lattice and type of traps.
14:5 Which is the effect of an anodic or cathodic polarisation on the susceptibility
of steels to hydrogen embrittlement (HE)?
14:6 Explain the difference between the mechanism of high temperature
hydrogen-induced damage (HT-HID) and Hydrogen embrittlement (HE).
14:7 Explain the trend of the delayed fracture curves for ferritic low alloy steel
saturated with hydrogen and exposed to high temperature for different times
(Fig. 14.12): which is the main factor that explain the effect of the time?
14:8 Explain the effect of temperature and strain rate on hydrogen embrittlement
susceptibility of steels; compare the effect of temperature on hydrogen
embrittlement and SCC by slip dissolution mechanism.
14:9 Why a-b and b titanium are more susceptible to HE by hydrides than a-Ti?
14:10 List the methods for the prevention of LT-HID caused by: pickling, welding,
formation of cathodic hydrogen (corrosion reactions or cathodic protection);
for each method explain briefly which mechanism is exploited.
Bibliography
Barth CF, Steigerwald EA, Troiano AR (1969) Hydrogen permeability and delayed failure of
polarized martenstic steels. Corrosion 25(9):353–358
Beachem CD (1972) A new model for hydrogen-assisted cracking (hydrogen “embrittlement”).
Metall Mater Trans B 3(2):441–455
Devanathan MAV, Stachurski Z (1962) The adsorption and diffusion of electrolytic hydrogen in
palladium. Proc R Soc A 270:90
Flis J (ed) (1991), Corrosion of metals and hydrogen-related phenomena. Elsevier, Amsterdam,
Nederland, PWN—Polish Scientific Publishers, Warszawa, Poland
Hochmann J, Staehle Rw, McCrigth RD, Slater JE (eds) (1977) Stress corrosion cracking and
hydrogen embrittlement of iron base alloys. NACE International, Houston
Hudson PE, Snavely Jr ES, Paune JS, Fiel LD, Hackerman N (1968) Corrosion. NACE, 24, 7
Lynch SP (2007) Progress towards understanding mechanisms of hydrogen embrittlement and
stress corrosion cracking. In: NACE corrosion conference, Paper n. 07493, NACE
International, Houston, TX, pp 1–55
Oriani RA (1970) The diffusion and trapping of hydrogen in steel. Acta Metall 18:147–157
Oriani RA, Hirth JP, Smialowski M (1985) Hydrogen degradation of ferrous alloys. Noyes
Publications, Park Ridge
Pundt A, Kirchheim R (2006) Hydrogen in metals: microstructural aspects. Ann Rev Mater Res
36:555–608
Thygeson JR, Molstad MC (1964) High pressure hydrogen attack of steel. J Chem Eng Data 9:2
Chapter 15
Intergranular and Selective Corrosion
The most part of piping was stainless steel, and you know
that stainless steel is a great material but does not allow,
I mean does not yield if cold but if warmed up it’s not
so much anymore stainless.
Primo Levi, The Wrench
Abstract Metals consist of micrometric size crystalline grains. The border between
these grains, called grain boundary, is a peculiar and delicate region, due to a distorted
crystallographic structure and possible segregation of impurities and second phases.
These characteristics of non-equilibrium make grain boundaries particularly reactive,
and weaker in terms of corrosion resistance, so that in some cases a localized corrosion,
called intergranular corrosion, can occur. This corrosion-type attack is very severe
because it leads to grain detachment, then to a reduced mechanical resistance, despite
the negligible metal consumption; in some environments and in the presence of tensile
stresses it triggers stress corrosion cracking. In this chapter the most common inter-
granular corrosion forms are described, including stainless steel sensitization, knife-line
attack, exfoliation of aluminium, and selective corrosion of brass and cast iron.

https://doi.org/10.1007/978-3-319-97625-9_15
298 15 Intergranular and Selective Corrosion
15.1 Impurities and Segregations
Sometimes intergranular attack is caused by the presence of specific alloying ele-

ments or impurities. This occurs on tin containing small content of aluminium in
hydrochloric acid; on copper when the concentration of arsenic exceeds 0.5%; on
silver alloyed with about 2% of gold, and others. In the past, cast Zn-Al alloy
containing impurities of lead exposed to steam or warm marine atmospheres, fre-
quently showed some spectacular effects as bulges or cracks due to intergranular
corrosion.
Some concerns deal with intergranular attacks that are caused by phase pre-
cipitation at grain boundaries. This is the case of aluminium alloys strengthened by
precipitation hardening, by which intermetallic compounds, often of
sub-microscopic size, form at grain boundaries. For example, in 5000 (Al-Mg) alloy
series, intermetallic Mg2Al8 precipitates which is more reactive than the aluminium
matrix, and therefore corrodes selectively. Similarly, in 7000 (Al-Mg-Zn) series
alloys, MgZn2 precipitates: as it is less noble than the matrix, it is selectively
attacked. In high-strength alloys, series 2000 and 7000, containing copper, CuAl2
precipitates then depleting the surrounding adjacent areas from copper: this leads to
a galvanic effect between the noble precipitate (cathode) and the surrounding matrix
(anode) with an intergranular attack at the matrix side.
However, the most important case of intergranular corrosion involves austenitic
stainless steels (one example is given in Fig. 15.1).
15.2 Sensitization of Stainless Steels
Austenitic stainless steels are supplied by steelworks as stabilized, which means

that carbon, with maximum content of 0.08%, is dissolved in the metal matrix. This
condition is achieved by a heat treatment, called solubilization, which consists of a
thermal cycle as follows: maintenance at 1050 °C for 1 h per thickness of 1 inch
(25.4 mm) in which carbides dissolve and carbon solubilizes in the metal matrix,
then followed by a rapid cooling to avoid carbides to form again. Without further
heat treatments these steels do not suffer intergranular corrosion; instead, if brought
and maintained for some time in a temperature range approximately between 500
and 850 °C, chromium carbides, of Cr23C6 type, form and precipitate at grain
boundaries. Since chromium carbide is enriched in chromium (chromium to carbon
ratio is 16:1 by weight) this precipitation of chromium carbides at grain boundaries
depletes chromium in the near matrix from 18%—as typical of stainless steels of
most common use—to even below 12% as Fig. 15.2 shows, then jeopardizing
passivity build up. This process, called sensitization, is the prerequisite for inter-
granular corrosion to occur as soon as sensitized stainless steels are exposed to a
mildly aggressive or strongly oxidizing environment.
15.2 Sensitization of Stainless Steels 299
Cr (%) Grain boudary

Cr depleted
zone
passive
Cr profile
12
Grain
active
boundaries
Cr carbide
precipitates
Distance
Fig. 15.2 Schematic representation of chromium carbides precipitation and % Cr profile at grain
boundaries
0.06
800
0.05
Temperature (°C)
700 0.04
0.03
600
0.02
500
400
1 min 10 min 1h 10 h 100 h 1000 h
Time
Fig. 15.3 Time of sensitization of an AISI 304 steel with changes in temperature and carbon
content
The sensitization tendency of austenitic stainless steels depends on composition,

in particular, the time required decreases as carbon content increases (Fig. 15.3).
Also other alloying elements, such as nickel, molybdenum or nitrogen, influence the
time of sensitization, but to a lesser extent than carbon. For example, a few seconds
at 600 °C are sufficient for sensitization when carbon content is 0.08% and higher,
while times longer than an hour are necessary for carbon content below 0.03%.
Also ferritic stainless steels can be sensitized through a different and more
complex mechanism; because in this case the solubility of carbon and nitrogen in
the ferritic matrix is much lower, sensitization time is shorter. The critical tem-
perature interval for both chromium carbides and chromium nitrides is 500–900 °C;
however, because chromium diffusivity in the ferritic matrix is much higher than
that in austenite, the permanence of ferritic steels at temperatures between 700 and
900 °C, while causing carbides and nitrides separation, does not give rise to sen-
sitization because the high chromium diffusivity favours homogeneous chromium
redistribution. The critical temperature range for the sensitization of ferritic steels is
therefore limited between 500 and 700 °C; in practice, sensitization occurs once a
permanence at temperatures above 900 °C (where most of carbides and nitrates are
dissolved) is followed by a rapid cooling to the range of 500–700 °C.
As far as other materials are concerned, austenitic-ferritic steels have good re-
sistance to sensitization, while nickel super-alloys do not.
15.3 Corrosion Rate
Figure 15.4 shows an intergranular attack of austenitic stainless steel with 0.06% C,
sensitized at 600 °C for several hours.
A schematic representation of the electrochemical mechanism of intergranular
corrosion is shown in Fig. 15.5 in which reference is made to two curves, relating to
the anodic behaviour of an austenitic stainless steel with a chromium content equal
to that of the core of the grain (18% Cr) and of a steel with a chromium content
equal to that of the sensitized grain boundary (10% Cr). The weakness of the grain
boundary is reflected by the increase in activity and transpassivity intervals and the
reduction of passivity interval. A sensitized steel is subject to intergranular corro-
sion in environments where the cathodic process brings the potential close to E2 or
E4 (grain core is passive and grain boundary is active); if the potential is more noble
or less noble than E2 or E4 (for example, close to E1 or E5) generalized and uniform
corrosion takes place; finally for potential between E4 and E2 (for example close to
E3) there is no corrosion, being both grain core and grain boundary passive. In
short, environments promoting intergranular corrosion are those with weak
Fig. 15.4 Intergranular

corrosion of an austenitic
stainless steel AISI 304 with
0.06% of C, sensitized at
600 °C for several hours
15.3 Corrosion Rate 301
E
Fe 18%Cr - 10%Ni
Fe 10%Cr - 10%Ni
E1
Intergranular
E2
corrosion
E3
E4 Intergranular
corrosion
E5
log i
Fig. 15.5 Electrochemical conditions for intergranular corrosion in sensitized alloys
oxidizing power (E4) or strong oxidizing power (E2). Typical hazardous environ-
ments include: nitric and sulphuric acid, sulpho-nitric, sulpho-acetic,
nitric-hydrofluoric and nitric-lactic acid mixtures, pickling solutions, organic acids
such as lactic and acetic acids. The presence of ions characterized by two valences,
for example iron (Fe2+, Fe3+) and copper (Cu+, Cu2+), are of remarkable impor-
tance, because the oxidized-to-reduced activity ratio determines the cathodic pro-
cess potential, hence conditions for intergranular attack occurrence.
15.4 Prevention of Intergranular Corrosion
Sensitized austenitic stainless steels can be recovered by repeating the solubilisation

heat treatment; in practice, this operation is rather difficult to carry out on final
assembled structures or equipment, because of the risk of permanent deformation
and induction of internal stress.
There are two main ways to prevent intergranular corrosion: by decreasing the
carbon content and by the addition of stabilizing elements which form stable
carbides. By the first one, which is the most followed, carbon content is reduced
below 0.03%: AISI 304L or 316L (L means low carbon) are the most known
commercial grades. These low carbon grades have the drawback to exhibit lower
mechanical strength. By the second one, a typical German tradition, an element
forming dispersed carbides in the lattice is added, with the aim to subtract carbon
from the matrix and to avoid chromium carbides precipitation: these elements are
titanium and niobium added by a content 5 and 10 times greater than carbon
content, respectively. These modified stainless steels are called stabilized; typical
grades are AISI 321, titanium stabilized, and AISI 349, niobium stabilized, as
variant of classic AISI 304, and AISI 316Ti and AISI 316Nb as variants of
classic AISI 316.
15.5 Weld Decay
Welding is without doubt the main cause of sensitization of stainless steels and may
give rise to different types of attacks: the most important one is called weld decay.
To understand where and why weld decay localizes, let’s consider a
head-to-head welded joint. At the centre of the weld bead, called molten zone, the
microstructure is a wrought-like structure as result of a mixture of base metal and
weld metal, after complete fusion and solidification. Aside, there is a region, more
or less extended, according to the heat input, generally of the order of the thickness
of the joint, in which the base material undergoes one or more thermal cycles (in
relation to the number of weld passes) with a temperature profile shown in
Fig. 15.6. This zone, which is called the heat affected zone, comprises the sensitized
steel that is between two zones where temperature or residence time are not critical
for sensitization.
The exact location of the sensitized zone depends primarily on steel composition
and all those factors that govern the thermal gradient during welding time such as
thickness of steel, welding procedure, number and velocity of passes, heat input per
pass, any pre and post welding heating. As rule of thumb, the sensitized area in
austenitic stainless steels is one to two centimetres from the weld bead and even less
in ferritic stainless steels.
≈ 1250°C
900°C
500°C
Austenitic Ferritic Stabilized

stainless stainless stainless steel
steel steel (knife-line corrosion attack)
Fig. 15.6 Thermal gradient and location of the corrosion areas for austenitic steels and sensitized
ferritic and austenitic steels
15.5 Weld Decay 303
15.5.1 Knife-Line Attack
Stabilized stainless steels need a specific comment. Welding processes do not

sensitize stabilized steels because titanium or niobium have sequestered carbon.
However, near the melted zone, in a very narrow area, temperature is so high to
dissolve also carbides of stabilizing elements, then releasing carbon which can
combine with chromium, once steel is rapidly cooled within the critical temperature
range of 500–800 °C for a sufficient time. In some oxidizing environments, such as
those based on nitric acid, this particular sensitization gives rise to an attack limited
to a few crystalline grains parallel to the weld bead and penetrating steel thickness
up to cut off the weld: for this reason, this attack is called knife-line attack
(Fig. 15.7).
15.6 Intergranular Corrosion of Nickel Alloys
Also nickel alloys can be sensitized, then undergoing intergranular attack. It is

worth mentioning the case of Hastelloy C employed in annealed solution condition
for its excellent resistance to oxidizing environments. It suffers intense intergranular
corrosion if it is sensitized by heating in the range of 500–700 °C: accordingly, it is
used only after solubilization heat treatment in the range 1150–1250 °C, hence
welds are not accepted without post-welding solubilization heat treatment.
Figure 15.8 shows the intergranular corrosion of Ni-Cr alloy-20 (standard
composition is Cr 20, Ni 25, Mo 4.5, Cu 1.5; Fe balance) in a 50% sulphuric acid
solution containing chlorides at 50 °C. Sometimes corrosion occurs near welds
Fig. 15.7 Knife-line corrosion attack on an AISI 321 stainless steel plate welded with an AISI
304L stainless steel (nitric acidic solution)
Fig. 15.8 Intergranular corrosion of nickel alloy
Fig. 15.9 Intergranular corrosion and knife attack on nickel alloy
where knife-kind attack can also take place, as shown in Fig. 15.9 for a
nickel-based alloy. Corrosion at welds has twofold causes: micro-inhomogeneity in
dendritic structure and knife attack due to sensitization in heat affected zone.
Since nickel alloys are often used at high temperature (for example, in nuclear
industry for superheater tubes) sensitization is possible also during operating.
15.7 Intergranular Corrosion Without Sensitization
Non-sensitized stainless steels are susceptible to intense intergranular attack when

exposed to particularly aggressive environments containing a strongly oxidizing
ion, for example boiling nitric acid solutions and high temperature aqueous solu-
tions. Susceptibility is determined by the presence of some impurities, in particular
15.7 Intergranular Corrosion Without Sensitization 305
Fig. 15.10 Intergranular

attack on titanium in
nitric-hydrofluoric acid
mixture
Fig. 15.11 Silver coin Incusa

(sixth century B.C.)
phosphorus; instead, a high content of silicon is beneficial. Today, silicon-rich ELI

(Extra Low Interstitial) stainless steels are not subject to this form of attack.
Intergranular attack without sensitization is also observed on other metals. For
example, Fig. 15.10 shows the intergranular attack on titanium in nitric-
hydrofluoric acid mixture. Figures 15.11 and 15.12 are related to a silver coin
‘Incusa’ of the VI century BC of a Greek colony in Magna Graecia (Metaponto,
Basilicata, Italy) affected by intergranular attack that has led to its embrittlement. In
this case, it is possible that the attack was favoured by the presence of internal
stresses originating from the drawing process of the coin which was not followed by
an annealing.
Fig. 15.12 Micrograph of intergranular attack on coin of Fig. 15.11
15.8 Exfoliation of Aluminium Alloys
It is a special type of intergranular corrosion typical of aluminium alloys which

proceeds through preferential intergranular paths, usually parallel to the direction of
extrusion or rolling. The corrosion product that forms has a greater volume than the
volume of the parent metal. The increased volume forces the layers apart, and
causes the metal to exfoliate or delaminate. It is also called lamellar corrosion.
Al-Cu-Mg, Al-Zn and Al-Zn-Mg alloys are typically susceptible to this type of
attack, which is enhanced if a galvanic action with noble metals is present.
Figure 15.13 shows an example of this form of corrosion obtained in a testing.
Fig. 15.13 Exfoliation on aluminium plate exposed to atmosphere

15.8 Exfoliation of Aluminium Alloys 307
In addition it is worth mentioning that some kind of exfoliation corrosion is

sometime found in forged steel characterized by excessive internal growth of oxide,
which has a volume some seven times that of the steel.
15.9 Intergranular Corrosion Tests
An important quality control test is the check of susceptibility of intergranular

corrosion of stainless steels and nickel-based alloys, if sensitized because of
incorrect heat-treatment or improper welding. Aim of the test is revealing of
chromium-depleted areas caused by the precipitations of carbides and sigma phase.
Three tests are used.
Huey Test, ASTM A262—Practice C. The specimen is immersed in a boiling 65%
solution of nitric acid for five periods, each of 48 h. Corrosion rate is calculated from
weight loss measurements. If there is no sensitization, i.e., grain is homogeneously
passivated, nitric acid maintains passivity and weight loss refers to some oxide dis-
solution, only. When sensitized, intergranular attack occurs on chromium-depleted
zones, which are not passive so that galvanic corrosion occurs between these zones
and passive surrounding ones. The cathodic reaction is hydrogen evolution (reduction
of nitrate anion does not contribute to the cathodic process), therefore corrosion rate is
given by the cathodic current density of hydrogen evolution reaction multiplied by the
surface area ratio which normally exceeds 10. Hence corrosion rate is often of the
order of tens mm/y which is easily measured by weight loss.
Strauss Test, ASTM A262—Practice E. The specimen is immersed in a boiling
Cu/CuSO4—16% sulfuric acid solution. After exposure for 1 h, the specimen is
180° bent over a rod with diameter equal to the specimen thickness and visually
examined: no cracks are allowed. The cathodic process is copper ion reduction
and to a smaller extent hydrogen evolution. Corrosion rate, much higher than in
Huey test, is difficult to predict.
Streicher Test, ASTM A262—Practice B. The specimen is immersed in a boiling
Fe2(SO4)3—50% sulfuric acid solution for 24–120 h. As in Huey test, corrosion
rate is calculated from weight loss measurements. The cathodic process is reduction
of ferric to ferrous ion and to a smaller extent hydrogen evolution. Corrosion rate is
more difficult to predict than in Huey test, however it can be assumed that corrosion
rate is the same or higher.
15.10 Selective Corrosion of an Alloying Element
Selective attack of a constituent of an alloy is fairly common: the most important

example is brass dezincification, but other copper alloys show selective etching of
aluminium, manganese, nickel and cobalt. In copper-silver alloys, copper is
selectively attacked; in gold-silver and lead-tin alloys, silver and tin are attacked,
respectively. As a rule of thumb, the more reactive element corrodes while the more
noble or passive does not.
Selective corrosion often affects a surface layer only without producing struc-
tural damages; in some cases it can cause an indirect damage, for example, when it
causes the leaching of the less noble metal, there can be the setup of galvanic
corrosion on closer metals.
15.10.1 Dezincification of Brass
Selective etching of zinc in brass is easily diagnosed by the change of colour toward
copper appearance (Fig. 15.14). It affects both alpha and alpha-beta brass types and
is produced mainly in stagnant or slow-flowing solutions, that is, conditions
favouring deposit formation.
This attack occurs as either spread or localized, the latter preferably in neutral or
weakly alkaline solutions on brass with low zinc content (20–30%), while the former
on brass with high zinc content, for example on Muntz metal (60% Cu, 40% Zn). In
biphasic brass, at least in a first stage, the zinc-rich phase is attacked preferentially.
The corrosion mechanism involves in some cases a selective corrosion of zinc,
or dissolution of both zinc and copper, followed by a re-deposition of copper in a
typical spongy form.
Brasses with high copper content (>85% Cu) do not suffer dezincification attack.
A strong increase in the dezincification resistance of alpha brass is obtained by
adding small contents (0.02–0.06%) of arsenic, antimony or phosphorus; instead,
no elements to inhibit dezincification on alpha-beta or beta brass types are known:
in this case, inhibitors are used.
Fig. 15.14 Selective etching of zinc in brass

15.10 Selective Corrosion of an Alloying Element 309
15.10.2 Cast Iron Graphitization
In saline environments, in certain types of water and even in weakly acidic solu-
tions or in soils, the so-called graphitization of grey cast irons can occur; it consists
of a selective etching of iron so the content of graphite on the surface increases. As
the attack grows, graphite remains with no change of size and shape of the com-
ponent, instead mechanical properties drop down. Unlike grey cast iron, thite,
spheroidal and malleable cast iron do not suffer graphitization (Fig. 15.15).
• ASTM A 262, Standard practices for detecting susceptibility to intergranular

attack in austenitic stainless steels, American Society for Testing of Materials,
West Conshohocken, PA.
• ASTM A 763, Standard practices for detecting susceptibility to intergranular
attack in ferritic stainless steels, American Society for Testing of Materials,
• ASTM G 28, Standard test methods of detecting susceptibility to intergranular
corrosion in wrought, nickel-rich, chromium-bearing alloys, American Society
for Testing of Materials, West Conshohocken, PA.
• ASTM G 67, Standard test method for determining the susceptibility to inter-
granular corrosion of 5xxx series aluminium alloys by mass loss after exposure
Fig. 15.15 Graphitization of cast iron pipe buried in the 1930s

to nitric acid (NAMLT test), American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G 110, Standard practice for evaluating intergranular corrosion resis-
tance of heat treatable aluminium alloys by immersion in sodium chlo-
ride + hydrogen peroxide solution, American Society for Testing of Materials,
• ISO 3651-1, Determination of resistance to intergranular corrosion of stainless
steel. Part 1: austenitic and ferritic-austenitic (duplex) stainless steel. Corrosion
test in nitric acid medium by measurements of mass loss (Huey Test),
steel. Part 1: ferritic, austenitic and ferritic-austenitic (duplex) stainless steel.
Corrosion test in media containing sulfuric acid (Strauss Test), International
• ISO 9400, Nickel based alloys. Determination of resistance to intergranular
corrosion, International Standard Organization, Geneva, Switzerland.
• ISO 11846, Corrosion of metals and alloys—Determination of resistance to
intergranular corrosion of solution heat- treatable aluminium alloys,
15:1 Why do grain boundaries become sensitive to the corrosion attack in case of
precipitation of chromium carbides?
15:2 Discuss the effect of temperature, time and carbon content on sensitization
of austenitic stainless steels.
15:3 Why isn’t the intergranular attack prevented in ferritic stainless steel even if
carbon is reduced to 0.3%? What is the temperature range in which it can
occur?
15:4 Which information does the time-temperature sensitization curve provide?
Determine the sensitization time for an AISI 304 stainless steel with 0.05%
carbon content during a heat treatment at 650 °C. Consider the
time-temperature sensitization curve of Fig. 15.3.
15:5 What is a stabilized steel? How can the use of a stabilized steel prevent
sensitization of stainless steels?
15:6 Why do stabilized stainless steels undergo knife-line attack?
15:7 Consider a head-to-head welded joint. Where is the sensitized zone loca-
ted with respect to the molten zone? Consider: (a) a ferritic stainless steel;
(b) an austenitic stainless steel; (c) a stabilized stainless steel.
15:8 Discuss the two approaches used to prevent intergranular corrosion of
stainless steels.
15:9 A sensitized austenitic stainless steel suffers intergranular corrosion in a

strong oxidizing environment. Discuss the electrochemical behaviour of the
metal by using Evans diagram.
15:10 Dezincification of brass is a typical example of selective corrosion of an
alloying element. Discuss the corrosion mechanism. What are the methods
to prevent dezincification of alpha brass and beta brass?
Bibliography
Cihal V (1984) Intergranular corrosion of steels and alloys. In: Materials science monographs, vol
18. Elsevier, Amsterdam
Steigerwald RF (1978) Intergranular corrosion of stainless alloys, ASTM special publication N
656. American Society for Testing of Materials, Philadelphia
Chapter 16
Erosion-Corrosion and Fretting
In the cycling return of many solar years a ring, furiously

worn on finger, thins inside, a water drop falling continuously
carves the stone, curved ferrous plough wears hidden in soil,
on streets people feet have consumed the pavement, and on
doors bronze statues show worn by the frequent right
hand touch of those who greet when passing through.
Lucretius, De rerum natura, I, 311–318
Abstract This chapter presents the forms of corrosion related to the contact of a
metallic surface with something moving on it, be it a fluid or another material. In
the former case, erosion-corrosion phenomena may onset due to the rapid flow of a
fluid on a metal, which combines corrosion with physical-mechanical interactions
as turbulence, cavitation or impingement of particles on its surface. On the other
hand, if a solid body slides on a metal surface, typically in the form of cyclic
micrometric slips such as those created by vibration, fretting corrosion establishes,
causing a range of damages from simple loss of brightness to the formation of
craters that then trigger fatigue cracks.

https://doi.org/10.1007/978-3-319-97625-9_16
314 16 Erosion-Corrosion and Fretting
16.1 Erosion-Corrosion Forms
Erosion-corrosion is defined as the conjoint action of erosion and corrosion and

consists of the progressive loss of material from a solid surface due to corrosion and
to the mechanical interaction between the surface and a flowing, single or multi-
phase fluid. It includes erosion of protective films in a turbulent fluid, solid and
liquid particles impingement corrosion, and cavitation corrosion. Otherwise,
flow-induced corrosion is defined as the increased corrosion resulting from
increased fluid turbulence intensity and mass transfer because of the flow of a fluid
over a surface, without mechanical interaction (Uhlig 2000).
An erosion-corrosion attack is the consequence of a continuous local damage of
the protective film by the mechanical action of an aggressive environment, which is
followed by the oxidation of bare areas, sometimes also accelerated by the galvanic
action exerted by the surrounding passive areas, acting as cathode.
Figures 16.1, 16.2, 16.3, 16.4, 16.5 and 16.6 show some examples of this type of
attack.
Fig. 16.2 Corrosion-erosion

on a choke valve made of
AISI 304 in oil production
wellhead

on carbon steel in naphthenic
acid containing oil
16.1 Erosion-Corrosion Forms 315
Fig. 16.4 Corrosion by

turbulence on a carbon steel
pipe in the presence of CO2,
at a cross section reduction

on top of a reactor made of
stainless steel (AISI 304
grade), caused by liquid
droplets in turbulent water
vapour
16.1.1 Corrosion by Turbulence
Metals exposed to flowing liquids are potentially subject to such attack, especially
pump impellers, turbine blades, agitators, tube inlets in heat exchangers and all
conditions where there is a sudden change of hydraulic regime for the presence of
obstructions of any kind (for example weld beads, gaskets, valves) or due to sharp
changes of fluid direction (Fig. 16.3) or of cross section area (Fig. 16.4).
Corrosion by turbulence is closely related to surface conditions; surface defects
often originate and localize the attack, which, once started, contributes to further
increase the turbulence locally, then accelerating the attack. The morphology of the
Fig. 16.6 Corrosion in

seawater by impingement on a
copper alloy plate (Muntz
metal)
attack, different in each case, is always defined by hydrodynamics as shown in

Fig. 16.5: there are smooth grooves, hydro-dynamically profiled, flaming-like or
wavy streaks, sometimes reminding desert dunes.
The onset of corrosion-erosion depends on the synergy between the mechanical
action exerted by the fluid and corrosion resistance properties of the metal. The
former, i.e., mechanical action, depends on the kinetic energy of the liquid, which
goes with the square power of the fluid velocity, and the latter with the metal
surface hardness. An empirical relationship proposed by API (American Petroleum
Institute) for a two-phase flow system and often extended to one phase fluids as
water streams, provides a link between fluid kinetic energy and material property as
follows (API-RP 14-E):
C
vf ¼ pffiffiffiffi ð16:1Þ
cf
where C is a constant depending on the metal, vf (m/s) and cf (kg/m3) are fluid
critical velocity and gas/liquid mixture density at flowing pressure and temperature,
respectively. Industry experience indicates that for solids-free fluids constant C used
in design phases for metal selection is 40 for copper, 60 for copper-nickel 70/30,
120 for carbon steels and 500 for stainless steels; these values are generally con-
sidered conservative. When fluid velocities are particularly high, hard and corrosion
resistant coatings such as stellites (i.e., cobalt-chromium alloys designed for wear
resistance) and ceramic coatings are used.
Copper alloys suffer corrosion-erosion easily (low constant C). Attacks are
favoured by the presence of gas bubbles crushing against metal walls (called
impingement attack) as shown in Fig. 16.6, so the protective film is damaged. The
attack is characterized by sharp edges and, inside tubes, appears as craters oriented
in direction opposite to the flow, showing a typical horseshoe shape, also called
horseshoe attack (Figs. 16.7 and 16.8). If suspended solids are present (gravel,
Fig. 16.7 Horseshoe-attack

due to erosion-corrosion in a
copper tube
Fig. 16.8 Typical shape of (a)

horseshoe-attack
Flow
Flow
(b)
sand, silt, catalyser dust, coating debris, shell debris) the mechanical action
increases and the API equation (Eq. 16.1) is not valid anymore (not conservative);
abrasion is enhanced and localizes at elbow extrados, as depicted in Fig. 16.9.
Other zones particularly affected by corrosion-erosion are those where sus-
pended solids are trapped in geometric recesses; for example, deep corrosion-
erosion attacks are produced on pumps body near seals where sand particles are
entrapped because of the lack of appropriate conductors for continuous removal.
Also zones where solids accumulate are affected by corrosion-erosion, for instance
at the bottom of vertical pipes where accumulated solids are in constant agitation
(Fig. 16.10).
16.1.2 Cavitation Corrosion
Cavitation corrosion is caused by the formation and collapse of vapour bubbles in a

liquid in contact with a metal surface. Cavitation removes protective surface scales
by the implosion of gas bubbles in a fluid. This attack occurs when fluid pressure
Fig. 16.9 Extrados zone of a More intense

curve with more intense abrasive action
abrasive action
Flow
Fig. 16.10 Foot of a vertical

tube, where abrasives
accumulate
Flow
Damaged zone due to
abrasion and impact
locally drops below the vapour tension of the transported liquid, especially in high
elevation parts of large equipment or on pump impellers, or in presence of vibra-
tions (for example, inside cooling sheaths of cylinders in diesel engines). The
mechanism is as follows: a pressure drop produces gas bubbles which rapidly
collapse where pressure becomes again normal, then generating violent shock-
waves, with a mechanical damage or also a permanent deformation or even fatigue
of the metal. In aggressive environments, cavitation can result in typical localized
attacks, characterized by numerous deep craters looking like a spongy appearance
(Fig. 16.11). Calculations have shown that implosions produce shock waves with
pressures approaching 60 ksi (about 410 MPa).
The severity of the attack depends on either mechanical factors or fluid
aggressiveness; passivating substances and the presence of gaseous bubbles, present
in the fluid or locally produced by cathodic processes of hydrogen evolution, have a
beneficial effect because they dampen the shockwaves effect.
Fig. 16.11 Cavitation on the

impeller of a pump in
stainless steel AISI 304
16.1.3 Metal Affecting Properties
The corrosion resistance of metals to turbulence, abrasion or cavitation depends

primarily on metal hardness, so that films formed on soft metals are easily removed
together with the metal itself. For example, equipment or pipes made of lead can
resist dilute sulphuric acid exposure for years in stagnant conditions, while only few
days under flow.
Naturally, metal hardness does not influence a pure corrosion process, while it
does influence the resistance to erosion; however, hardening processes, as alloying
or heat treatments, improve erosion resistance if the resulting structure is homo-
geneous: on the contrary, inhomogeneous structures lead to a decrease in resistance.
For instance, among inexpensive materials, silicon-based cast iron, which is a high
hardness homogeneous solid solution containing 14.5% silicon, is certainly the one
which better resists corrosion-erosion and abrasion, then widely used in chemical
industry, despite its poor workability and impact resistance.
More than hardness, self-healing properties of surface films are the key
parameter which determines the resistance to abrasion and corrosion-erosion. As a
rule of thumb, thick films, such as those formed on copper alloys, are easily
removed and difficult to repair because too thick; conversely, thin films, such as
those formed on stainless steels, are more resistant also because of their easier
self-repairing ability. Often, the combination of mechanical action and galvanic
coupling provokes corrosion-erosion also in environments which are safe for the
involved metals separately. A weakening of the protective film is usually observed
when the metal is cathodically polarized without achieving immunity condition.
16.1.4 Environment Affecting Properties
The nature and mechanical strength of protective film as well as its ability to
re-build depend on both the environment and the metal. The presence of oxidizing
or passivating species is beneficial for film consolidation; for example, addition of
chromates to cooling water of diesel engines prevents cavitation attacks. On the
other hand, corrosion rate on bare zones depends on the environment: if it is not
aggressive, the local mechanical breakdown of surface film is not followed by any
corrosion attack. For example, copper alloys in oxygen-free seawater practically do
not suffer corrosion-erosion on damaged surfaces: for this reason, aluminium brass
tubes resist higher water velocity in a desalter than in a heat exchanger, because in
the former water is deaerated.
Figure 16.12 summarizes the influence of the fluid velocity for different industry
used metals and alloys.
16.1.5 Prevention
Prevention methods, which are different in each case, comply with all considera-
tions carried out so far; therefore, they are based on:
• An appropriate choice of materials in relation to flowing conditions
• Protection, at least of most stressed areas, by thick coatings, such as rubber or
ebonite or solvent-free epoxy coatings
Ni-Mo-Cr alloy 59 No corrosion

Titanium No corrosion
Copper-Nickel alloy 70/30 (0.5 Fe) <0.025 <0.25 1.27+
Copper-Nickel alloy 90/10 (1.5 Fe) <0.025 >0.13
Aluminium brass <0.5 >0.13
Admiralty brass <0.05 >0.13
Copper <0.075 >0.13
Carbon steel 0.13-0.25 0.25-0.5 0.5-0.75 0.75-0.9 Increase up to 7.6
Nickel-Copper alloy 400 X <0.025
Stainless steel AISI 316 X <0.025
Stainless steel AISI 304 XX <0.025
Nickel-Chromium alloy XX <0.025
Nickel X <0.025
Nickel- Aluminium brass <0.25 0.75+
Zinc bronze <0.25 0.75+
Nickel austenitic cast iron <0.25 1.0+
Manganese bronze <0.25 0.75+
0 0.4 0.6 0.9 1.5 2.4 3.7 4,6 6.1 15 21 36 43

Flow rate (m/s)
Fig. 16.12 Corrosion-erosion chart (inside boxes: corrosion rate corresponding to the specific
condition, in mm/y) (NiDi 1987)
• A design intended to eliminate all possible causes of turbulence or cavitation, by

suitable choice of shapes and sizes and characteristics of equipment (e.g., pumps
should be chosen with a value of NPSH—Net Positive Suction Head—lower
than that of the system operating condition), fluid flow rate and pressure
conditions
• Environment control as far as particles in suspension are concerned.
16.2 Fretting Corrosion
Fretting corrosion is a form of damage that occurs between two metallic surfaces,
subject to cyclic slips with an amplitude not higher than a few tens of microns,
generally caused by vibrations. Sometimes, this form of attack only shows a loss of
brightness, other times the formation of craters filled and surrounded by corrosion
products as fine powder of metal oxide, typically red rust in case of steel or black
debris in case of aluminium; these craters often trigger fatigue cracks. The for-
mation of oxide powder can cause malfunctioning because of loss of tolerance
limits or galling effects.
Fretting corrosion occurs in machinery and structures subject to vibrations such
as:
• In aeronautics and railways related structures
• Between wires of metallic ropes
• In chemical equipment (plate heat exchangers where vibrations are caused by
fluid flow or pulsing action of pumps; in safety valves)
• In electrical contacts, then causing change of contact resistance, as in telephone
junction boxes
• In the core of nuclear reactors due to the flow of cooling fluid.
16.2.1 Mechanism
Two mechanisms have been proposed to explain fretting corrosion depending on

the sequence of mechanical action and chemical oxidation. According to the first
mechanism, the mechanical action is the first step, consisting of a micro welding of
contact points which are subject to very high pressures due to their limited contact
surface, then followed by the mechanical break of such bridges with production of
metal debris, which are immediately oxidized for the high temperatures reached due
to the friction. The second hypothesis starts from the observation that the majority
of metals is covered by an oxide film, so the slip between the two surfaces produces
the destruction of the oxide film at contact points forming oxide powder and leaving
bare and most likely work hardened areas which are particularly reactive, hence
re-oxidizing immediately, and repeating a new destructive cycle.
According to both theories, the produced debris act as abrasive agents, hence
increasing the damage. It is proved by practice that both mechanisms apply,
depending on the environmental conditions: in inert environments or under vac-
uum, where metals cannot oxidize, fretting occurs according to the first mechanism,
while the second occurs in oxidizing environments. Indeed, the presence of oxygen
accelerates the fretting attack of many metals, in particular of ferrous alloys.
16.2.2 Main Factors
Fretting corrosion occurs when a small cycling slip, generally of shear type, exists
between two metallic surfaces. However, there are conditions where a fluctuating
load is perpendicular to the surfaces, as in the case one of the metallic objects is a
sphere or a cylinder; in these cases, the process is called hammering and the damage
is extremely severe.
Fretting damage increases as applied load, number of cycles and slip amplitude
increase.
As far as the environment is concerned, fretting corrosion of steel surfaces is
almost identical in air or in oxygen; instead, in vacuum or in oxygen-free protective
atmosphere, for example nitrogen or helium, the fretting damage is much lower.
Humidity is very important in oxygen containing environments, while it has a very
modest effect in protective atmospheres.
Among metal-related factors, hardness is the most important. As rule of thumb,
as surface hardness increases, fretting damage is less severe. A further important
factor is the oxide hardness compared to that of the metal: the higher the oxide
hardness the higher the grinding effect on the metal surface.
Surface treatments such as carburizing, nitriding, shot peening, which increase
surface hardness, should reduce the wear damage; instead, experimental data
assessed by weight loss testing showed that these treatments have little influence,
while confirming an increase in fretting induced fatigue resistance.
16.2.3 Fretting Corrosion Fatigue
Fretting represents a fatigue initiation stage when shear stresses cause micro-cracks
exceeding about 100 lm in length. The stress level is generally lower, often by a
factor of 3–6, than that needed for smooth non-corroded specimens. Typically, the
fatigue crack initiation zone is between the corroded area, where slip takes place,
and the adjacent non-corroded one. In fact, fretting micro-cracks propagate diag-
onally to the surface to originate a true fatigue crack which proceeds perpendicular
16.2 Fretting Corrosion 323
to the stress direction. Sometimes, two or more micro-cracks from opposite sides of
the affected zone merge and cause metal spall off.
The effect of fretting on corrosion fatigue of metals is similar to the one of a
severe notch; indeed, metals with high sensitivity to notches are also particularly
sensitive to fretting corrosion. It should also be noted that fretting corrosion, in
regimes characterized by low loads and high number of cycles, reduces fatigue
strength more than in case of the presence of notches.
The most dangerous conditions seem to be those characterized by small slip
amplitude, between 7 and 15 µm, that is, unfortunately, the most common ones in
engineering applications. It appears that slips with higher amplitude, which show a
higher wear rate, are able to eliminate larger micro-cracks and, conversely, to
promote the development of numerous smaller cracks which hardly reach the
critical size to trigger fatigue cracks.
Finally, it is observed that fatigue does not occur when a considerable quantity
of powder is produced, because powder works as a lubricant and also eliminates
micro-cracks through its abrasive action.
16.2.4 Prevention
Prevention of fretting corrosion is based on the following measures:

• Elimination of slips by design
• When slip is unavoidable, reduction of stress concentration on affected areas
• Use of lubricants for a twofold aim: hindering oxygen access and reducing
friction coefficient
• Choice of suitable surface treatments.
16.2.5 Lubricants
Good lubrication conditions help reduce fretting. Lubricants are liquid and, for not
easily accessible parts, solid fats. Liquid lubricants are made of hydrocarbons
(mineral oils) with the addition of additives; solids ones (fats) consist of hydro-
carbons thickened with soap, clay, carbon black, silica gel and additives. Lubricants
which are generally considered not corrosive can become aggressive as a result of
deterioration processes. There are two ways in which the lubricants deteriorate in
service: by contamination with substances such as dust, wear products, fuels,
combustion products, water, and through physical-chemical modifications due to
oxidation which leads mainly to the formation of acidic substances.
To improve the properties of lubricants and additives, inhibitors are added. It
should be paid particular attention to the additives which have the function of
binding the lubricant to the metal material. Generally these substances are
carboxylic acids, alcohols, sulfonic acids, which contain functional groups that
react with the metal surface locally forming an extremely thin layer. If the operating
conditions are very harsh, these layers are continuously formed and destroyed,
resulting in a corrosion itself.
Among solid lubricant coatings for applications on steel there are sulphur rich
layers (sulphide process) and molybdenum sulphide, MoS2.
• API RP-14E, Recommended practice for design and installation of offshore

production platform piping systems, American Petroleum Institute, Northwest
Washington, DC.
• ASTM D 2809, Standard test method for cavitation corrosion and
erosion-corrosion characteristics of aluminium pumps with engine coolants,
American Society for Testing of Materials, West Conshohocken, PA.
• ASTM E 2789, Standard guide for fretting fatigue testing, American Society for
Testing of Materials, West Conshohocken, PA.
• ASTM G 32, Standard test method for cavitation erosion using vibratory
apparatus, American Society for Testing of Materials, West Conshohocken, PA.
• ASTM G 73, Standard test method for liquid impingement erosion using
rotating apparatus, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM SPT 1425, Fretting fatigue: advances in basic understanding and
applications, American Society for Testing of Materials, West Conshohocken,
PA.
• ISO 16203, Corrosion of metals and alloys. Guidelines for the selection of
methods for particle-free erosion corrosion testing in flowing liquids,
16:1 API equation provides a relation between fluid critical velocity and its mass
density. What does the constant C represent? (Hint: consider the mathe-
matical equation by an energetic approach).
16:2 Based on API equation for erosion corrosion assessment, calculate the fluid
critical velocity of seawater (mass density 1100 kg/m3) for a copper-nickel
70/30.
16:3 Based on API equation, indicate the minimum diameter of different spools
used in a loop for the following fluids: seawater; oil; oil + gas; brine +
oil + gas. The fluid density is 1100–880–1.5 kg/m3 for seawater, brine,
oil + gas (in standard condition), respectively. Composition is GOR
(gas-oil-ratio) 1000 m3/m3, WC (water cut) 10%. Flow rate is 0.1 m3/s.
[Hint: density of multiphase fluids is the weighted average].
16:4 Why are copper alloys less resistant than stainless steels to
erosion-corrosion?
16:5 A heat exchanger consists of an AISI 316L stainless steel water box, an
AISI 316 shell, a Cu-Ni tube-sheet and pure Cu tubes. Cooling fluid into the
pipes is seawater. After 2 years operation, a leakage of copper tubes was
detected. Eddy current analysis revealed a corrosion attack on the internal
surface of some tubes. Seawater total flow rate is 104 m3/h. Pipes cross
section is 1 m2. Which is the cause of corrosion? Is pure copper a correct
material selection? Does the use of Cu-Ni solve the problem?
16:6 Discuss the effect of the presence of oxidizing or passivating species on
erosion corrosion.
16:7 Describe the mechanism by which cavitation occurs.
16:8 Cavitation occurs on pump impellers. Explain why and how it is more risky
when pumping seawater than gasoil.
16:9 Discuss the two main mechanisms proposed to explain fretting corrosion.
16:10 Try to explain why and how the addition of molybdenum sulphide to
lubricants is beneficial to reduce fretting damage. How can phosphatizing
the surface reduce the fretting hazard?
16:11 Discuss the difference between the expected fretting damage in a metallic
rope when used in air with an incorrect lubrication and in full immersion in
seawater. Explain why and how cathodic protection could be beneficial.
16:12 What is the effect of metal hardness on fretting corrosion resistance?
16:13 Discuss the effect of fretting on corrosion fatigue.
16:14 Water jet is used to cut many metallic alloys. Explain the principle on which
it is based. Do you think that corrosion prevails on erosion?
Bibliography
Nickel Development Institute, NiDI (1987) Nickel stainless steel for marine environments, natural
waters and brine. Guideline for selection, series 11 003, London, UK
Waterhouse RB (1972) Fretting corrosion. Pergamon Press, New York
Chapter 17
Corrosion Prevention by Coatings
A tin coating applied to the buccal makes it more pleasant to the

taste and halts the virus of rust and, wonderful to say, the
weight does not increase.
Pliny, Nat.Hist., 34.160
Abstract This chapter deals with the method of corrosion prevention based on the use
of a physical barrier to separate the metal surface from the environment. This barrier
consists of a coat that can be classified, as often generally agreed, into four types,
namely: metallic coatings, conversion coatings, inorganic coatings and paints. In this
Chapter, only corrosion protection related coatings are considered, although other
characteristics, such as mechanical strength, hardness, wear resistance, appearance, and
electrical, optical or thermal properties are also of remarkable importance.

https://doi.org/10.1007/978-3-319-97625-9_17
328 17 Corrosion Prevention by Coatings
17.1 Metallic Coatings
The use of metallic coatings is one of the most common methods adopted for
corrosion prevention. Metallic coatings are usually named according to the metal
used, for example, copper, zinc, nickel, gold coatings. This nomenclature is rather
generic as any coating may have a crystalline or amorphous structure, a fibrous
morphology, or columnar, yet coarse or fine, lamellar or strip banded; furthermore,
they present a variable chemical composition through small percentages of metals
and/or impurities as hydrogen, oxygen, carbon, sulphur.
17.1.1 Coating Defects
From a corrosion point of view, continuity, uniformity as well as the absence of

porosity are of particular importance for the coating performance. In fact, when a
coating is continuous and non-porous, the base metal is thoroughly covered, so cor-
rosion takes place on the coating metal as it would happen on a solid plate (Fig. 17.1).
If the metallic coating is porous, galvanic couples form between the metal of the
coating and the base metal on uncovered areas; the result of galvanic coupling can
lead to a cathodic protection effect exerted on the base metal or, conversely, to an
accelerated anodic dissolution of it, depending on the practical nobility of the two
metals, as discussed in Chap. 10.
Coating defects are primarily produced in the application phase. The coating
metal may not deposit or adhere to the base, or result porous due to poor surface
preparation or inappropriate pre-treatment or incorrect application conditions—for
instance, in case of galvanic deposits, excessive operating current densities. For
example, a coating applied to cast iron may be non-adherent due to graphite powder
left on the surface by a previous pickling, as well as on titanium a metallic coating
shows poor adhesion because of a titanium oxide film, which forms immediately
after pickling. On the other hand, the technique used can set up a high porosity, as
for example in the case of sprayed coatings.
Other defects arise during manufacturing or processing (cutting, drilling,
welding) or during operating events as mechanical damage, wear or corrosion
attacks.
17.1.2 Cathodic Coatings
Let's consider first the case study of a metallic coating made of a metal nobler than
the base, hence with a cathodic behaviour against the base metal that is anodic. As
Fig. 17.2a shows for the case of a copper coating applied on carbon steel, the
coating metal, i.e., copper, is nobler than the base, i.e., carbon steel, so that
17.1 Metallic Coatings 329
PbSO4
(a) (b) (c)
Copper Lead Platinum
Carbon steel Carbon steel Titanium
Fig. 17.2 Effect of porosity in a cathodic-type coating
corrosion takes place on the latter metal in coating defects, favoured by the small
overvoltage of the anodic process (active metal dissolution). These considerations
can be extended to the use of coating metals such as nickel, silver, lead, all nobler
than carbon steel, and materials with active-passive behaviour such as chromium,
titanium and stainless steels, having a practical noble behaviour. For the estimation
of corrosion rate, reference is made to Chap. 10.
Metallic coatings made of passive metals are generally less effective in accel-
erating corrosion rate than active noble metals (for instance, stainless steel versus
copper) because the overvoltage associated with oxygen reduction is much higher.
Furthermore, if the passive film is an insulator as in the case of anodized alu-
minium, the galvanic effects stops.
Noble metallic coatings can be used when corrosion products seal defects and
pores of the coating in which corrosion initially takes place, then impeding cor-
rosion to proceed. For example, this occurs to porous lead coatings on carbon steel
operating in industrial environments, where the coating porosities are filled with
lead sulphate as initial corrosion product (Fig. 17.2b); or when exposed to hard
fresh water where, due to the alkalinity produced on the surface by the cathodic
reaction, a mixture of carbonates and iron corrosion products forms.
In atmospheric corrosion or in low conductivity solutions, the influence of
porosity is less important because the galvanic effect is modest or even negligible,
as the ohmic drop between cathodic and anodic areas is high and the geometry of
the condensate film makes the surface area ratio unitary.
If the base is an active-passive metal, corrosion conditions are different from
what previously described. For example, a coating made of platinum or gold on
titanium, which is passive, has no dangerous consequences (Fig. 17.2c); the same
applies to stainless steels in chloride-free environments.
17.1.3 Anodic Coatings
If the coating metal is less noble than the base, any porosity or defect of coating is
not intrinsically harmful because the coating metal itself works as anode, also
ensuring a cathodic protection effect (Fig. 17.3a).
Carbonates
(a) (b) (c)
Zinc Zinc Zinc
Carbon steel Carbon steel Carbon steel
Fig. 17.3 Effect of porosity on an anodic-type coating: a porosity; b coating defect larger than a
critical diameter; c sealing effect by corrosion products
Typical coatings of this type for carbon steel are zinc, aluminium and, for
specific environments, tin. Industrially, zinc coatings are often referred to as gal-
vanized goods. The critical size of a coating defect which allows a sufficient pro-
tection effect depends on conductivity and geometry of the aggressive environment.
For example, for outdoor galvanized carbon steel, the critical defect size is slightly
more than 1 mm in diameter (the electrolyte is condensed water, i.e., distilled
water); for larger size, evidence of a corrosion attack, i.e., a rusting point, appears in
the middle (Fig. 17.3b). In brackish water or seawater the critical defect size
increases by at least one order of magnitude. Also for anodic-type coatings, sealing
effects can arise, as for example on galvanized steel exposed to hard fresh waters by
the precipitation of carbonates triggered by the alkalinisation on cathodic areas, that
is, on the carbon steel surface (Fig. 17.3c). Anodic coatings can lead to hydrogen
evolution as cathodic reaction on the base metal, therefore, if the latter is susceptible
to hydrogen embrittlement, the use of these coatings has to be carefully analysed
case by case.
17.1.4 Multilayer Coatings
A single metal layer is not always possible or convenient as metallic coating, while
a multiple layer can solve smartly corrosion concern.1
The presence of defects in the coating causes consequences similar to those
already described for single-layer systems. However, as corrosion penetrates and
inner layers arise, the electrochemical system changes accordingly. For example, in
the multilayer depicted in Fig. 17.4, composed of—from external to internal—
chromium, nickel and copper on the base carbon steel (i.e., iron), copper and nickel
are initially anodic versus chromium and become cathodic versus iron, once the
electrolyte reaches the inner layer, enhancing galvanic corrosion on the latter.
1
For some applications, for example for electronic components, multi-layered coatings are used for
functional requirements and not for corrosion prevention.
Fig. 17.4 Corrosion damage

in a multilayer Cr-Ni-Cu-Fe
coating due to a coating
defect
Nickel-chrome coatings. A good example that illustrates the behaviour of multi-

layer coatings is the so-called decorative chrome plating, largely used in the past in
automotive industry (chromate bumpers and slips of cars). Despite their name, these
coatings are not a monolayer of chromium, instead they are one or more layers of
nickel for a total thickness of some tens of µm, covered by a thin layer of chro-
mium, 0.25–0.8 µm thick, to give shiny appearance and resistance to abrasion.
Only chromium is not used because it would be cathodic to iron, then accelerating
galvanic corrosion beneath coating defects and the formation of rust that would be
difficult to remove by washing, so consumers would not accept it essentially for
aesthetic reasons. Unfortunately, it is not possible to obtain thin, defect-free chro-
mium films, because even in the presence of little deformation they suffer
micro-cracking, then exposing the iron beneath.
The presence of a nickel layer does not change the electrochemical scenario
because nickel is less noble than chromium, so nickel corrodes as iron does in
correspondence of chromium defects, but nickel corrosion products are almost
invisible and easily washed out.
A layer of nickel below chromium could therefore appear as the correct solution,
because nickel layers can be obtained almost without defects and they do not crack
in operating due to its ductility. However, this solution may appear weak because
the nickel layer is still stimulated to corrode at chromium film defects; luckily, the
passive chromium surface is a bad catalyst for oxygen reduction, so the corrosion
process is under cathodic control. This leads to the final result that even a high
porosity chromium layer reduces the penetration rate on nickel. In fact, the effective
cathodic surface does not change with the defectiveness of chromium, so the
available oxygen amount is constant as well as the total amount of dissolved nickel,
therefore the nickel corrosion rate decreases as chromium porosity increases
(Fig. 17.5a).
(a)
Cr
Ni Chromium
low porosity
Fe
(b) Cr
Ni Chromium
high porosity
Fe
(c) Cr
Ni Chromium
optimal porosity
Fe
(d) Cr
Ni-S Duplex
Ni coating
Fe
(e) Cr
Ni
Ni-S Triplex
Ni coating
Fe
Fig. 17.5 Schematic representation of corrosion behaviour of different types of nickel-chromium

deposit
A promising solution could be the use of a high porosity chromium film with
distributed micro-cracks that spread the corrosion process on the whole surface
(Fig. 17.5b). These high porosity coatings can be obtained by depositing on the
nickel layer a thin chromium film (0.25 µm) enriched with small particles of alu-
mina, or a highly micro-cracked chromium layer, with high thickness (0.8 µm) that
ensures high stresses and therefore film micro-cracking.
For each thickness value of the nickel film there is a critical value of the coating
defect density that maximizes the time required for nickel consumption
(Fig. 17.5c). Such value can be found assuming that defects in the chromium film
are pores, and that corrosion of nickel proceeds by forming hemispherical cavities;
on this basis, pores spacing in the chromium film should be twice the nickel layer
thickness. These coatings are typically used in environments with moderate
aggressiveness.
In polluted environments, such as those in contact with the bumper of cars, these
nickel-chromium coatings show a too short duration, therefore a different philos-
ophy is adopted by switching to so-called duplex coatings. These consist of two
layers of nickel: one, non-porous and ductile, on steel and a second one,
sulphur-enriched, less noble, defective and brittle, working as galvanic (sacrificial)

anode (Fig. 17.5d) on top of the first. These duplex coatings are also used to
prevent corrosion in different environments (for example in chemical reactors) by
acting as an efficient and reliable barrier. This solution is also recommended when
small quantities of corrosion products are permitted. These coatings last propor-
tionally to the thickness of the sacrificial layer.
In the specific case of bumpers, duplex coatings are not always working prop-
erly. In fact, as corrosion of the external nickel layer proceeds, adhesion of the
chromium layer decreases up to delaminate (Fig. 17.5d). To strengthen the coating
a three-layer nickel coating is used (Fig. 17.5e), where the third layer is again
nickel. It is curious to note that once the best coating to protect bumpers was
eventually developed, chromate steel bumpers were abandoned.
17.1.5 Methods for Obtaining Metallic Coatings
Metallic coatings are obtained by different methods:

• Mechanical. By hot rolling (cladding), by jacketing or by spraying a molten
metal
• Physical at high temperature. By immersion in molten metal (zinc, lead, alu-
minium, tin and tin-lead alloys); by diffusion of metals from powders (zinc,
aluminium, chromium or silicon); by welding (for example stainless steel).
These coatings show high adhesion to the base metal, due to the formation of
alloys as result of a metal diffusion at the interface
• Physical at low temperature. A physical method at low-temperature is evapo-
ration under vacuum. The adhesion of coatings is merely mechanical
• Chemical at high or low temperature. Among the former, chromium, silicon and
aluminium coatings are obtained from reduction or dissociation of the respective
chloride through chemical vapour deposition technique; or from molten salts by
displacement or electrodeposition. These coatings are characterized by a good
adhesion based on the formation of alloys at the interface. Low temperature
methods are electrodeposition, displacement and chemical reduction.
In the following, some details are provided.
Sprayed coatings. The metallic coating is obtained by spraying molten metals or
alloys directly on the metal surface. It is used particularly for zinc and aluminium
and their alloys. By employing a plasma flame it is also possible to deposit
high-melting metals, oxides (Al2O3), compounds (carbides, nitrides, borides),
which are materials with high mechanical characteristics (in particular wear resis-
tance) and corrosion resistance. Sprayed coatings have special features. First of all,
adhesion to the base metal is poor being purely mechanical; an increase in
roughness is generally beneficial. The porosity of these coatings is high, since they
are obtained by the impact of small drops of liquid metal covered by a layer of
oxide; this leads to the conclusion that only anodic coatings can provide good
protection. Furthermore, because of their porosity they can be easily painted,
obtaining the sealing of pores. The greatest advantage of this method is that the size
of the component is not a limit, either considerable or tiny such as riveting or
bolting.
Immersion coatings. This is the oldest, easiest and often cheapest method. The
metallic coating is obtained by dipping the goods, previously degreased, deoxidized
and dried, in a bath of molten metal or alloy for a short period. In practice, this
method is used to coat carbon steel with low melting metals, such as zinc, lead and
their alloys, tin and aluminium. The cross section of a metallic coating obtained by
immersion shows a range of compositions, varying from the base metal through
gradual alloying up to the composition of the metallic coating. The formation of
these alloys, often consisting of intermetallic compounds, is the necessary condition
for obtaining a good adhesion. For example, iron and copper, which do not form
alloys with lead, cannot be covered directly with it, because of lack of wetting
conditions; to obtain adherent coatings, an intermediate layer is used to bind the
base metal to the final coating, as for example tin and antimony as intermediates for
iron and lead. The main advantages of this technique are simplicity and high
production speed. There is a limitation for complex geometries for which it may be
difficult to obtain uniform thickness. The presence of small holes or cracks should
be avoided. This method has some disadvantages, such as the decrease of ductility.
The process to obtain zinc coating by immersion is known as galvanizing or hot-dip
galvanizing and is the most world widespread.
Chemical reduction. This process exploits a redox reaction which reduces the ions
of the metal to form the metallic coating by a suitable reducing agent. The reduction
reaction of metallic ions occurs, for kinetic reasons, preferentially or exclusively on
the surfaces to be coated and not within the solution. The metal deposition is
obtained on a variety of materials, from metals to non-conducting ones such as
ceramics, polymers, glass. The most used reducing agents are: sodium hypophos-
phite to deposit nickel, cobalt and their alloys, gold, silver, palladium (with
simultaneous deposition of phosphorus that is derived from the decomposition of
hypophosphite) and formaldehyde to deposit copper. For nickel, cobalt and pre-
cious metals also boranes are used, which lead to a co-deposition of nickel-boron
alloy, and hydrazine. Coatings obtained by this method, either with microcrystalline
or amorphous structure, show low porosity, high hardness, almost uniform thick-
ness regardless the shape, therefore particularly suitable for profiled surfaces as
threads, holes, valves. The nickel coating, called chemical or electroless nickel,
which is in practice the most popular obtained by this method, can be hardened by a
precipitation heat treatment because of the presence of phosphorus or boron,
reaching hardness values comparable with those of the chromium coating, making
the coating highly resistant to wear.
Electrodeposition. This is the most used method for obtaining metallic coatings,
and is generally performed in aqueous solutions. Since in aqueous solutions
hydrogen evolution can take place in competition with metal deposition, metals less
noble than zinc are excluded: in those cases molten salts or non-aqueous solutions
have to be used. Common electrodeposited coatings are: gold, silver, copper, lead,
tin, zinc, cadmium, chromium, nickel, iron, cobalt, platinum, rhodium and others,
either as pure metals or alloys. The obtained thickness is regulated and varies from
fractions to hundreds of micrometres. Physical and mechanical properties, such as
brightness, porosity, hardness or mechanical strength, can be controlled and varied
over a wide range by changing nature and composition of solution and setting
current density, temperature and stirring. The most used solutions are based on salts
of the metal to be deposited as sulphates, cyanides, pyrophosphates, fluoroborates
and sulphamates, with a complex composition due the addition of substances with
various purposes, as:
• Substances with buffer effect, for pH control at the cathodic boundary layer
where the hydrogen evolution process produces alkalinity
• Complexants
• Substances increasing conductivity
• Catalysts
• Substances increasing cathodic overvoltage to increase the throwing power for
obtaining more uniform deposits
• Depassivating substances to have a uniform attack of the anodes
• Levellers or brighteners to get levelled or bright deposits
• Wetting agents or surfactants to get rid of hydrogen bubbles which would shield
the cathode then impeding the metal deposition.
These substances, especially organic ones, can dope the deposit and modify
chemical-physical or mechanical properties as hardness, corrosion resistance or
electrical conductivity. Sometimes, neutralizing agents are added; for example,
brighteners or levellers can promote tensile or rarely compressive stresses within
the deposit, accordingly other substances are added to balance opposite effects.
Current density influences many properties as appearance, uniformity, porosity,
mechanical and chemical-physical characteristics; therefore, it is maintained in
proper ranges of values, generally increasing as temperature, concentration of metal
ions and agitation increase. Outside those validated ranges (i.e., if current density is
too high or too low) non-uniform coatings, very porous or even spongy, often
polluted with oxides or hydroxides, and poorly adherent are obtained. Among
aspects worth of discussion, those dealing with microstructure, adhesion,
mechanical and more generally physical-chemical properties, homogeneity (i.e.,
throwing power) and alloying should be remembered. In the following, only
throwing power is mentioned, because impacting also on the more general problem
of current distribution in galvanic cells as established in galvanic corrosion and
cathodic protection.
Throwing power and uniformity of metallic coatings. In an electrolytic cell of
cylindrical geometry, where electrodes are the two parallel bases, perpendicular to
the cylinder axis, current lines are parallel and perpendicular to the electrodes, and
current density is uniform, so that a homogeneous coating is obtained. For all other
geometries, conditions are different. In practice, current density is never uniform on
the cathode because current lines concentrate where facilitated, for instance where
anode-to-cathode distance decreases or on edges, and their density is lower where
screens, recesses and cavities are present. As a result, metallic coating thickness is
not uniform. As discussed in Chap. 9, current distribution is primary when the
overvoltage is negligible on both electrodes, accordingly it follows the Ohm’s law
and depends on geometry, only; conversely, when overvoltage prevails, current
distribution becomes secondary and depends also on resistivity. In primary distri-
bution conditions, either current density or coating thickness depends on the anode-
to-cathode distance. When the secondary distribution applies, ohmic drop in so-
lution and overvoltage on electrodes lead to a compensation which in practice
makes the current distribution more uniform, which means that throwing power is
high. For instance, this is the case of cyanide-based salts and more in general of
complex salts used as electrolyte. Various tricks are used to achieve uniform current
distribution even in low throwing power conditions. For instance, by making round
corners and edges; or shaping the anode as the cathode; or by placing insulating
screens, or auxiliary electrodes (cathodes) called current thieves as parasite
electrodes.
17.1.6 Zinc Coatings
Zinc coatings, called galvanizing, are widely used for protecting carbon steel in
atmospherically exposed structures. Their anodic behaviour reduces the require-
ments regarding uniformity and porosity, facilitating the application and reducing
costs. Their performance is a function of environmental conditions and their lasting
is proportional to the thickness. Typical corrosion rates are the following:
• 0.2–3 lm/year in rural areas
• 0.5–8 lm/year in marine environment
• 2–16 lm/year in urban and industrial environment.
The corrosion rate of zinc is 10–30 times lower than the one of carbon steel
according to environmental conditions; in water, zinc behaviour is good in the pH
range 7–12.
As temperature increases the difference in nobility between iron and zinc
decreases. In fresh aerated waters at temperatures around 40–60 °C, zinc and iron
undergo a polarity reversal which makes zinc cathodic versus carbon steel, then the
beneficial protection effect in correspondence of coating porosity or defects is lost.
This behaviour derives from the formation of a conductive zinc oxide which allows
oxygen reduction, while the normal zinc hydroxide does not, being a good insulator.
Galvanizing is obtained through two techniques: by immersion in a bath of
molten zinc or by electrodeposition. By the hot immersion method, high
thicknesses are obtained, in the order of 100 lm, while by electrodeposition typical
thicknesses are in the range 2–5 lm. Because corrosion duration depends on the
zinc layer thickness, electro-galvanizing is used only as primer for painting systems,
as is typical in automotive industry.
17.1.7 Tin Coatings
Among metallic coatings for laminated products, tinplate is the most manufactured.
It is produced by electrodeposition. The first output from the electrolytic cell is a
matt, porous product which has to be heat treated at the tin melting temperature
around 250 °C to make it brilliant, more compact and more adherent to the base.
Tin is an amphoteric metal, corrosion resistant at pH close to neutrality. As low
melting metal, the overvoltage of the hydrogen evolution process is very high, so
corrosion rate in non-oxidizing acidic environments is very low.
The use of tinplate for food cans derives from two fortunate circumstances:
• Tin salts are not toxic, although human tolerance is limited to very low contents
• Tin exposed to food substances becomes anodic versus iron, then giving pro-
tection effects, because organic anions present in food form complexes of
stannous ions and help passivate iron, leading to this final result: tin potential
decreases and that of iron increases.
As a result, iron does not corrode due to the cathodic protection effect given by
tin and tin does not corrode due to the high overvoltage for the hydrogen evolution
process. Conversely, without that beneficial mechanism, the usual nobility sets up,
therefore iron rapidly corrodes at tin coating defects and because of extremely
unfavourable cathodic-to-anodic area ratio with two injuries on the cans: a rapid
perforation and an evident bulging due to hydrogen formation.
17.1.8 Nickel Coatings
Nickel coatings are widely used for a variety of features, such as mechanical
resistance, hardness, ductility, as well as corrosion resistance to industrial atmo-
sphere, waters, alkaline solution, basic molten salts, and solvents; it is also used for
decoration purposes.
Decorative coatings exposed to atmosphere, typically 10–50 lm thick, are
covered by a thin layer of chromium, about 0.3–0.8 lm thick, to prevent the lack of
gloss; this also increases the resistance to wear. Used in chemical plants with
thickness as high as 250 lm, nickel coatings are obtained by electroplating as well
as by chemical reduction (known as electroless nickel deposition) when equipment
has complicated shape.
As far as electroless nickel is concerned, which consists of nickel-phosphorus

based coating, its use is typically in car parts, machine parts, electronic parts, office
automation apparatus parts, precision product and other applications. Thickness
varies from 25 to 75 lm. The content of phosphorus in the film is in the order of 6–
13%. The altered composition gives to the coatings higher mechanical character-
istics, wear resistance and hardness, especially after annealing. Corrosion resistance
is improved in the as-deposited state, especially to organic acids and caustic
environments, due to the formation of a protective, amorphous glassy film, where
the absence of grain boundaries eliminates the risk of SCC.
Since many years, nickel coatings have been prohibited for personal goods as
glasses and jewellery because it causes allergic reactions.
17.1.9 Chromium Coatings
Chromium coatings are bright, hard, brittle, highly tensioned, porous (if thin) and
cracked (if thick). They can be divided in two main types: thin coatings for dec-
orative purposes and thick ones (also called hard chrome) for corrosion prevention.
Decorative chromium coatings, about one micron thick, are generally deposited on
a layer of nickel; hard coatings are much thicker, about 200–300 lm thick, and are
used to resist wear and corrosion even at high temperature.
Chromium plating is more recent than others like copper, nickel or gold plating,
which appeared in the nineteenth century, while chromating dates back to 1920s. It
is interesting to note that chromating is obtained in an unexpected condition: the
electro-deposit is obtained from chromic acid and not from chromium salts, pro-
vided the presence of a catalyst which is usually a small percentage of sulphuric
acid, or hydrofluoric acid and fluosilicic acid. Since chromium plating baths have
poor throwing power, it is difficult to deposit chromium on objects with compli-
cated shape; furthermore, current efficiency zeros below a critical current density
value, while above it efficiency grows as current density increases.
17.1.10 Copper Coatings
Copper plating finds less applications than nickel and chromium, although today
high throwing power baths are available, able to give perfectly polished and uni-
form deposits. The reason is that copper plating is rarely used for decorative pur-
poses, because of easy oxidation unless protected with lacquers or special surface
treatments. On the contrary, there are a lot of industrial applications. It is used on
cast zinc before nickel plating, which occurs in acidic baths (pH = 4) where zinc
would dissolve, jeopardizing the adhesion: a previous copper plating in an alkaline
bath allows to overcome the problem. A second example is the use of copper on
plastic objects before nickel plating, with the purpose to absorb the differential
thermal expansion between plastic and metal.
17.1.11 Precious Metals
In the past, the deposition of precious metals was limited to gilding and platinizing
for decorative purpose and protection of electrical contacts. Nowadays, gold
deposits are widely used in electronic industry to avoid oxidation of contacts and
because of good thermal and electrical conductivity.
Among other precious metals, rhodium should be remembered, which is very
hard, wear-resistant, resistant to acids, even aqua regia, used to produce mirrors
with very uniform reflectivity and resisting to scratching. Coatings made of oxides
of precious metals such as ruthenium and iridium, called mixed-metal-oxides
(MMO) are used on titanium since 1970s in industrial electrochemistry and for
anodes employed in cathodic protection applications, because such oxides show
low overvoltage and good resistance to aggressive environmental conditions (high
acidity and chlorine evolution) while ensuring good conductivity.
17.2 Conversion Coatings
These types of coatings are formed on the surface of various metals as the result of
chemical or electrochemical reactions after immersion in suitable solutions. Most
popular processes for obtaining conversion coatings are phosphatizing, chromating
and anodic oxidation.
17.2.1 Phosphate Coatings
Phosphate coatings are obtained on carbon and galvanized steels by immersion in

acidic phosphate solutions that form on the metal surface a porous, crystalline
phosphate layer strongly adherent to the metal. This layer, which works by itself as
a mild corrosion prevention, is an excellent and economical primer for anchoring
paints or as temporary protection of semi-finished products. It was extensively used
in automotive industry and presently it is widely adopted for indoor goods as
metallic scaffolds and household machines.
Manganese and zinc phosphates are employed, which—as well as iron—may
form the following relevant phosphates:
• Primary phosphates of M(H2PO4)2 type, very soluble in water

• Secondary phosphates, MHPO4, slightly insoluble
• Tertiary phosphates, M3(PO4)2, insoluble in phosphoric acid solutions.
In acidic solutions with pH between 2 and 4, the above phosphates are in
hydrolytic equilibrium according to the following reactions:
MðH2 PO4 Þ2 ! MHPO4 þ H3 PO4 ð17:1Þ
3MHPO4 ! M3 ðPO4 Þ2 þ H3 PO4 ð17:2Þ
As soon as the metal, for example iron or zinc, is exposed to the solution, the first
stage is a corrosion reaction, such as the following for iron:
Fe þ 2H3 PO4 ! FeðH2 PO4 Þ2 þ H2 ð17:3Þ
with a local reduction of acidity on the metal surface, which pushes reactions (17.1)
and (17.2) rightward, causing the separation of the tertiary phosphate. This happens
in the narrow range of the free acid to phosphate ratio of 0.12–0.15: in other words,
this ratio must be sufficiently low to allow the precipitation of phosphates but not
too low to have also precipitation inside the solution. Hydrogen evolution is the
slow stage of the process and tends to shield the metal surface; to avoid these
drawbacks some oxidizing substances, such as nitrites, nitrates, chlorates and
peroxides are added, to oxidize hydrogen into water. Depending on the applica-
tions, composition, thickness and morphology can vary.
Conversion coatings can be used as primers for painting cycles as composed of the
phosphates of the three metals, Fe, Mn and Zn, to obtain a weight of 10–30 g/m2.
Phosphatizing obtained by spraying is often preferred to the one by immersion,
especially for temporary protection.
17.2.2 Chromate Filming
In the past, chromate filming treatment was employed for finishing aluminium, zinc,
cadmium and magnesium (but not for steel), either as corrosion prevention or as
primer for painting cycles. The former is based on the presence of hexavalent
chromium as strong passivating agent; however, due to its toxicity the treatment has
been banned. Alternative treatments based on non-toxic trivalent chromium are
much less effective.
Chromate-based coatings are obtained by immersion for a few minutes in an
acidic chromate solution, usually sodium bichromate, Na2Cr2O7, containing
depassivating additives that co-precipitate in the coating as chlorides, fluorides and
also phosphates. Composition and pH of chromate filming solution vary according
to the metal. A chromate coating is generally yellow or even transparent, amor-
phous, thin (a fraction of a micron thick) and with semiconductor characteristics.
17.2 Conversion Coatings 341
It is believed that the mechanism of film formation entails, initially, the disso-
lution of substrate surface (metal or oxide), then the partial reduction of hexavalent
chromium and simultaneous separation on the metal surface of a film consisting of
chromium chromate, Cr2(CrO4)3, mixed with oxides of the treated metal and other
species that are present in solution such as phosphates.
17.2.3 Anodic Oxidation
Anodic oxidation is an electrochemical process carried out in order to thicken the

oxide film naturally present on metals, with the aim to improve the corrosion
resistance or the aesthetic look or to obtain oxide films with insulating properties.
Anodic oxidation of aluminium. Aluminium anodizing is certainly the most
widely used electrochemical process of anodic oxidation for the production of
aluminium goods, known as anodized. Anodizing improves corrosion resistance
and gives a good pre-treatment for further painting especially after chromate filming
has been banned. Aluminium anodizing goes through three stages:
• Surface preparation
• Anodizing, possibly followed by a colouring treatment
• Sealing.
Surface preparation aims to remove all contaminants, in particular iron inclusions,
which often remain after mechanical processing.
Table 17.1 summarizes the parameters relating to the three most used processes
for aluminium anodizing. The properties of oxide films depend on bath composition
and operating conditions (i.e., temperature and current density). Oxide thickness
ranges from a few microns to about 50 µm as depending on time and current
applied. Figure 17.6 shows the aluminium oxide structure, which is composed of an
inner barrier layer covered by a porous layer, with a typical porous honeycomb
structure, obtained in less than one hour with applied voltage of 20–60 V; these
films are used typically as anticorrosive coating. For other applications, such as for
electrolytic capacitors, other solutions are used, for example, boric acid or
ammonium phosphate solutions which allow to obtain oxide films with only the
barrier layer structure.
Table 17.1 Characteristics of the three most frequently used processes for aluminium anodizing
Acid (% by weight) T (°C) Cell voltage (V) Current density Thickness (µm)
(A/m2)
Sulphuric 10–15% 15–25 10–20 100–300 3–50
Chromic 3–10% 30–40 30–50 30–40 2–8
Oxalic 3–8% 20–40 30–60 100–300 10–60
Porous layer
Barrier layer
Aluminium
Fig. 17.6 Schematic representation of the barrier layer and of the porous oxide film produced by
anodic oxidation of aluminium
To eliminate the porosity of the porous layer, a sealing process is necessary,

which consists of the hydration of aluminium oxide which seals the pores by
swelling. In the past this treatment was done by immersion in boiling water for
about 5–20 min or exposure to steam at 150 °C; today cold-sealing catalysed
processes are used, for example by immersion in a nickel fluoride solution. During
this operation, some substances can be conveniently entrapped into pores, such as
corrosion inhibitors, or pigments to colour the film.
Anodic colouring of titanium. A few years after Volta’s pile invention, the Italian
physicist Leopoldo Nobili (1784–1835) discovered that by anodizing some metals,
such as lead and tin, amazing interference colours could be obtained: he called this
electrochemical technique metallocromia. Today this anodic colouring technique is
applied to titanium and other so-called valve metals. Stainless steels can also be
oxidised to obtain a colouring effect, but the treatment is a chemical one, based on
the immersion of the metal in a suitable chemical bath.
On titanium, anodic oxidation gives rise to beautiful interference colours, as
Pietro Pedeferri obtained for artistic decorations and as new painting technique. By
varying operating conditions and bath composition, amorphous or crystalline films
are obtained. The latter, in the form of rutile or anatase crystal structures, can
exhibit interesting antibacterial, photocatalytic and superhydrophilic properties.
In many solutions, with the application of very high cell voltage for anodic
oxidation, an electrical sparking occurs which perforates the anodic film (anodic
spark deposition), giving brown or grey coloured oxides, several microns thick. It is
interesting to note that the oxide film can incorporate ions present in the used
solutions as sodium, potassium, calcium, phosphorus and others. As shown in
Fig. 17.7, a typical morphology of such anodic films is observed at the microscopic
scale, showing the presence of craters that sparks form.
Figure 17.7 shows another interesting structure consisting of oxide nanotubes
obtained in fluoride ions containing solutions, which are characterized by a huge
surface, tens or hundreds of times the nominal one.
17.2 Conversion Coatings 343
Fig. 17.7 Micro and nanostructure of films of titanium dioxide obtained by anodic oxidation: left,
anodic spark deposition; right, nanotubes
17.3 Other Inorganic Coatings
17.3.1 Hot Enamels
Metals as cast iron, copper, aluminium and mostly carbon steel can be coated with
enamels applied at high temperature (glass lining) which result very adherent to the
metal surface, resistant to abrasion and corrosion especially in acidic environments
(except hydrofluoric acid) and produced with pleasant finishing and stable colours.
Enamels are obtained from a mixture of silica, titanium oxides, feldspars, clay
and melting additives as borax, fluorosilicates, nitrates and carbonates of lithium
and potassium, melted at a temperature between 1000 and 1400 °C to obtain
alkaline aluminium borosilicate compounds, then rapidly cooled in water and
successively grinded. This powder, added with coloured pigments, is sprayed on the
metal surface and heated in oven at 750–850 °C for some tens of minutes.
Chemical resistance in acidic environments increases with the addition of silica,
titanium oxide and zirconia and decreases with the addition of boron oxides.
To ensure a good adhesion to the metal surface, which is enhanced by nickel and
cobalt oxides, and a good resistance to abrasion despite the possible increase in
brittleness, the enamel must have a thermal expansion coefficient compatible with
the one of the metal, which is normally higher.
Since chemical resistance grows as thermal expansion coefficient decreases, acid
resistant silica-rich coatings have very low coefficient and consequently poor
resistance to thermal shock. To minimize the risk of cracking due to thermal shocks,
multilayer enamels are used: the inner one with low expansion coefficient, the
external one with greater resistance to corrosion.
17.3.2 Thick Cementitious Coatings
Due to their alkalinity (pH 13) cementitious mortars applied on carbon steel offer
a perfect protection, as proved by successful long lasting results offered in the last
century by reinforced concrete structures. Cementitious coatings have been used for
internal protection of pipelines for water mains, applied by a centrifugation process,
for submerged marine pipelines, where concrete has also a weighting function, and
for the external protection of oil and gas well casings.
The behaviour of steel embedded in concrete is illustrated in Chap. 23.
17.3.3 Thick Corrosion Resistant Coatings
To resist very high aggressive corrosion conditions, such as those found inside
chemical reactors, thick layers of corrosion resistant materials are used: glassy
materials, cured inorganic silicates, ceramics, sulphur, graphite and carbon, often
applied in the form of tiles or bricks stuck with suitable adhesives. To absorb the
inevitable differential expansion strains, membranes made of resins, asphalt or
synthetic elastomers are often interposed.
Glassy and ceramic materials are resistant in all environments, except in
hydrofluoric and caustic ones. For their use, their properties must be remembered:
insulating, brittle, with poor mechanical strength, and sensitive to thermal shock.
Graphite and carbon are conductive with a good resistance to rapid temperature
changes. Sulphur bricks which stuck each other at temperatures above 120 °C show
good resistance in oxidizing environments and in hydrofluoric acid.
Photocatalytic and Superhydrophilic Properties of Titanium Dioxide.

A photocatalytic reaction is a chemical process occurring on a surface hit by a
radiation because of the presence of a photocatalytic agent. Anatase and rutile
titanium oxides are the best photocatalytic substrates for oxidation or re-
duction of many organic and inorganic substances. Anatase is better than
rutile for degradation of pollutants; yet, both titanium oxides need UV
radiation to activate, therefore they are proposed for the sunlight-activated
degradation of air pollutants or inside UV reactors for water purification.
Other applications deal with the degradation of inorganic compounds,
removal of metal ions from water, photovoltaic cells, antifouling,
self-cleaning and antibacterial surfaces, which have found interesting appli-
cations in civil constructions.
Anatase shows interesting self-cleaning capacity through its photoacti-
vated properties. In detail, anatase is normally slightly hydrophilic as proved
by a drop of water on its surface, which remains stably of semi-spherical
shape. As soon as the surface is irradiated with UV light the drop of water
17.3 Other Inorganic Coatings 345
spreads on the surface because anatase becomes highly hydrophilic, due to

the formation of hydroxyl groups. By this process, the wettability of the
surface increases to allow the formation of a continuous water film instead of
drops, inducing a tiding and antifogging effect.
17.4 Paintings
Paints are heterogeneous systems formed by solids dispersed in a film-forming

component, said binder, whose viscosity is regulated by adding suitable solvents
and thinners, then applied to a metal surface to form in time a solid and adherent
film. This chapter deals with anti-corrosion paints only, then regardless those for-
mulated for other purposes as decoration or signalling.
The use of organic coatings based on oils, greases, waxes and bitumen for
protective aims dates back to antiquity, however, for the protection of steel, prac-
tical applications started in England in the eighteenth century employing linseed oil,
pigmented with red lead oxide. The extension of its use to resist aggressive
chemicals as acids, bases, saline solutions and hot corrosive fumes is more recent;
for example, chlorine-rubber and vinyl paints were introduced in the late 1920s and
epoxy and polyurethane resins only after World War II.
17.4.1 Components
Paints are composed of two parts: a liquid one and a solid one. The former contains
the binder, the solvent and additives as plasticizers and auxiliaries. The latter is a
mixture of pigments and fillers.
Binders. Once based on natural oils and resins, now based on synthetic polymers,
the binder is the constituent of the paintings that gives body to the paint film, whose
filming properties derive primarily from solvent and diluent evaporation—so-called
physical filming—or from chemical reaction, or crosslinking. Some of the
best-known physical filming binders are:
• Vinyl resins: highly used as anti-corrosion paints due to their high chemical
resistance, elasticity and ease of application. They are mostly composed of
copolymers of polyvinyl acetate and polyvinyl chloride. Other polymeric and
carboxylic radicals can be introduced in the polymer chain to improve adhesion
to the metal surface. The chemical resistance of these polymers is excellent in
contact with chemicals, seawater, electrolytes, as well as with industrial and
marine atmospheres
• Chlorinated resins: they are obtained by chlorination of natural or synthetic

polyolephins and polydiolefins, as chloro-caucciu and chlorinated polyethylene
or polypropylene. The presence of a high percentage of chlorine in the molecule
makes these paints less flammable. They are highly resistant to a wide range of
environments, but their brittle character requires the use of plasticizers
• Bitumen (coal tar) and asphalt: the former is obtained as by-product of crude oil
distillation, then having a very variable composition; asphalts are natural
products found in quite big reservoirs. These hydrocarbons dissolved in a sol-
vent give low-cost and thick coatings (0.1–1 mm), largely used for water-
proofing membranes of buried structures.
Crosslinking filming is obtained by a chemical reaction which links polymer
chains to form a three-dimensional structures. Binders of this type are:
• Epoxy resins: their chains contain reactive compounds, hydroxyl and epoxy
groups, which react with a crosslinking agent, for instance a polyamide, to form
highly cross-linked structures with exceptional chemical resistance. When the
crosslinking reaction occurs at room temperature, as when using polyamides in
suitable percentages, the paint is of two-component type; conversely, when
crosslinking occurs at high temperatures, typically with amines or phenolic
resins as curing agents, paints are provided ready to use as a mono-component
system. Epoxy resins are formulated in a wide variety of compositions to obtain
different properties for various applications. The main types are: (1) solvent-free
epoxy resins, neither porous nor subject to shrinkage because the solvent is
eliminated, then also showing the advantage of being less dangerous in terms of
flammability and harmfulness; (2) epoxy systems with solvents, which are the
usual epoxy paints, particularly resistant to highly aggressive marine or indus-
trial atmospheres; (3) modified systems that consist of epoxy resins to which
other resins are added to improve resistance to aggressive environments:
epoxy-tar, with excellent corrosion and chemical resistance; epoxy-vinyl, which
have excellent adhesion to the support and excellent mechanical properties;
epoxy-phenolic, having excellent water resistance; epoxy-silicones, very resis-
tant to high temperatures
• Phenolic resins: offer excellent resistance to aggressive chemicals as diluted
acids and weak alkalis and seawater due to the presence of unreactive bonds.
Their mechanical properties are rather low; besides, they are hard, rigid with low
adhesion property. For this reason they are modified with oleoresins or with
alkyd resins. Curing is obtained in air or in oven
• Polyurethane resins are obtained by reaction of a polyester or a polyether
containing reactive hydroxyl groups, with an isocyanate group-containing
compound which acts as curing agent. The latter is obtained by condensation of
an aromatic poly-isocyanic derivative with a polyfunctional hydroxyl com-
pound: by this way a pre-polymer of poly-isocyanic derivative is obtained,
avoiding harmful effects, as volatility and toxicity. Polyurethane resins are used
to prepare anti-corrosion paints, with excellent resistance to chemicals,
17.4 Paintings 347
industrial atmospheres and abrasion. They are bright glossy and stable to sun-
light exposure, then used as final coats.
For other binders, the curing agent is oxygen, as for example:
• Linseed and similar vegetable oils: although no longer in use, it is interesting to
review their mechanism. The binder consisted of a mixture of glycerol esters
with unsaturated fatty acids. Once applied as a film, these oils polymerize
producing a crosslinking process triggered by atmospheric oxygen. To accel-
erate this curing process, special treatments were used: for example, for linseed
oil a boiling process with addition of oxides or soaps of cobalt, manganese, lead
or zinc, or heating by blowing air or an inert gas
• Alkyds: they are widely used for the reasonable cost, good aesthetic features,
good elasticity and adhesion on non-sandblasted surfaces, good performance in
non-polluted atmospheres; conversely, they are not suitable for aggressive
environments, especially if alkaline. They are high molecular weight polyesters
obtained from reaction of poly-alcohols with fatty acid mixtures. As far as fatty
acids are concerned, there is a wide variety of available substances; the choice
depends on the properties required for the resin. Fatty acids are generally added
in the form of vegetable oils (linseed, coconut, soy oils), which are tri-esters of
glycerol and fatty acids. Alkyd resins are classified based on the percentage of
oil: long oil (55–65% oil), medium oil (45–55%) and short oil (45%) resins.
Depending on the percentage and type of oil, dry and non-drying resins are
obtained. The first, long oil and in some cases also medium oil, are characterized
by the presence of a high percentage of double bonds, which react with atmo-
spheric oxygen, then bridging polymer chains. Non-drying alkyl resins include
most of medium oil and all short oil resins, containing a few number of double
bonds: curing is obtained by increasing the temperature. To improve finishing
aspects, as for cars or household machines, low percentages of amine resins, as
urea, formaldehyde and/or melamine-formaldehyde are added
• Silicone binders: these resins have a –Si–O–Si–O– structure, with some organic
side groups to improve their solubility. Curing takes place by action of atmo-
spheric humidity by a hydrolysis process of poly-silicates, which eliminates
organic groups as volatile compounds. The –O–Si– bond, similar to that in glass
or in quartz, is stable to oxidation processes. For this reason, silicone resins have
excellent resistance to high temperatures (normally up to 250 °C and, if pig-
mented with aluminium, up to about 500 °C). This type of binder is also used
for the preparation of zinc paints, which exhibit excellent resistance to many
near-neutral pH environments.
Solvents and thinners. They are fundamental constituents of paints to facilitate

their application and allow the formation of the film. Usually, they consist of
volatile organic substances, as aliphatic and aromatic hydrocarbons, alcohols,
esters, ketones and, for so-called green formulations, water. The most requested
property is an easy application, to help avoid formation of film defects and drops
and as long as possible to give the polymer the best mechanical properties. Once the
paint film has been applied, solvents and thinners must evaporate rapidly and
thoroughly. To meet all of these requirements, a mixture of components is used,
paying attention to prevent variations of solvent composition during the evaporation
process which can jeopardize the integrity and resistance properties of the film
paint. Solvents and thinners are dangerous to health and flammable; however, fire
hazard disappears after paint drying.
Plasticizers. For crosslinking polymers, paint properties depend on type and
amount of the curing agent; conversely, for thermoplastic polymers film properties
are improved, by modifying the chemical composition of the polymer, by the
addition of plasticizers, consisting of polymers or monomers which interact with
polymer chains to improve their flexibility and consequently film plasticity.
Other constituents. So-called auxiliary and filler constituents are substances that
optimize film performance, such as dryers, suspensive wetting agents, antioxidants
and resin stabilizers.
Pigments and additives. Pigments and additives are solid constituents sparsely
dispersed in the binder. Pigments usually indicate synthetic substances, while
additives derive from natural minerals after grinding, washing and thermal treat-
ments. Additives are selected to resist the chemical action of exposed environments;
for example, for coatings exposed to acidic environments, a low content of car-
bonates is allowed. Pigments are classified as active or inert. Active ones have the
primary function of stopping the anodic or cathodic process, accordingly they are
used for the formulation of primers; conversely, inert pigments aim to reduce the
permeability of the film and improve adhesion properties. Typical inert additives
are metal oxides (titanium oxide, iron oxide, alumina, silica, and zinc oxide) and
some inorganic salts as carbonates and sulphates or complex silicates (mica, talc,
kaolin). Their function is twofold: to improve paint thickness and physical and
mechanical properties such as hardness, abrasion resistance and flexibility, and
furtherly to increase chemical resistance and decrease film permeability. For paints
applied to structures exposed to intense solar action, among other pigment types,
aluminium flakes are used to form a low porosity fish skin-like scale barrier,
enabling to reflect solar radiations and to resist the action of ultraviolet rays as well
as of heat.
To classify the added pigments, a parameter called volumetric concentration of
pigments, VCP, is used which is the pigment-to-dry paint volume ratio. There is a
maximum value, called critical VCP (CVCP), for which paint properties change
drastically once exceeded. A high VCP is required for some paints to facilitate the
absorption of water needed for the migration of active metal ions toward the metal
surface, however, it should not be too high because also aggressive ions such as
sulphates and chlorides may be transported.
Figure 17.8 shows the classification of anti-corrosion paintings on the basis of
VCP-to-CVCP ratio. As this ratio increases, paint protection mechanism switches
from barrier-based to active-type paints (see also Sect. 17.4.3).
17.4 Paintings 349
Increase of VCP/CVCP ratio
Pigment <1.0 >1.0
CVCP
Binder around particles Interstitial binder Voids
Steel
Physical barrier Organic zinc-rich

primer
Inhibitive primer
Inorganic zinc-rich primer
Fig. 17.8 Volumetric fraction of pigment in paint for different classes of anticorrosive coatings
17.4.2 Corrosion Under Paintings
Until World War II, although the anti-corrosive action of some pigments—in
particular red lead oxide—was known, it was opinion that paints acted only as a
physical barrier with the purpose to prevent the penetration of water and oxygen
from an aggressive environment.
For the truth, physical filming paints are never an efficient barrier because water
and oxygen can diffuse through by a quantity higher than the one needed for the
corrosion process of the bare metal, hence the anticorrosive action is more complex
than that of a simple barrier. In practice, only in dry atmospheres the reduction of
water diffusion determines the stop of corrosion processes under paint, while in wet
atmospheres water supply is always in excess. Instead, oxygen diffusion can
become the controlling stage for high thickness paints.
Besides by water and oxygen diffusion, corrosion rate is also controlled by the
electrical resistance of the paint, the so-called ohmic control, which is effective if
paint conductivity is low. This parameter depends first of all on the amount of water
absorbed by the paint, which in turn depends on the chemical-physical properties of
paint binders and pigments; for example, bituminous-based paints have little ten-
dency to absorb water. In addition, also the salt content of the exposed solution
determines paint conductivity.
When ionic groups form in the binder as a result of hydrolysis caused by the
absorbed water, the paint may become an anionic or cationic semipermeable
membrane, then selective for ion migration (positive or negative). This behaviour
setups in many paints a saline concentration gradient, which determines a beneficial
effect when the ionic concentration decreases toward inner layers; the presence on
the metal surface of corrosion products or oxides not removed before painting,
which retain moisture, vanishes that beneficial effect.
17.4.3 Protective Action of Paints
The protective action of paints follows two mechanisms:

• Barrier effect: which reduces oxygen and water diffusion
• Active effect: when specific pigments, adsorbed onto the metal surface, exert an
active protective action by changing the electrochemical condition (promoting
passivity or increasing overvoltage or setting up cathodic protection conditions).
The barrier effect is adopted when exposure electrolytes, as acids, bases or saline
solutions, react with active pigments, making their use unsuitable. For atmo-
spherically exposed components, active based paints are preferred; however, usual
painting cycles, composed of different coats, take advantage of both mechanisms.
Barrier effect. An efficient barrier effect is obtained by acting on composition,
chemical-physical characteristics of components and thickness. The first action
deals with the molecular structure of the binder, which must ensure a dense film as
obtained by thermosetting polymers with a high degree of crosslinking or partially
crystalline thermoplastic ones; both these polymers are hydrophobic and have a
strong resistance to diffusion of water, oxygen and ions. Among thermoplastic
binders, high molecular weight polymers, such as fluoropolymers and
polyvinyl-chloride, are particularly attractive; as regards thermosetting polymers,
epoxy, urethane, polyester and vinyl esters are used. Water absorption and oxygen
permeability are also influenced by the nature, shape, content and size of pigments
such as mica or aluminium of flake-shape type. Other influencing parameters are the
composition and quantity of solvents and the method of application in combination
with the filming process. In general, it is known that the lower the amount of
solvent used, the lower the permeability of paint films. In addition, some solvent
may remain trapped even in small quantities in the hardened film, then favouring
water absorption.
Thickness. The barrier effect increases with thickness: in practice, to reduce paint
permeability enough to withstand aggressive environments, a minimum thickness
of 200–300 lm is necessary. Ordinary paints reach a maximum film thickness of
30–35 lm per coat because of the filming process, which is triggered by atmo-
spheric oxygen, starts from the outer surface and proceeds inward hardly;
accordingly, higher thicknesses require multiple coats. Conversely, thermosetting
paints develop a fully hardened film regardless the thickness, allowing the appli-
cation of a single high thickness coat. Thickness homogeneity on the entire metal
surface is of great importance in determining the barrier effectiveness. Many causes
affect local film thickness variations: first of all the substrate roughness profile,
17.4 Paintings 351
which depends on surface preparation (for example, sandblasting may offer a peak
type profile instead of a rounded one). With rough profiles, small quantities of paint
produce uneven films. Secondly, the design complexity of the structure to be
painted due to the presence of cracks, sharp edges, recesses. Typical defects are in
these cases: brush strokes, crinkles, orange skin, spraying fumes, glides on vertical
surfaces or micro slit with peak emersion.
Non-stick coatings. A further improvement to coatings with barrier effect is to
produce a non-stick surface, i.e., coating the metal with a polymers with very low
surface free energy. This involves the use of fluorinated polyols as precursors,
which can be applied either directly to the metal surface or as topcoat of urethane or
epoxy primers, and then cured to obtain a fluoropolymer, whose fluorinated groups
demonstrate the non-stick function. Such coatings are particularly appreciated in
industrial, marine and automotive applications where having a clean surface is a
primary requirement, for instance to prevent soiling or fouling which may com-
promise the functionality of components.
Paints with active primers: cathodic protection mechanism. The most impor-
tant cathodic pigment for steel protection is zinc. Relevant primers, called zinc rich
primers, consist of zinc powder with particle size between 3 and 20 lm. To give
cathodic protection effect, the zinc content should exceed 90% by weight to ensure
an efficient electrical connection between zinc grains and steel (Fig. 17.9).
Attempts to use aluminium or magnesium dust instead of zinc failed because
these metals do not give electrical continuity, being the oxide which covers each
particle an insulator: manganese would show a similar behaviour as zinc, but for
economic reasons it has found little application.
Two types of zinc rich primers are used:
• Organic zinc-rich primers: the binder is typically based on epoxy, urethane,
styrene or chloro-caucciu polymers, as many other paints; the zinc powder
content is as minimum 85% by weight in dry film. A thin paint layer covers each
zinc particle for a twofold function: sticking particles to each other and to the
Conduction at the zinc Conduction trough

particle interface zinc particle
Zinc
primer
Steel
Conduction at zinc-metal
particle interface Conduction in the metal
Fig. 17.9 Electric conduction in an organic zinc paint

steel surface, and ensuring electrical continuity, which requires it to be very thin
(Fig. 17.9)
• Inorganic zinc-rich primers: zinc content is up to 95% by weight. The binder is
an inorganic silicate that forms a hard conductive film, more adherent and
porous than the polymeric binder. These inorganic zinc rich primers provide a
higher protection than organic ones, but require a more stringent surface
preparation.
These primers provide a protection degree comparable to galvanizing and, unlike
other paints, they do not suffer from filiform or under paint corrosion starting from
gaps or scratches. Protection conditions continue also after corrosion of zinc par-
ticles, although the electrochemical action fades, because zinc corrosion products,
as hydroxides and carbonates, seal the pores giving an efficient barrier effect (see
also Sect. 17.1).
Paints with active primers: inhibition mechanism. The aim of these pigments is
the formation or the strengthening of a passivating protective film on the metal
surface, according to the mechanisms of passivating inhibitors, through the estab-
lishment of alkaline environment or by passivating mechanism (see Sect. 17.2.3).
Others, as silicates and phosphates, form a barrier film on the metal surface.
Chromates, which are excellent passivating inhibitors, have been banned because
carcinogenic; before that, also red lead was prohibited because of its toxicity,
causing saturnism.
Self-healing coatings. Self-healing coatings can be included among coatings with
an active function. Mechanisms of protection vary from the above described pas-
sivating effect, by inhibition or cathodic protection, to the actual sealing of defects
and holes that may form in the coating by a shape recovery effect, or by the release
of swelling compounds or of chemically reactive molecules that react with the
matrix, sealing it. The active components are generally encapsulated, so that they
exert the sealing or inhibiting action only in presence of a stimulus—be it
mechanical, thermal, or a pH variation—in order to reduce risks of deactivation or
leaching, which is why they are also referred to as smart coatings.
Although the matrix incorporating the active component is generally organic,
mostly epoxy, in some cases oxide matrices (e.g., SiO2, ZrO2, TiO2) are used,
applied either by sol-gel or by chemical vapour deposition. As active principles,
chromium compounds were initially used, being the formation of chromium oxide
the mechanism of self-repair. Due to the restrictions on the use of Cr(VI), other
systems were then investigated, and currently span from natural oils (for instance,
linseed oil or tung oil) to synthetic organic or inorganic compounds (e.g., alkyl
ammonium salts, alkoxysilanes, mercaptobenzothiazole, hydroquinone, MoO4 2 ,
Ce3+).
Few commercial products are currently available, with current applications in
industrial and marine sectors, especially as above water heavy duty corrosion
protection technique; field tests indicated a threefold up to six-fold coating lifetime
extension.
17.4 Paintings 353
17.4.4 Paint Film Properties
A painting can last for the entire design life exploiting either the barrier effect or the
inhibition mechanism, provided that the film can show:
• A good chemical resistance to withstand environmental exposure conditions
• A good adherence to the metal surface, to avoid either spontaneous or
mechanically caused macro defects as peeling off, to ensure total protection. In
the case of poor adherence, under paint corrosion attack occurs starting from
micro defects as pinholes
• A mechanical hardness to withstand hits, abrasion and erosion, and elasticity as
well as flexibility to avoid cracking when stressed
• Suitable rheological properties, as per nature and composition of the film, in
particular binder, solvent and curing components, which influence the appli-
cation method (brush, spray or immersion) and the filming process. A paint is
thixotropic when it shows the ability to change viscosity while stirred, being
then suitable for brush or spray applications because once spread it becomes
viscous, hence avoiding dripping.
The above requirements are often in conflict; for example, thermoplastic poly-
mers should have high molecular weight to resist mechanical impact but the ease of
application worsens.
17.4.5 Painting Cycles
One single paint coat can hardly show all required features, hence the so-called
painting cycle, composed of multiple coats, is used. A painting cycle consists
basically of:
• A primer or first coat in contact with the metal surface
• An intermediate coat
• A final or finishing coat, directly in contact with the environment.
The cycle is called homogeneous when there is only one binder, conversely it is
called heterogeneous. The primer has a twofold aim: to stick to the metal surface
and provide the active pigment. The finishing coat must resist the environmental
aggressiveness. The intermediate coat has the purpose to thicken the paint and
reduce permeability while using less expensive components than primer and fin-
ishing coats.
Figure 17.10 shows the effect of a wrong painting cycle where no primer was
used.
Primer. The primer, as first coat, must ensure the maximum adherence to the metal
surface. Adherence mechanism can be a simple mechanical anchoring enhanced by
the roughness of the metal surface, generally obtained by sandblasting, and in
Fig. 17.10 Corrosion under painting of a gate in Venice due to the absence of the primer
addition chemical-physical interactions between the binder and the metal. Adhesion
properties refer to the binder wetting capability, which varies greatly with type of
binder and relevant modifications; for example, for chloride-acetate type vinyl
resins, the insertion of a few hydroxyl or carboxylic groups greatly improves
wetting, while for pure vinyl chloride acetate copolymers wetting is very low.
Adhesion is modified by the presence of pigments, fillers, plasticizers and additives.
It also depends on the nature of the metal: for example, it can be entirely different
for carbon steel and galvanized steel, often worse for the latter. Adherence is
strongly influenced by the cleanness of the metal surface to an extent that depends
on the type of binder. For instance, an oleo-phenolic binder does not require a
particularly accurate cleaning, unlike an epoxy based binder that requires a white
sandblasted metal surface. For a primer, adhesion is more important than chemical
resistance or appearance, which may be opaque; conversely, the feasibility of the
over coating application is important. In this regard, the opaque appearance is
generally associated with poor binder content in the paint that facilitates the
adhesion of the subsequent coat, which is always problematic in the case of ther-
mosetting binders. It is worth mentioning the so-called shop-primers, for example
based on epoxy-phenols, used in factory for a temporary protection of maximum
1 year, before final assembling. Of course, shop-primers must be easily coated with
the widest spectrum of paintings to avoid restriction in the selection of intermediate
and finishing coats.
Finishing coat. Aesthetic aspects are of primary importance for the formulation of
the finishing coat, hence chemical resistance comes first rather than adherence. Inert
binders and chemically resistant pigments with a high volumetric concentration are
privileged to obtain maximum waterproofness. This leads to a film with glossy or
semi-glossy appearance. For example, in contact with aggressive chemical envi-
ronments, vinyl epoxy, chloro-caucciu or polyurethane resins should be chosen.
17.4 Paintings 355
Instead, alkyd resins, oleo-resinous binders, and generally all binders containing
reactive ester groups or reactive pigments have to be avoided. Sometimes, finishing
coats may require special features besides those of chemical resistance and, of
course, in addition to aesthetic ones. For example, in moderate polluted atmo-
spheres aluminium containing binders are used, which also give protection against
solar and ultraviolet rays as well as effective protection against heat (for example,
they are used for coastal tanks of petroleum products). For the same reasons, a
urethane finishing is used on epoxy cycles. For marine structures such as ship hulls,
the finishing coat must also have anti-fouling properties to prevent or limit marine
fouling growth. Fillers used for this aim are: copper oxide or organometallic
compounds containing arsenic, lead or zinc.
Intermediate coat. The aim of the intermediate coat is to give thickness and to
increase waterproofness of the cycle. Provided a good compatibility and proper
adhesion with primer and finishing coats, cost-effective materials are generally
used.
17.4.6 Pre-treatments
Before painting or performing any other surface treatment as metal deposition, the
surface must be accurately cleaned by removing oxides, corrosion products, fat, oil
and dirt of various origin and nature, and subjected to a further roughening to
increase adhesion.
Such treatments vary with type of metal as well as nature of paints. For example,
an alkyd linseed oil paint requires much less accurate treatment than epoxy or
urethane based ones; an inorganic zinc-rich primer requires higher surface prepa-
ration than an organic zinc-rich primer. Similarly, surface treatment in galvanic
deposition is different whether the solution is acidic or alkaline: the latter tolerates
higher amount of adsorbed organic substances than acidic ones.
The choice of a suitable pre-treatment depends on a variety of parameters. In
general, reference is made to international agreed standards promoted by recognized
organizations, such as in USA the SSPC (Society for Protective Coatings, formerly
the Steel Structures Painting Council) with its “Surface Preparation Specifications”;
in Europe, CEN-ISO and the Swedish Standard Association, which reports widely
used photographic standards as a practical guide.
Degreasing with solvents and detergents. The aim of this practice is cleaning
from fats, oils, dirt, especially animal fat, by means of solvents, emulsions or
detergents. To remove dust particles that remain stuck on the metal surface even
after degreasing a mechanical action is necessary, as produced by impingement
made by liquids or gas bubbles in electrochemical treatments or by ultrasounds.
Degreasing agents are classified as: organic solvents, emulsions, biphasic detergents
and alkaline detergents.
Pickling. It consists of dipping the metal in strong inorganic acids to remove

oxides that form on the surface during manufacturing at high temperature or by a
corrosion attack. This surface treatment is quite ideal for the application of coatings.
Common acids used for treating steels are: sulphuric, hydrochloric, phosphoric,
nitric, hydrofluoric or a mixture of them at a temperature higher than the ambient
one. The most suitable acid as well as the concentration recommended for the
treatment depend on steel composition and nature of oxide. It is good practice to
add proper corrosion inhibitors to reduce metal wastage during the treatment as well
as hydrogen evolution, then reducing risks of hydrogen embrittlement and
entrainment of acid in vapours (so-called acidic fumes). Pickling is followed by
rinsing in neutralizing solutions and drying. For hot laminated carbon and low alloy
steels sulphuric acid, as solutions of 1–50%, is used; also the more reactive
hydrochloric acid is used—at room temperature, for being volatile. For titanium and
stainless steels, a mixture of nitric and hydrofluoric acids is used. It is worth
remembering that pickling requires treatment of exhaust solutions before sewage
disposal and precautions for health.
Pickling of hot rolled steels. After hot rolling, steels are covered by an oxide
scale, the rolled scale, also called calamine. If rolling has been carried out at a
temperature above 575 °C, the scale consists of three layers:
• Internal layer in contact with the base metal, made of wüstite, FeO
• Intermediate layer consisting of magnetite, Fe3O4
• External layer, of hematite, Fe2O3.
The ease of pickling relies primarily on the inner layer composition and on the
porosity of the outer layers. Both composition and porosity depend essentially on
the transformations of oxides occurring during cooling below 575 °C: a rapid
cooling does not affect the wüstite layer and pickling becomes more difficult;
similarly, pickling is also difficult when the scale forms at temperatures below 575 °
C because no wüstite forms.
Conversely, a slow cooling from 575 °C partially decomposes wüstite into
magnetite and metallic iron dust, so that pickling is favoured because acid pene-
trates through the pores and easily detaches wüstite, also thanks to the development
of hydrogen produced by the corrosion of iron dust (Fig. 17.11).
Fig. 17.11 Illustration of

pickling action on carbon
steel sheets, laminated at high Acidic solution H2 evolution
temperature (>575 °C), and
then cooled slowly Fe2O3 Fe2O3
Fe3O4
Fe FeO H+ H+ FeO Fe3O4
Fe3O4 H+ Fe
Steel
17.4 Paintings 357
Sandblasting. Sandblasting is the best technique for preparing steel surfaces. It

consists of spraying at a high-speed abrasive powder onto the metal surface, then
removing hot rolled scale and rust until obtaining a so-called white metal surface.
Silica sand, whether natural or obtained by grinding, is now generally discarded as
grinding medium as it causes silicosis, and replaced with other abrasives as
corundum, cast iron and steel granules, whose use is restricted to continuous cycle
production plants, being very expensive. It is still preferred if old paints of very
high hardness have to be removed from the surface and if steel, just released from
production, is completely or nearly coated with very adherent rolling scales.
Sandblasting can be performed dry or wet; in the latter, abrasive particles are
dispersed in a water stream containing a corrosion inhibitor. Dry sandblasting is
normally preferred due to the shorter working time and because the steel surface
remains dry, then allowing a long storage time before further painting.
The degree of blasting (not to be confused with the sandblasting profile that
indicates surface roughness) defines the percentage of removed scales, rust and old
paint. In current practice, the following sandblasting grades are defined, according
to ISO 8504:
• White metal (grade SA 3)
• Almost white metal (grade SA 2½)
• Commercial (grade SA 1)
• Brushing or coarse sandblasting.
17.4.7 Paint Application
The good performance of a painting depends on:

• Appropriate painting cycle to withstand the aggressive environment
• Proper surface preparation
• Correct application.
To select proper painting cycles, including surface preparation, reference is made to
specialized literature and standards. Excluding the description of application sys-
tems (brushing, rolling, spraying, with or without air, electrostatic, by immersion,
by electrophoresis) for which reference is made to specialized handbooks, in the
following, only the atmospheric and environmental conditions for the correct
application are considered.
Abnormal conditions of temperature and relative humidity or the presence of
wind must be avoided. As far as temperature is concerned, too low temperatures
(less than 7–10 °C) or an excessive cooling due to rapid solvent evaporation would
jeopardize the final result because curing stops or is altered, and once temperature
drops below the dew point, water condensation forms.
Also high temperatures (above 35 °C) of both ambient and metal surface are
harmful. In this case solvent evaporation is too fast, hence increasing porosity and
contrasting paint relaxation. Moreover, the higher the temperature, the lower the
pot-life time, or the maximum the time from the mixing of components. Painting
work should not be carried out when relative humidity exceeds 85%, and on rainy
days. This depends on the fact that non-polymerized binders tend to absorb water
physically or chemically, resulting in decreased adhesion and chemical resistance.
About the application time schedule, it is essential that the primer is applied
immediately after surface preparation, in particular after sandblasting, in order to
prevent the oxidation of the metallic surface that is very reactive after sandblasting,
which would compromise adhesion and the effectiveness of the paint. Also the
elapsed time between the applications of successive coats is limited. It is a stringent
requirement for two-component paints to avoid lack of adhesion, and less rigid for
solvent-based paints, although also in this case it should not be too long to avoid
total dryness and surface contamination by dust.
17.4.8 Painting Maintenance
To ensure the design life of a paint, preventative maintenance work, consisting of

periodical retouching or partial overlays, at a frequency determined on a cost
effective and exposure conditions basis, as well as programmed inspections are
necessary and usually planned. These interventions, which represent the cheapest
way to extend the painting life, require special attention for ensuring good adhesion
between old and new coats. For paints of thermoplastic binder type, since they are
soluble in solvents, maintenance work is possible at any time; conversely, with
thermosetting paints adhesion between old and new coat is difficult and always
poor, especially when crosslinking is tight, since any solvent is ineffective. In these
cases, it is necessary to completely remove old paint and corrosion products before
applying the new paint.
17.4.9 Threats at the Workplace
As final paragraph of this chapter, a mention of health threats for personnel

involved in all painting-related activities, from production plants to field applica-
tions, is mandatory. In short, risks deal with:
• Surface preparation by sandblasting because of the presence of dust (risk of
silicosis with siliceous sand), noise and vibrations
• Degreasing operation with risk of inhalation of solvent vapours (in particular for
chlorine containing and aromatic compounds)
• Chemical and electrochemical treatments, risk associated to handling of acids,
bases or poisoning solutions (for example cyanide) and exposure to poisoning
metal ions (lead, zinc and chromate)
17.4 Paintings 359
• Metal hot dipping, risk of inhalation of metallic vapours

• Painting application for risk of inhalation or contact with solvents, pigments,
dusty charges, toxic curing agents.
• ASTM D62, Standard Test Methods for Holiday Detection in Pipeline Coatings
—West Conshohocken, Pa.: American Society for testing of Materials
• ASTM D714, Standard Test Method for Evaluating Degree of Blistering of
Paints, West Conshohocken, Pa.: American Society for testing of Materials
• ASTM D1653, Standard Test Methods for Water Vapor Transmission of
Organic Coating Films—West Conshohocken, Pa.: American Society for testing
of Materials
• ASTM D3359, Standard Test Methods for Rating Adhesion by Tape Test—
West Conshohocken, Pa.: American Society for testing of Materials
• ASTM D4541, Standard Test Method for Pull-Off Strength of Coatings Using
Portable Adhesion Testers—West Conshohocken, Pa.: American Society for
testing of Materials
• ASTM D5162, Standard Test Method for Discontinuity (Holiday) Testing of
Nonconductive Protective Coating on Metallic Substrates—West
Conshohocken, Pa.: American Society for testing of Materials
• ASTM F941, Standard Practise for Inspection of Marine Surface Preparation
and Coating Application—West Conshohocken, Pa.: American Society for
testing of Materials
• ISO 8504, Preparation of steel substrates before application of paints and related
products. Surface preparation methods, International Organization for
Standardization, CH-1211 Geneva 20
• ISO 10309, Metallic coatings—Porosity tests—Ferroxyl test, International
Organization for Standardization, CH-1211 Geneva 20
• ISO 21809, Petroleum and natural gas industries—External coatings for buried
or submerged pipelines used in pipeline transportation systems, International
Metallic coatings
17:1 Grounding systems are typically made of: bare copper, galvanized steel and
copper-coated steel. Illustrate (suggest) the process for obtaining galvanized
and copper-coated earthing rods. Explain the advantages or drawbacks of

these goods compared to the solid copper rods.
17:2 Explain the advantages of chromating the galvanized steel as finishing or
surface preparation for further painting.
17:3 Al-Zn coatings obtained by hot spraying are used, also on submerged sur-
faces, as bare. Discuss why and give a reason for being a bad active primer.
Conversion coatings
17:4 Explain why anodizing of titanium cannot be adopted as surface preparation
for painting.
17:5 Phosphatizing is sometime used as surface preparation for painting. Explain
why it is used for indoor application and not recommended for marine
applications.
17:6 Anodized aluminium if often painted. Discuss about the surface preparation
needed.
Painting
17:7 Calculate the water and oxygen diffusion rate through a paint film if cor-
rosion rate is the same as in atmospherically exposed bare metals. These
values represent the threshold for which the barrier effect becomes benefi-
cial. Assuming that the minimum paint thickness for reaching the threshold
value calculated above is 100 lm, and the dependence with the paint
thickness is parabolic, suggest a thickness for a solvent based paint for an
effective barrier effect.
17:8 Based on the results of exercise 17.1, predict the minimum thickness of an
epoxy-based paint if water and oxygen diffusion rates for a paint thickness
of 100 lm is 10 and 30 mg/m2 d, respectively.
17:9 Explain which is the mechanism by which red lead oxide and zinc chromate
would work. Try to compare the two mechanisms by a representation on the
Evans diagram. Estimate the minimum primer thickness required for a
duration of 10 y, assuming that VCP is unitary.
. Explain the mechanism by which zinc-rich primers work. Show the dif-
ference with a primer based on phosphatizing treatment.
17:11 Try to estimate the consumption rate of a primer based on an inorganic
zinc-rich and a hydroxyl zinc chromate.
17:12 Give all justifications you find reasonable on why the adopted painting
cycle world-wide used for offshore structures, either atmospherically or
submerged, typically consists on: sandblasting, inorganic zinc-rich primer,
epoxy based for the intermediate coat and polyurethane for the final one.
17:13 An acid pickling treatment is carried out at about 60 °C in 20% sulphuric
acid solution. Suggest the maximum dipping time if no corrosion inhibitor
is added.
17:14 With reference to the previous exercise, suggest an inhibitor for the acid
pickling treatment and the associated dipping time.
17:15 The Golden Gate Bridge is continuously maintained, with a period of about
two years (that is the time required for the team involved to run from one
side to the opposite). Suggest a painting cycle and the nature of the most
suitable binder taking into account the environment.
17:16 Explain the difference between a painting cycle for a galvanized steel and
the one for anodized aluminium. Explain the influence of the total coating
thickness.
Bibliography
Munger CG (2014) Corrosion prevention by protective coatings, 3rd edn. NACE International,
Huston
Parkinson R (2001) Properties and applications of electroless nickel. Nickel Development Institute
Roberge P (2008) Protective coatings, corrosion engineering—principles and practice. McGraw
Hill, New York, pp 587–662
Stankiewicz A, Barker MB (2016) Development of self-healing coatings for corrosion protection
on metallic structures. Smart Mater Struct 25:084013
Chapter 18
Environmental Control
Boil the amurca down to one-half of its volume and use

it as a polish for any kind of copper vessel, […],
Each object will have a lustre and will be protected from rust.
Catone, De agri cult., 98, 108, 99
Abstract An effective and widely used corrosion prevention method is obtained

through a modification, often called conditioning, of the aggressive environment. The
rationale of the approach is to influence cathodic or anodic processes or both, in order
to decrease the corrosion rate below an acceptable limit to meet the design require-
ment about design life and safety. The main actions, illustrated in the following, are
based on the modification of pH, the reduction of oxygen content to slow down the
cathodic process, the use of biocides to control microbiological activity, or on the
injection of specific chemicals, as scaling agents and corrosion inhibitors, to slow
down both anodic and cathodic processes. In particular, for corrosion inhibitors, the
mechanism (anodic, cathodic, mixed) is described and the effectiveness is discussed.

https://doi.org/10.1007/978-3-319-97625-9_18
364 18 Environmental Control
18.1 pH Control
To inhibit the hydrogen evolution as main cathodic process in slightly acidic

solutions, as industrial waters, the pH is increased. This pH modification is also
beneficial on the anodic process of many metals as a high pH favours passivation.
More common pH corrections are:
• Alkalization of boiler water to annihilate the hydrogen evolution and induce the
formation of a magnetite film on carbon steel
• pH variations to promote scaling in waters
• Addition of alkaline substances to avoid acidic condensates.
The latter treatment refers to the conditioning of steam for the presence of acidic
substances such as CO2 and HCl, which are harmless in dry steam while give very
aggressive conditions in condensates. Addition of neutralizing agents, such as
ammonia or amines by direct injection in the steam, is adopted for example, in
distillation columns of crude oil.
In waters, injection of NaOH, ammonia based salts or amines is adopted.
18.2 Oxygen Control
The presence of oxygen is the main cause of corrosion in waters and natural
environments (Fig. 18.1). In particular, the corrosion rate is proportional to the
amount of oxygen dissolved (see Chap. 8); accordingly, an easy and effective
corrosion control is the oxygen removal regardless the need to establish passive
conditions.
Two methods are adopted for oxygen removal:
• Physical
• Chemical.
The principle of the first method is based on the temperature and pressure
dependence of oxygen solubility: as the temperature increases or pressure decreases,
oxygen solubility zeros. Therefore, oxygen is almost totally removed by heating up
the water close to boiling temperature or in vacuum columns, or even by gas strip-
ping. Typically, a physical treatment reduces the oxygen content to less than 1 ppm.
A residual oxygen content as low as 0.015 ppm, as required for feeding water of
low or medium pressure boilers, can be achieved in industrial plants only com-
bining the physical method with a chemical process.
Chemicals most frequently used for oxygen removal are sodium bi-sulphite and
amines (hydrazine, hydroxylamine) according to the following reactions:
2Na2 HSO3 þ O2 ! 2Na2 SO4 þ 2H þ ð18:1Þ

18.2 Oxygen Control 365
N2 H4 þ O2 ! 2H2 O þ N2 ð18:2Þ
Sodium bi-sulphate is effective up to 60 °C, while hydrazine only reacts sensibly

with oxygen at temperatures above 140 °C. Compared to sodium sulphate,
hydrazine has the advantage of not increasing either the acidity or the salinity.
In the case of Na2HSO3, attention should be paid to the scavenger dosage; as a
rule of thumb, for each ppm of oxygen about 8 ppm of sodium bi-sulphite should
be added. A higher dosage will reduce the pH of the solution, making the elec-
trolyte more acidic.
On the other hand, hydrazine can partially decompose to give ammonia, which
increases alkalinity, then facilitating the formation of the protective magnetite film:
N2 H4 ! 4NH3 þ N2 ð18:3Þ
The mechanism involving hydrazine as passivating agent is effective if its con-

centration exceed 100 ppm. Due to toxicity problems, hydrazine is partially
replaced by less toxic compounds such as hydroxylamine.
18.3 Corrosion Inhibitors
Corrosion inhibitors are substances added in small quantities to the aggressive

environments in order to slow down and practically zero the corrosion rate without
changing the environment composition. There is a variety of substances having
these characteristics.
A corrosion inhibitor can work in various ways: through the modification of the
metal surface as a result of a physical adsorption or a chemical interaction, by
increasing the overvoltage of cathodic or anodic reactions, by preventing oxygen
from reaching on the metal surface, and by favouring passivation conditions.
An inhibitor must be compatible with the environment where it is injected.
Characteristics such as pH, the nature of the metal, dissolved ions, temperature, the
presence of microorganism, aeration and flowing conditions can affect the perfor-
mance of a candidate corrosion inhibitor. In particular, pH plays an important role
because it influences the anodic and cathodic reaction. If pH enables passivation,
the inhibitor helps strengthen the oxide existing film. Conversely, when an oxide
film cannot form, the inhibitor builds a protective film by adsorption at the surface.
Inhibitors for acidic environments are generally not effective in neutral or alkaline
solutions, and vice versa. The electrical charge, present on the metal surface and the
nature of the inhibitor are also important factors as they control the adsorption of
the inhibitor onto the metal.
The use of inhibitors, although this constitutes an excellent and tested method to
prevent corrosion, can exhibit considerable side effects such as fluid contamination,
environmental pollution and damage to subsidiary parts. For example, some inhi-
bitors, injected to protect a part of a plant can be aggressive to others.
Table 18.1 presents some inhibitors that have been used with success in typical
environments, and Table 18.2 summarizes most common inhibitors used for the
corrosion protection of some metals.
Table 18.1 Typical inhibitors used in industry

Environment Inhibitor Metal Dosage
Waters Drinking water Polyphosphate Fe, Zn, 5–10 ppm
Cu, Al
Silicate Fe 10–20 ppm
Ca(OH)2 Fe, Zn, 10 ppm
Cu
Cooling Ca(HCO3)2 Fe 10 ppm
System Chromates Fe, Zn, 0.1%
Cu
NaNO2 Fe 300–500 ppm
Polyphosphates Fe 10–20 ppm
Silicates Fe 20–40 ppm
Boiler NaH2PO4 Fe, Zn, 10 ppm
Cu
Polyphosphates Fe 10 ppm
Engine cooling Na2CrO4 Fe, Pb, 0.1–1.0%
circuit Cu, Zn
Nitrites Fe 300–500 ppm
Brine and Na2SiO3 Fe 0.01%
seawater Zn 10 ppm
Amines quaternaries Fe 10–25 ppm
NaNO2 Fe 0.5–3%
NaNO2 + NaH2PO4 Fe 0.5% + 10 ppm
Pickling Sulphuric acid Phenylthiourea Fe 0.003–0.01%
solution Orthotoluenthiourea
Mercaptans
Sulphides
Hydrochloric Organic compounds with N Fe 100–200 ppm
acid and N rings
Hexamethylenetetramine Fe 5%
Nitric acid Amine, thiourea Fe
Aromatic amines Cu
Petroleum Extraction Various amines Fe 100–500 ppm
industry Refining Imidazoline and derivatives Fe 100–1000 ppm
Concrete Marine CaNO2 Fe 10 kg/L
De-icing salts Amines Fe 1% versus
Alkanol-amines cement weight
Carboxylate salts
18.3 Corrosion Inhibitors 367
Table 18.2 Typical corrosion inhibitors for metals in different environments

Metal Environment Inhibitor
Carbon steel Citric acid Cadmium salts
H2SO4 diluted Aromatic amines
H3PO4 concentrated Dodecyl-amine 0.01–0.5%
Brine containing oxygen Methyl, ethyl or propyl-dithiocarbamates
0.001–3%
Mixtures glycol Tri-sodium phosphate 0.025%
ethylene-water Phosphates or alkaline borates
NaCl 0.5%—neutral pH Sodium nitrite 0.2%
Brine containing Formaldehyde
sulphides
Water Benzoic acid, polyphosphate, silicate
Hydrocarbons and water Sodium nitrite
Concrete Calcium nitrite
Amines or carboxylates
Aluminium HCl 1N Phenilacridina, Naphthoquinone, Acridine,
Thiourea
HNO3 10% Hexamethylenetetramine 0.1%
H3PO4 20% Sodium chromate 0.5%
H2SO4 concentrated Sodium chromate 5%
Chlorinated water Sodium silicate
Seawater Amyl stearate 0.3%
Na2CO3 1% Sodium silicate 0.2%
Na2S Sodium metasilicate 1%
Mixtures glycol Nitrite or molybdate of sodium
ethylene-water
Chlorinated aromatic Nitroclorobenzene 0.1–2%
Commercial ethanol Carbonates, Lactates, Acetates or alkaline
borates
Cadmium (on Mixtures glycol Fluophosphate sodium 1%
steel) ethylene-water
Magnesium Alcohols Alkali sulphides
Tri-chloro-ethylene Formamide 0.05%
Water Potassium dichromate 1%
Lead Neutral solutions Sodium benzoate
Copper and brass H2SO4 diluted Benzilthiocianate
Mixtures glycol Borates or alkaline phosphates
ethylene-water Mercaptobenzothiazole
Benzotriazole
Neutral solutions Mercaptobenzothiazole
Benzotriazole 0.2–0.3%
(continued)

Metal Environment Inhibitor
Tin (steel) Alkaline soaps Sodium nitrite 0.1%
NaCl 0.05% Sodium nitrite 0.2%
Titanium HCl Oxidizing Agents
H2SO4 Oxidizing Agents
Zinc (galvanized Water Calcium and zinc metaphosphates 15 ppm
steel)
The main use of inhibitors deals with:

• Neutral or lightly alkaline waters and solutions with a pH between 5 and 9
• Acidic environments such as in pickling processes, chemical cleaning and
descaling
• Hydrocarbon production and refining
• Concrete that is expected to be contaminated by chlorides.
18.3.1 Classification of Inhibitors
The usual inhibitors are classified based on:

• The chemical nature: organic or inorganic inhibitors
• The electrochemical mechanism: anodic, cathodic or mixed inhibitors
• The application: inhibitors for feeding water of boiler, for pickling, for
descaling, for packaging, for concrete, for hydrocarbons, for chloride containing
environments and others
• The effectiveness, which can always be beneficial (safe inhibitors), or detri-
mental where the corrosion rate sometimes increases (unsafe or hazardous
inhibitors) because of an insufficient dosage.
Hereinafter, inhibitors will be classified according to their electrochemical mech-
anism as summarized in Fig. 18.2 by distinguishing among cathodic, anodic (ox-
idizing or non-oxidizing) and mixed inhibitors:
• Cathodic inhibitors increase cathodic overvoltage and thus lowering the corro-
sion potential (Fig. 18.2a)
• Anodic inhibitors, instead, increase anodic overvoltage and therefore an enno-
blement of corrosion potential is expected (Fig. 18.2b)
• Mixed inhibitors, which act on both anodic and cathodic processes, can give rise
to a slight change of potential (Fig. 18.2c).
(a) (b) (c)

E E E
2 Inhibitor Inhibitor
Ecorr,1
Ecorr,1 1 Ecorr,1 2
Ecorr,2 Ecorr,2 1 Ecorr,2 1
2 Inhibitor Inhibitor
icorr,2 icorr,1 log i icorr,2 icorr,1 icorr,2 icorr,1

log i log i
Fig. 18.2 Electrochemical mechanism of inhibition: a Cathodic; b anodic; c mixed. Point 1:

Operating point without inhibitor. Point 2: Operating point in the presence of an inhibitor
In all cases, inhibitors cause a reduction of the corrosion rate from icorr,1 to icorr,2
(Fig. 18.2).
18.3.2 Cathodic Inhibitors
Acidic solutions. When cathodic reaction is hydrogen evolution, inhibitors are

those substances that increase the cathodic overvoltage. Typical substances are
some inorganic compounds, as salts of arsenic, antimony, bismuth, sulphuric or
hydrogen halide ions, and many organic substances. The latter sometimes can also
act also on the anodic process. When cathodic inhibitors stop the recombination of
atomic hydrogen, the risk of hydrogen embrittlement increases on high-strength
steels (see Chap. 14).
Neutral or slightly alkaline solutions. Effective inhibitors for these environ-
ments include deoxidizing substances, pH correctors and substances that give rise
to the formation of hydroxides or scaling on a metal surface, such as for instance
salts of zinc, magnesium, manganese, nickel and calcium that give hydroxides or
carbonates, which start forming on cathodic surfaces due to the locally pH increase.
Since anodic and cathodic surfaces overlap in uniform corrosion, scales formed on
the cathodic side interact with anodic reaction products to form a compact mixture
of iron and calcium carbonates.
18.3.3 Anodic Inhibitors
These inhibitors increase the anodic overvoltage by promoting the formation of

protective or passivating films. They can be oxidant (or passivating) or non-oxidant.
Non-oxidizing anodic inhibitors. These inhibitors modify the anodic overvoltage

according to the electrochemical behaviour of the metal. On active metal, the
inhibitor promotes the passivity. On a passive metal, the inhibitor strengthens the
passivity and reduces the primary passivation current density. Typical non-oxidant
anodic inhibitors are hydroxides, borates, phosphates, polyphosphates, silicates and
benzoates. These inhibitors only work in the presence of oxidizing species as shown
in Fig. 18.3, since the operating point does not move from point 1. A more noble
cathodic process is mandatory to reach a passivity condition (point 2).
Oxidizing (or passivating) anodic inhibitors. These inhibitors have a twofold
action as illustrated in Fig. 18.4:
2 Inhibitor
Ecorr,2
Ecorr,1
1
icorr,2 icorr,1 log i
Fig. 18.3 Mechanism of action of an anodic inhibitor non-oxidizing
(a) (b)
E E
Inhibitor
1st effect
2
Ecorr,2
2nd effect
Inhibitor
Ecorr,3 3
Ecorr,1 Ecorr,1
1 1
icorr,2 icorr,1 log i icorr,2 icorr,1 icorr,3 log i
Fig. 18.4 a Electrochemical effects of a passivating anodic inhibitor; b electrochemical effects of

a unsafe inhibitor in proper concentration (point 2) and inadequate dosage (point 3)
• Modify the anodic curve

• Provide a more noble cathodic process in order to bring the metal to passive
condition.
Chromates, nitrites, permanganate, molybdates, tungstates and, obviously, oxygen,
are inhibitors of this type. Because of their toxicity, some of them are banned as
chromates; in many cases, it may be useful to employ mixtures of passivating
inhibitors to also reduce the critical passivation current.
Oxidizing anodic inhibitors work by setting up passivity conditions, then
reaching point 2 of Fig. 18.4b, provided a threshold is exceeded, because, con-
versely, corrosion may accelerate by reaching point 3. For this reason, these inhi-
bitors are called unsafe. Instead, inhibitors are safe when even a low dosage does
not accelerate the corrosion rate.
Therefore, the use of these inhibitors may be dangerous when the environment
composition changes due to a local increase of de-passivating agents such as
chlorides, or when passivity conditions are not reached due to locally insufficient
inhibitor concentration. These circumstances typically happen in dead spaces and
low flow conditions where the inhibitor is not renewed.
Once passivity conditions are reached, the consumption rate of the inhibitor is of
the order of the passivity current density, thus depending on temperature, pH and
chloride content, which are the same factors affecting passive conditions. The
consumption of an effective inhibitor is very low; conversely, consumption is high
when an inhibitor works badly.
18.3.4 Mixed Inhibitors
Adsorption inhibitors, for vapour phase or packaging, work by a mixed mechanism.

Figure 18.5 shows the chemical structures of the most used organic substances.
Absorption inhibitors. Normally used in acidic environments, for example in
pickling, they consist of:
• Substances that contain elements of the 5th and 6th group of the periodic table,
as N, P, As, S and O, with pairs of free electrons
• Organic compounds with double or triple bonds
• High molecular weight compounds such as proteins and polysaccharides, which
should not be considered strictly mixed inhibitors.
Due to their functional groups, these inhibitors are absorbed to the metal surface
where they form a protective monomolecular layer.
Volatile corrosion inhibitors. Volatile corrosion inhibitor (VCI), also known as
vapour phase inhibitors, are organic substances characterized by high vapour
pressure, typically between 10−2 and 10−7 mmHg, so they easily vaporize and
condense on a metal surface in a close environment. They are employed to prevent
CH3 CH2 CH3 CH2

CH3 NH2 NH2 CH3 (CH2)9 NH2 O NH2
CH3 CH2 CH3 CH2
Methylamine Diethylamine n-Decylamine Morpholine
H 2C CH O
C
H 2C N H 2 ONa
N N
Allylamine Pyridine Quinoline Sodium benzoate
N C H2
R C NH N CH2 SH
N CH2 N
N NH
R'
Imidazoline Imidazole Benzotriazole Benzilmercaptane
NH O
C S C H2 (CH2)2
NHHO C NH HNO2
NH2 C H2 (CH2)2
Phenylthiourea Esametylenimine-m-Nitrobenzoate Dicycloesilamine Nitrite
H 2C N H 2S
H 2S CH C H2 O
H 2C C C18H37 S
N H 2S S
CH C H2
C H2 C H2 NH2 H 2S
1-Etylamine-2-Octadecilimidazoline Di-sec-Butylsulphide Diphenylsulfoxide
Fig. 18.5 Organic substances frequently used as corrosion inhibitors
atmospheric corrosion in indoor spaces, for example within plastic containers,

during storage or shipment, as well as for packaging equipment. VCIs are
impregnated in polymeric films, in cardboard sheets or in papers, then wrapped
around the metallic component to be protected. They are also inserted in polymeric
boxes and sponges, placed in the environment where the metals are stored.
VCIs offer an important advantage over conventional inhibitors since they can
spontaneously penetrate into inaccessible crevices, gaps and slots, reach surfaces of
complex-shaped articles that are difficult to coat, and get adsorbed on the surface
from the vapor phase.
It has been found that the most effective VCIs are made up of a weak volatile
base and a weak volatile acid. Amine nitrite and carboxylate are susceptible to
hydrolysis and provide inhibition as follow:
R2 NH2 NO2 ! R2 NH2þ þ NO

2 ð18:4Þ
18.3.5 Inhibitor Adsorption Mechanism
Organic corrosion inhibitors work by adsorbing on the metal surface. This process
is governed by two factors: the residual electrical charge at the metal surface and the
chemical structure of the inhibitor. The former plays an important role: it produces
an electrical field that modifies the orientation of the solvent molecules, and attracts
(or repels) the ions present in the solution. The interactions are of physical nature,
hence calling this type of adsorption physisorption. The presence of certain func-
tional groups in the structure of a substance indicates whether a substance is more
favoured to adsorb onto a substrate: the presence of polar groups such as −NH2,
−OH or −COOH contributes to the formation of bonds with the surface, involving
interactions of chemical nature. This type of adsorption is denominated
chemisorption.
Physisorption. Physical adsorption is due to the electrostatic attraction between the
inhibitor and the electrically charged surface of the metal. The surface charge, /, is
defined by the difference between the free corrosion potential of the metal, Ecorr,
and its zero charge potential (ZCP). At ZCP the net charge on the electrode is zero:
/ ¼ Ecorr ZCP ð18:5Þ
This potential is fundamental for adsorption because it controls the kind of species
adsorbed onto the surface: as this potential becomes positive, the adsorption of
anions is favoured and as it becomes more negative, the adsorption of cations is
favoured. It also controls the electrostatic interaction of the metal with dipoles in
adsorbed neutral molecules, and hence the orientation of the dipoles and the
adsorbed molecules.
As an expression of the charge present on the surface, the /-potential is
dependent on the nature of the metal, on the cathodic process and on the chemical
nature of the adsorbed substance.
Chemisorption. It is probably the most important type of interaction between the
metal surfaces and an inhibitor molecule. The adsorbed species is in contact with
the metal surface, and a bond is formed between them, almost as strong as in
stoichiometric compounds. Electron transfer between the metal and the inhibitor
forms this bond through a coordinate link. In the metal, this process is favoured by
the presence of vacant electron orbitals of low energy, as observed in transition
metals. Conversely, in the adsorbed species the electron transfer is favoured by the
presence of relatively loosely bound electrons, such as may be found in anions
(–COO–, –O−), and neutral organic molecules containing lone pair electrons on the
donor atom (–NH2, –OH) or p-electron systems with multiple bonds or aromatic
rings.
These groups, either reactive or active, are the sites used by the organic mole-
cules to adsorb onto the metal. The strength of the coordinate bond between the
metal and the reactive groups depends upon the electron density on the donor atom
of the functional group and the polarizability of the group. Therefore, increasing the
polarizability by adding electron-donor groups to the inhibitor molecule provokes
an increase in the strength of the coordinating bond, which raises the corrosion
inhibitorefficiency. However, not only the ability to affect the electron density is
important in the adsorption of an organic inhibitor: the molecular area, molecular
weight and molecular configuration also have a great effect on its corrosion inhi-
bition efficiency. For example, an increase in the hydrocarbon chain may increase
the inhibition efficiency due to steric effects and the hydrophobic nature of the
chain. Under other circumstances, an increment in the hydrocarbon chain can
produce opposite effects.
18.3.6 Adsorption Isotherm
An adsorption isotherm describes the relationship between the coverage of an

interface with an adsorbed species (the amount adsorbed) and the pressure of gas or
concentration of the species in solution; in electrochemical reactions, the coverage
will depend also on the potential difference at the interface. The isotherm is typi-
cally used to verify the performance of organic adsorbent-type inhibitor.
Usually three types of isotherms are considered to describe this relationship:
Langmuir, Freundlich and Temkin isotherms.
In order to apply the Langmuir isotherm to an adsorption process, the following
assumptions must be taken into account: there is no lateral interaction between the
adsorbed species; the surface is smooth and defect free; and eventually the surface
can be saturated by the adsorbate. It is described by the following equation:
h
Kads C ¼ ð18:6Þ
1h
where Kads is the equilibrium constant for the adsorption process, C is the bulk
concentration of the adsorbate, and h is the fractional surface coverage.
The Freundlich isotherm is the most common isotherm equation due to its
simplicity and its ability to fit a variety of adsorption data. It is based on four
assumptions: all of the adsorption sites are equivalent and each site can only
accommodate one molecule; the surface is energetically homogeneous and adsor-
bed molecules do not interact; there are no phase transitions; at the maximum
adsorption, only a monolayer is formed. Adsorption only occurs on localized sites
on the surface, not with other adsorbates. These assumptions are seldom all met:
there are always imperfections on the surface, adsorbed molecules are not neces-
sarily inert, and the mechanism is clearly not the same for the very first molecules to
adsorb to a surface as for the last.
The Freundlich isotherm can be expressed as:

h
Kads C ¼ efh ð18:6Þ
1h
where f is molecular interaction constant. The Langmuir isotherm can be seen as a

special case of the Freundlich isotherm, when the interaction constant, f, is equal to
zero, i.e. there are no interactions between the adsorbate molecules. If f is negative,
lateral interactions must be of attractive character, while positive values indicate
repulsive lateral interactions.
The Temkin isotherm makes the same assumptions as the Freundlich isotherm
for the presence of heterogeneities on the surface and interaction between the
adsorbed molecules. It is defined by the following equation:
Kads C ¼ efh ð18:7Þ
where f is the molecular interaction constant. This isotherm can be considered a

special case of the Freundlich isotherm as well.
Once adopted the proper isotherm, the equilibrium constant for the adsorption
process, Kads, can be used to define the standard free energy of the adsorption as
follow:
DGads ¼ RT lnð55:5 Kads Þ ð18:8Þ
where R is the ideal gas constant, T is temperature (in K) and 55.5 is the molar
concentration of water in solution. Chemisorption generally requires a standard free
energy in the order of −100 kJ/mol, while lower values are typical of a physical
adsorption.
18.3.7 Inhibitor Effectiveness
Inhibitor effectiveness depends on a variety of factors such as nature, concentration

and chemistry of the inhibitor as well as nature and surface condition of the metal,
and composition and operating conditions of the aggressive environment, as tem-
perature and velocity; further factors as those affecting the inhibitor availability to
the metal surface (agitation, structure geometry and the presence of cracks).
The effectiveness of a corrosion inhibitor, ninib, is the reduction of the corrosion
rate as follows:
0
Crate Crateinhib
ninib ¼ 100 0
ð18:5Þ
Crate
0
where Crate and Crate-inhib are corrosion rates in the absence and in the presence of
an inhibitor, respectively.
Concentration. Corrosion inhibitors work properly if the dosage exceeds a mini-
mum, typically lower for oxidant inhibitors and higher for the others, which often
also act as pH correctors. The minimum dosage depends on surface conditions
(smooth and clean surfaces are better than rough surfaces or those covered by
corrosion products or scales), as well as on the environment composition (inhibitor
concentration should be increased when contrasting species are present).
Obviously, minimum concentration must be exceeded on the metal surface and
for the entire operating life by continuous or alternating refurbishing, in order to
compensate for any chemical and mechanical losses. The start-up is critical since
inhibitor consumption can be high for the film formation or by reaction with
contaminants. Accordingly, in the start-up phase, the rule of thumb is to maintain
the highest concentration especially for the anodic inhibitor.
In stagnant environments and in the presence of scales or porous deposits,
inhibitor concentration on a metal surface may be insufficient due to a lack of
supply: it follows that in these circumstances, dosage and dispersion efficiency must
be significantly increased.
As far as the influence of dosage is concerned, Fig. 18.6 schematically
demonstrates the influence on the corrosion rate of a safe and an unsafe inhibitor: if
the inhibitor concentration is less than the minimum effective one, there is a risk of
an increase in the corrosion rate only in the case of unsafe inhibitors.
The nature of metal. Most inhibitors are suitable only for a specific metal. For
example, benzotriazole and mercaptobenzothiazole are specific for copper and its
(a) (b)
Crate Crate
C0rate C0rate
Cinib
rate Cinib
rate
Concmin Conc Concmin Conc
Fig. 18.6 Concentration effect in the case of a safe inhibitors (a) and an unsafe inhibitor (b)
alloys, benzoates for steels, fluorides for magnesium, silicates for iron, zinc and
magnesium, and polyphosphates for steel and zinc. Conversely, chromates show a
general inhibiting action in neutral or slightly alkaline environments. Table 18.3
summarizes the degree of effectiveness of the commonly used inhibitors in industry.
In the case of equipment made with different metals, proper mixtures of inhibitors
are adopted. For example, in cooling circuits in cars, copper alloys, steel, cast iron
and aluminium are present, hence the cooling liquid, composed of ethylene glycol
and water in a ratio of 1 to 3, is added of phosphates, benzoates, nitrites and borates
to protect iron and aluminium, and mercaptobenzothiazole or benzotriazole to
protect copper-made components. It is worth noting that if there is a lack of inhi-
bitor for copper, aluminium suffers the greatest damage because of a displacement
reaction of the copper with aluminium (see Chap. 7), thus causing localised attacks.
Environmental condition. Inhibitors may lead to adverse effects when used in
unfavourable conditions. We already discussed the danger of oxidant inhibitors
used in environments containing de-passivating species, such as chlorides. Similar
considerations apply to their use in critical pH ranges. For example, chromates
works in the pH range 8–8.5; inhibitors for neutral or alkaline solutions become
ineffective below pH 5 for nitrites, 6 and 7.2 for benzoates and phosphates,
respectively. Inhibitor dosage normally increases as the temperature increases. For
some inhibitors, effectiveness fades if a critical temperature is exceeded.
18.4 Biocides
Biocides are chemicals used to control microbiological-related activity, which can

influence the corrosion behaviour as MIC. Typically they can be divided into two
categories:
• Non-oxidizing agents, as formaldehyde, glutaraldehyde, acroleine, quaternary
ammonium salts, bisthiocyanate, isothiazolines and dodecylguanidine
hydrochloride
• Oxidizing agents, as chlorine and its derivate, chlorine dioxide, hydrogen per-
oxide, ozone and per-acetic acid.
Non-oxidising biocides for industrial use are effective in controlling legionella,
slime-forming bacteria, sulphate reducing bacteria (SRB), algae and most of the
aerobic bacteria. They are able to penetrate deposits to access sessile bacteria. They
are compatible with many systems and with other chemicals, above all oxygen
scavengers.
Oxidising biocides are effective in controlling microbiological activity in com-
mercial cleaning, environmental hygiene, food and pharmaceutical industry, dis-
infection industrial and process water treatment activities. Among oxidizing agents,
chlorination is the most used treatment in food industry, pharmaceutic industry and
in public building, such as hospital of schools, where legionella and gallionella
must be eliminated. The source is typically sodium hypochlorite or chlorine
378
Table 18.3 Effectiveness of various inhibitors in solutions close to neutrality with respect to different metallic materials
Metal Chromatesa Nitrites Benzoates Borates Phosphates Silicates Tannin
Mild steel Effective Effective Effective Effective Effective Partially Partially
effective effective
Cast iron Effective Effective Ineffective Variable Effective Partially Partially
effective effective
Zinc and galvanized steel Effective Ineffective Ineffective Effective – Partially Partially
effective effective
Copper and its alloys Effective Partially Partially Effective Effective Partially Partially
effective effective effective effective
Aluminium and its alloys Effective Partially Partially Variable Variable Partially Partially
effective effective effective effective
Lead and lead alloys by – Aggressive Effective – – Partially Partially
welding effective effective
a
18
Banned in some European countries due to their toxicity

18.4 Biocides 379
dioxide, rarely chlorine gas. Since the storage of such biocides is harmful,
hypochlorite is often produced on site, combining an HCl and NaClO2, or by direct
electrolysis on site. The treatment is effective to reduce bacteria to less than 10
colonies/mL if the residual free chlorine content is about 0.5–1.0 ppm. An
under-treatment may contribute to the increase of bacteria colonies. An
over-treatment is not recommended; in fact, chlorine is a highly corrosive gas and a
strong oxidiser that may initiate corrosion on passive metals (pitting and crevice
corrosion). Moreover, the excess of chlorine may react with oxygen scavengers, if
present. Chlorine is not persistent: chlorination should be continuous to prevent
microbiological problems downstream. Chlorination does not reduce the effect of
SRB.
Although all biocides are efficient on the planktonic population (i.e., microor-
ganisms in the water phase), few are efficient in the case of microorganisms in a
biofilm, so that an increase in the dosage is needed. Besides, the use of biocides is
more and more limited by environmental legislation due to their toxicity to higher
organisms. Table 18.4 highlights applications, advantages and drawbacks of the
most commercially used biocides.
18:1 What are the effects of a pH increase on the corrosion behaviour of a carbon
steel water boiler? [Hint: consider the Pourbaix diagram of the iron-water
system. Is an oxygen removal still necessary?
18:2 Write the oxygen removal chemical reactions by sodium bi-sulphite and
hydrazine. What are the main difference between these oxygen scavengers?
18:3 In a water injection plant, oxygen content must be reduced to control carbon
steel corrosion. A physical treatment (a stripping column) is performed
before the use of oxygen scavengers. Which is in your opinion the reason?
Is it advisable to carry out firstly the chemical treatment?
18:4 The oxygen content of a room temperature process water is 3 mg/L. Which
is the oxygen scavenger dosage necessary to reduce oxygen content to
0.05 ppm?
18:5 Discuss the basic difference between anodic and cathodic inhibitors in terms
of variation of free corrosion potential.
18:6 Discuss the difference between non-oxidizing anodic inhibitors and oxi-
dizing (or passivating) anodic inhibitors. Provide some examples of inhi-
bitors of the two groups.
18:7 What is the difference between safe and unsafe inhibitors?
18:8 Due to a pump out of service, for 2 weeks the inhibitor dosage was lower
than the recommended one. Is there any risk on the corrosion of the pipe?
18:9 Discuss the inhibition mechanism of volatile corrosion inhibitors (VCI).
How do they work?
Table 18.4 Available biocides
380
Biocide Reaction Application Advantages Drawbacks

Oxydizing biocides
Chlorine Cl2 + H2O ! Freshwater – Economical – Operator hazard
HCl + HOCl pH 6–8 – Monitoring is simple – Ineffective for biofilm
HOCl ! H+ + OCl− – Broad spectrum activity – Ineffective for SRB
Sodium hypochlorite NaOCl ! Na+ + OCl− Freshwater – Economical – Expensive
pH 6–8 – Monitoring is simple
– Broad spectrum activity
Chlorine dioxide 2HCl + NaOCl ! Downhole cleaning and – Good oxidizing agent – Expensive
Cl2,aq + H2O + NaCl injection – Remove organic – Toxic
Cl2,aq + 2NaClO2 ! Wide pH range materials biomass – Special equipment is required for generation
2NaCl + 2 ClO2 – Dissolves FeS
Chloroamine Cl2 + H2O ! Petrochemical plant – More effective than – Ammonia injection is required
HOCl + HCl chlorine – More expensive than chlorine
NH3 + HOCl ! – Low toxicity
NH2Cl + H2O – Reduced corrosiveness
Hydrogen Peroxide H2O2 ! H+ + OOH− Freshwater – Safe – Contact with catalytic metal will accelerate its
35% Solution pH 6–8 – Non-foaming decomposition
– Decomposition products – Contact with concentrated acid, alkalis reducing
are completely safe agents, cause spontaneous decomposition
Peracetic Acid Food industry – Non-foaming – Contact with catalytic metal will accelerate its
18
Disinfection of medical – Broad spectrum activity decomposition

supplies – Contact with concentrated acid, alkalis reducing
agents, cause spontaneous decomposition
Bromine In water it releases Freshwater – More effective than – Expensive
1-bromo-3-chloro 5–5 HOBr and HOCl pH 6–8 chlorine
dimethylhydantoin – Broad spectrum activity
(continued)
18.5
Biocide Reaction Application Advantages Drawbacks

Ozone O3 + OH– ! Freshwater – Broad spectrum activity – Low stability
O2 + HO2− pH 6–8
Non oxydizing biocides
Formaldehyde 37% aqueous solution Petrochemical plants – Economical – Carcinogen
– High dosage required
– React with oxygen scavenger
Glutaraldehyde Used in a blend with Petrochemical plants – Broad spectrum activity – React with ammonia and oxygen scavenger
Questions and Exercises
other biocide – Insensitive to sulfide

Acroleine Effective biocide and Petrochemical plants – Broad spectrum activity – Difficult to handle
sulphide scavenger – Highly toxic
– React with ammonia and oxygen scavenger
Halogenated Widely used in drilling – Low toxicity – Unstable at high pH
compounds and produced fluid – Broad spectrum activity
2-bromo-2 nitropropane
1,3 diol
Quaternary ammonium Widely used in O&G – Broad spectrum activity – Form foams
compounds – Persistence – No tolerance for brine
– Do not interact with – Slow reaction
other chemicals
Quaternary Injection waters – Stable
phosphonium salts – Broad spectrum activity
– Tolerance for sulfide
381
18:10 What are the differences between physisorption and chemisorption? What
are the factors that govern them?
18:11 Which information provide an adsorption isotherm? What are the main
differences between Langmuir and Freundlich isotherms?
18:12 Corrosion rate of carbon steel in acidic solution, pH 4.5, is reduced by
adding amines as cathodic inhibitor. Calculate the inhibitor efficiency to
decrease corrosion rate from 1.1 to 0.01 mm/year.
18:13 What is the main drawback related to the chlorination over-treatment of
water?
18:14 NaClO is added to water to control bacteria proliferation in an AISI 304
stainless steel tank in a food plant used to clean apples. Due to problem in
the software controlling NaClO dosage, for one week a double dosage was
added to the water. Could the stainless steel tank suffer corrosion?
18:15 The cold-water plant in a hospital is treated with chlorine mainly to kill
Gallionella bacteria. As a rule of thumb, operators suggest to dose chlorine
in order to have at the end of the piping a maximum chloride content lower
than 0.1 mg/L. Which is the main reason of this limit?
Bibliography

Kuznetsov YI (1996) Organic inhibitors of corrosion of metals. Plenum Press, New York, USA
Sastri S (1998) Corrosion inhibitors: principles and applications. Wiley, Chichester, UK
Chapter 19
Cathodic and Anodic Protection
Electrical current [exchanged between metal and electrolyte]

modifies exceptionally the oxidation state.
A. Volta, Letter to Editors of Britannic Library of Geneva,
March 18th 1802
Abstract As Volta already observed in early 1800s, a current that is exchanged

between a metal surface and the electrolyte to which it is exposed modifies the
behaviour of the metal, increasing the corrosion rate or reducing it. Some years later,
Davy put in practice such concept demonstrating the possible implications, which,
after about a dormant century, started to have effective industrial use: with Davy,
cathodic protection was born. A century and a half from Volta’s observations,
Edeleanu showed that Hickling potentiostat could control corrosion by making an
anodic polarization and Riggs made the first commercial application of anodic
protection: hence, anodic protection was also born. Both techniques are set up by
establishing a cathodic or anodic current that is exchanged with the electrolyte,
which means supplying or taking electrons. The following chapter deals with these
techniques from a theoretical and practical point of view: mechanism, protection
criteria, protection potential and current density, applications, monitoring.

https://doi.org/10.1007/978-3-319-97625-9_19
384 19 Cathodic and Anodic Protection
19.1 Cathodic Protection (CP)
Cathodic protection is an electrochemical corrosion control technique used to

prevent the corrosion of metal structures, by lowering their potential by means of a
cathodic direct current supplied by an anodic system, such as the one reported in
Fig. 19.1. Some examples are:
• Underground facilities (gas pipelines, pipelines, aqueducts, tanks)
• Marine exposed structures (harbours, offshore platforms, ship hulls)
• Internal of heat exchangers or equipment often in contact with seawater
• Chloride-contaminated reinforced concrete structures.
As shown in Fig. 19.2, it is carried out by supplying electrons through a current
circulation between an electrode (anode) in contact with the environment and the
structure (cathode).
The mode by which the current circulation is performed defines the two types of
cathodic protection: galvanic (or sacrificial) anodes (GACP) and impressed current
(ICCP).
Figure19.2a shows the GACP obtained by galvanic coupling with a less noble
metal; for example, aluminium and zinc are used for the protection of steel in
seawater, magnesium in soils and in freshwater; iron is usually used to protect
copper alloys or stainless steels. Figure 19.2b shows the electrical scheme of ICCP
by the use of DC feeding systems with the negative pole connected to the structure
and the positive to an anode, which can be soluble, as iron, or inert as silicon-cast
iron, graphite or platinized and activated titanium.
19.1.1 Protection Potential
CP reduces or stops corrosion by two distinct effects as the result of potential

lowering, namely:
Metallic conductor DC Feeder
Metallic Galvanic Metallic Anode

structure anode structure
Fig. 19.2 Cathode protection principle: a by galvanic anodes; b by impressed current

19.1 Cathodic Protection (CP) 385
• Thermodynamic effect which reduces or cancels the driving voltage for the
corrosion process, DE
• Kinetic effect which increases reaction electrical resistances.
19.1.2 Thermodynamic Effect
When potential is brought below the equilibrium potential, E < Eeq, the tendency of
a metal to oxidize stops or instead reverses toward reduction of metal ions, if they
are present. This condition is called thermodynamic immunity. Table 19.1 shows
the equilibrium potential of different metals in contact with solutions containing
their ions at a concentration of 10−6 mol/L, which can be assumed as potentials for
immunity protection.
If potential decreases below the free corrosion potential, Ecorr, without zeroing
the driving voltage (i.e., Eeq < E < Ecorr), corrosion reduces rather than stops; from
an engineering point of view, provided that corrosion decreases below an agreed
threshold (10 lm/year), this condition, called quasi-immunity is acceptable as
shown in Fig. 19.3a. For example, quasi-immunity of steel immersed in seawater or
buried in soil, is achieved if potential is below −0.85 V CSE in aerated condition or
below −0.95 V CSE in anaerobic condition, when SRB are present.
19.1.3 Kinetic Effect
Rather than the reduction of driving voltage, kinetic effects associated to the po-
tential lowering derive from the increase of the corrosion reaction resistance when
the metal undergoes or strengthens passive conditions (Fig. 19.3b), like stainless
steels in neutral solution or carbon steel in alkalies, for example in concrete. This
condition is defined as CP by passivity.
Table 19.1 Immunity potential as equilibrium potential, Eeq

Metals Equilibrium potential as per Pourbaix
(V SHE)
pH = 0 pH = 7 pH = 14
Silver +0.44 +0.44 +0.32
Copper +0.12 +0.12 −0.38
Lead −0.31 −0.31 −0.74
Iron −0.62 −0.62 −0.92
Aluminium −1.78 −1.78 −2.06
(a) (b)
E E
Cathodic curve Cathodic curve
Ecorr Anodic curve
Ecorr Anodic curve
Eeq Eeq
log i log i
Fig. 19.3 Electrochemical conditions of CP for a metal a active (quasi-immunity condition) and
b active-passive (passivity)
19.1.4 Protection Criteria and Overprotection
The protection potential, Eprot, is a potential value lower than, or equal to one at
which an acceptable corrosion rate is reached for the metal considered. Some
practical values are listed in Table 19.2, which assure immunity or quasi immunity
or passive conditions.
If potential is reduced to more negative values, hydrogen evolution becomes the
predominant cathodic reaction and this condition is defined as overprotection. For
example, for carbon steel in aerated soil, overprotection is reached when the po-
tential is more negative than −1.2 V CSE, as reported on ISO 15589-1.
Overprotection has to be avoided, for economic reasons first, because for
example a 100 mV lowering of potential increases by one order of magnitude the
cathodic current according to Tafel law of hydrogen evolution reaction, hence the
cost of CP. Secondly, overprotection may have two negative effects due to the local
hydrogen evolution:
Table 19.2 Protection Metals Soil Seawater

potentials for most commonly
V CSE V Ag/AgCl V Zn
used metals in soil and
seawater Carbon steel:
– Aerobic −0.85 −0.80 +0.25
– Anaerobic −0.95 −0.90 +0.15
– In concrete −0.75 −0.70 +0.35
Copper −0.30 −0.20 +0.70
Lead −0.50 −0.45 +0.50
Zinc −1.00 −1.05 0
Aluminium −0.80 −0.90 +0.15
Stainless steel −0.40 −0.50 +0.55
• Disbonding of coating
• Hydrogen embrittlement of susceptible steels.
19.1.5 Protection Current Density
Protection conditions are achieved when an adequate cathodic current density is

supplied as Fig. 19.4 shows. It is called protection current density and corresponds
to the electrons taken by all cathodic processes occurring at the protection potential.
By applying Kirchhoff’s law, the cathodic external current, Ie, is given by:
Ie ¼ Ic Ia ð19:1Þ
where Ia is the residual anodic current and Ic is the cathodic current. Anodic current
zeros when the external current equals the cathodic current, then giving the pro-
tection current, Iprot:
Ie ¼ Ic ¼ Iprot ð19:2Þ
The protection current density, Iprot, is the ratio between the protection current, Iprot,
and the protected surface. It depends on environmental conditions in the same way
as the cathodic processes.
In natural environments, as soil and waters, the protection current density for
carbon steel equals the oxygen limiting current density, hence it depends on dis-
solved oxygen content, temperature and turbulence. For example, for steels in
seawater, the protection current density ranges from 1 to 20 mA/m2 in seamud;
50–70 mA/m2 in warm, stagnant water and 100–200 mA/m2 in cold and agitated
water, reaching 1000 mA/m2 for propellers zone in ships because of maximum
agitation and oxygenation. Table 19.3 shows the current density values used in
industrial applications.
In natural waters, protection current decreases with time because a calcareous
deposit forms after the alkalinization produced by the cathodic reactions. In general,
Fig. 19.4 Principle of Fe

cathodic protection from the Cathodic zone
ee ec
electrical viewpoint Ic
External Ie
electrons
ea
External
Fe++ Ia current
Fe++
Anodic zone
Table 19.3 Protection current density adopted in typical industrial applications

Environment Protection current density (mA/m2)
Bare steel
Soil
– Neutral aerated 20–150
– Water saturated 2–20
– Hot metal surface 30–60
Concrete
– Atmospherically exposed 2–20
– Water saturated 0.2–2
Fresh water
– Cold 30–160
– Warm 50–160
Seawater 50–600
Seamud 20–33
Acidic electrolytes 50–1500
Coated steel
Soil 0.01–1
Seawater 0.1–10
to reduce the protection current density, coatings are applied to limit the exchanged
current at the coating pinholes and defects then reaching a small percentage of the
exposed surface, typically less than 1%.
If the applied current density exceeds the protection values as reported above,
potential is reduced to more negative values, and overprotection conditions may
occur.
19.1.6 Anodic Reactions
On anodes, different reactions take place depending on anode type and environment
as follows.
Galvanic anodes. The anode reaction is the metal dissolution, typically zinc,
magnesium, aluminium and iron dissolution, followed by the hydrolysis reaction
which produces a local acidification:
M ! M z þ þ z e ð19:3Þ
Mz þ þ z H2 O ! MðOHÞz þ z H þ ð19:4Þ
This acidity increase plays an important role in avoiding passivation of anodes,

especially in the case of aluminium anodes. The chemical composition of the
anodes is very important. In the case of zinc anodes, the presence of some elements,
as iron with a content in excess of 50 ppm, can lead to passivation of the anodes or
may reduce its efficiency; in the case of aluminium anodes, iron or copper impu-
rities are harmful; conversely, the presence of other elements, such as indium,
mercury or tin, is necessary to keep anodes active.
Inert anodes. Anodes used in ICCP systems are in general insoluble. Therefore, the
anodic reaction is oxygen evolution and, in the presence of chlorides, chlorine
evolution, according to the following reactions:
2H2 O ! O2 þ 4H þ þ 4e ð19:5Þ
2Cl ! Cl2 þ 2e ð19:6Þ
Chlorine evolution prevails in the case of seawater applications if ia > 10 A/m2.

Oxygen evolution causes a local acidification which greatly increases the aggres-
siveness against the anode material.
19.1.7 Coatings and Scales
The application of an insulating coating reduces significantly the protection current

density, since only pores, pinholes, defects and damages can exchange the current.
Accordingly, the protection current density for a coated surface is given by the
following expression:
iprot ¼ i0 ð1 nÞ ð19:7Þ
where i0 is the protection current density of the bare metal and n is the coating
efficiency (or unitary coated surface fraction).
Coating efficiency varies over time; for example, for buried pipelines can reach
90% after 10–20 years; in seawater coating degradation might be even more
accelerated as for shiphulls for which efficiency can shift from 99.9 to 99% in the
first year exposure.
In seawater, cathodic protection causes the formation of a scale consisting of a
mix of calcium carbonate and magnesium hydroxide, called calcareous deposit; it
reduces favorably of about one order of magnitude the protection current density as
an effective barrier to the oxygen diffusion. Parameters affecting the quality of the
calcareous deposit are seawater composition (for instance, it hardly forms in low
salinity seas, as Caspian and Baltic seas), current density and mechanical actions
(abrasion and vibration). Once protection current is interrupted, the calcareous
deposit slowly starts to dissolve.
19.1.8 Current Distribution
The protection current must be uniformly distributed over the cathodic surface to
obtain even protection conditions. Conversely, non-uniform distribution can lead to
either over-protection or under-protection, with risks in the former case of hydrogen
embrittlement on high strength steels and disbonding of coatings and in the latter
case of some residual corrosion.
For structures with complex geometry, it may be difficult to achieve a good
current distribution, especially when high protection currents are required with high
resistivity electrolyte and small anode-to-cathode distance or linear structure as
pipelines. In the latter case, a considerable ohmic drop throughout the metal takes
place, which establishes so-called potential attenuation. Conversely, in the case of
reinforced concrete structures there is a strong ohmic drop in the concrete cover
although applied current densities are moderate. Finally, for offshore and marine
structures, ohmic drop is negligible despite the very high protection current
densities.
The usual adopted design procedures are based on empirical criteria regardless
the problem of electric field distribution. Nowadays, it has become a common
practice to verify for complex structures, as nodes of platforms and heat exchangers,
the current and potential distribution by the resolution of the electric field through
modelling (FEM and BEM). As discussed in Chap. 9, the analytical resolution of
the electric field, regulated by the Laplace equation, is possible only for very simple
geometries and with drastic simplification, for example, homogeneous electrolyte
and negligible overvoltage or linearly increasing with current. For some distribu-
tions, reference is made to Table 9.1.
Conditions for the application of modelling
The most commonly used numerical model is the finite elements method, devel-
oped some decades ago, especially in the field of structural engineering to solve
problems of strain and deformation analysis.
The method has been extended to solve a wide variety of physical, field-related
problems connected to a flow of some magnitudes, such as heat, mass or current
under the action of a gradient of temperature, pressure or electrical potential,
respectively. There are issues regarding heat transmissions, diffusion through por-
ous media, hydrodynamics, electrical and magnetic fields, and finally CP. The
common equation is the almost harmonic Poisson-Laplace equation. In the case of
CP, the potential field in the electrolyte follows the Laplace equation as follows:
r2 E ¼ 0 ð19:8Þ
By using the finite element method, the resolution of (19.8) is addressed by dividing
the global system into a finite number of elements, each of which interacts with
contiguous ones crossing the points of its outline, called nodes. The values of the
potential function, E, in the nodes are unknown to the discretized problem and are
obtained by introducing the following boundary conditions: on electrodes, i = f (η)
and Em = constant (equipotential electrodes) or dEm = r Ix dx (when an ohmic drop
occurs in the metal); on insulating surfaces, i = 0. Instead, curiously, Leopoldo
Nobili in 1835 gave a coloured solution of the Laplace equation (see Chap. 9).
19.2 CP Applications
CP is typically applied to structures exposed to natural environments and reinforced

concrete ones.
Galvanic anodes are used in high conductivity environments, such as seawater,
and in some cases when small currents are required even in low conductivity
environments, such as soil and in the cathodic prevention of reinforced concrete.
Impressed current systems are required in high resistivity environments such as
soil and concrete and are preferred for the protection of extended structures when a
limited number of anodes is mandatory. A significant advantage is that the system
has a great flexibility of operation, which can vary, allowing an easy regulation of
the current delivered.
Table 19.4 summarizes benefits and limitations of the two applications.
Table 19.4 Advantages and drawbacks of GACP and ICCP systems

GACP ICCP
Advantages • Feeding power not required • Voltages and currents can vary
• Current adjustment not required • High current output if necessary
• Easy and almost inexpensive • A single groundbed can protect large
installation surface structure
• No stray current arising • Suitable for high resistivity
• No maintenance costs required environments
• Almost uniform current • Effective for protecting bare or badly
distribution coated structures
• Additional areas not required
around facilities
Drawbacks • Low driving voltage • Stray current problems
• Low current output • Subject to vandalism
• Expensive installation after • Maintenance necessary
commissioning • Need of feeding
• Bare or badly coated structures • Operating cost
require many anodes • Overprotection risks
• Unsuitable in high resistivity • Risks of failure of cables and
environments connections
• Additional areas required around
facilities
19.2.1 Galvanic Anodes Cathodic Protection Systems

(GACP)
CP with galvanic anodes is mainly used to protect marine structures as offshore

platforms and submerged pipelines, internal surfaces of equipment: from domestic
boilers to chemical or petrochemical industry heat exchangers or condensers of
power plants, shiphulls and internal of doublewall tankerships and many more. In
principle, GACP can be made with any metal less noble than the one to be pro-
tected; in practice, for carbon steel structures, only aluminium, magnesium and zinc
alloys are used.
Two parameters characterize an anode: working potential and current capacity.
The former determines the current output of an anode and therefore the minimum
number needed to establish the protection current; the current capacity, i.e., the
charge by weight, determines the anode consumption, hence the minimum weight
to ensure the protection during the lifetime.
Anode capacity. A galvanic anode while working dissolves through its electrode
reaction (M ! Mz+ + ze−, where M is the anode metal and z is its valence). By
Faraday law, the product of electrochemical equivalent and charge gives the the-
oretical anode consumption, usually expressed in kg/A year. In practice, true anode
consumption is higher because the anode corrodes by its own as it occurs in gal-
vanic corrosion; for zinc and aluminium anodic alloys the efficiency is about 95%,
for magnesium alloys is as low as 50%. Often theoretical anode capacity is
used, defined as the inverse of theoretical consumption, hence expressed in A h/kg.
For ease of calculations, the product between theoretical capacity, A h/kg, and
theoretical consumption, kg/A year, is 8760. Table 19.5 shows the consumption
and theoretical abilities of aluminium, zinc and magnesium.
Table 19.5 Electrochemical properties of Mg, Zn and Al anodic alloys

Parameters Mg Zn Al
Atomic mass 24.32 65.38 26.97
Equivalent mass 12.16 32.69 8.99
Specific gravity a 20 °C (g/ 1.74 7.14 2.70
cm3)
Anode theoretical consumption 3.98 10.69 2.94
– kg/A year 2.3 1.5 1.1
– dm3/A year
Anode theoretical 2200 820 2980
capacity (A h/kg)
Anode working potential −1.55/−1.75 (V −1.00 (V −1.05 (V
CSE) SSC) SSC)
Anode efficiency (%) 50 95 90–95
19.2 CP Applications 393
Fig. 19.5 Equivalent electrical circuit for galvanic anode systems
Anode output. With reference to the equivalent electric circuit depicted in

Fig. 19.5, the current supplied by an anode, I, is given by the Ohm’s law:
I ¼ DE=R ð19:9Þ
where DE is the driving voltage, i.e., the energy available to overcome ohmic drops,
and R is the total electrical resistance of the circuit, expressed as:
R ¼ Ri þ Rcables ð19:10Þ
where Ri is the ohmic resistance of the electrolyte and Rcables is the resistance of the
metallic circuit, most often negligible unless in the case of big remote anodes. The
electrolyte resistance can be reduced to the anode resistance, Ra, which is calculated
by empirical equations as function of anode size and electrolyte resistivity
(Table 19.6). In order to decrease the anode resistance, elongated anodes are used,
as slender anodes for offshore applications and rod type anodes for soil applica-
tions; in soil, a low resistivity backfill is also used. The driving voltage, DE, is
obtained by subtracting the overvoltage from the electromotive force, hence it is the
difference between the working potential of the anode, Ea, and the protection
potential, Eprot. For example, for steel structures, driving voltage, DE, is 250 mV
for zinc anodes, 300 mV for aluminium and 800 mV for magnesium.
Anode selection. Anodes are selected on the basis of the metal-environment cou-
ple. Table 19.7 summarizes the types of anode for water and soil, suggested in
practice as function of environment resistivity. This rule of thumb derives from the
evidence that once fixed the anode size, the current output becomes a function of
the environment resistivity only. For soil applications, it is possible to lower the
resistivity by using a proper backfill, which also can help decrease overvoltage and
prevent anode passivation. Typical backfill composition is a mixture of gypsum,
bentonite and sodium sulphate in the weight ratio of 70:20:10. Gypsum (CaSO4)
has the main function to keep the anode active so to favour a uniform dissolution,
Table 19.6 Equations used for the calculation of the anode resistance
Type Notes
Slender anodes
q
4L
Dwight Ra ¼ 2pL ln r 1 Most used for offshore slender anodes
q
Peters Ra ¼ 2pL ln r
2L Little used
Shepard & Graeser Ra ¼ 6:2 2pL ffi qL
q
Valid for L/2r 64
Bracelet anodes
q When Sa > 500 cm2 is equivalent to Mac
Naval Research Ra ¼ ðS1:66
Þ0:727
a
Laboratory Coy’s. Little used
Mac Coy Ra ¼ ppq ffiffiffi
S
ffi Most used for bracelet anodes
a
Flat anodes
1:5 q
BKL Ra ¼ p ðL þ 0:8B þ 0:5 sÞ
For anodes with L/r < 10
q
Lloyds Ra ¼ 2L0
For anodes applied on flat surfaces
Suspended anodes
Lloyds Ra ¼ 4Lq 0 For thin, flat anodes
q = electrolyte resistivity (X.m); L = anode length (m); r = equivalent radius (m)
Sa = anodic surface (m2); B = width (m); s = thickness (m);
L′ = (a + b)/2 (m) where a and b are the sizes of flat anodes, b < 2a
Table 19.7 Galvanic anodes suitable for water and soil

Anode Resistivity (X m)
Water Soil
(plus backfill)
Aluminium Up to 1.5 Not used
Zinc Up to 5 Up to 15
Magnesium low potential (−1.5 V CSE) All Up to 40
Magnesium high potential (−1.7 V CSE) All Up to 60
bentonite to reduce resistivity by absorbing moisture and sodium sulphate (Na2SO4)

to increase electrolyte conductivity.
In particular applications, the choice of the anode material should comply
with safety criteria. For example, magnesium and to a lesser extent aluminium, can
cause sparks with a rusted steel surface due to a reaction with iron oxide if freely
dropped, which may ignite a deflagration of hydrocarbon vapors. For this reason,
within storage tanks or tankers used to transport flammable products, only the use
of zinc anodes is permitted without restriction, while magnesium anodes are always
excluded and for aluminium it is necessary to observe specific restrictions as
maximum height from the floor.
From the economic point of view, aluminium alloys are the cheapest ones, as the
cost to produce the same charge, taking into account the practical consumption and
average unitary cost follows an approximate ratio 100:300:750 for Al, Zn and Mg
respectively.
Anode number calculation. The design of CP involves, after the choice of the
anode type, the calculation of weight and number of anodes and eventually their
location on the structure. Among a variety of possible solutions as number, weight
and duration of anodes, the adopted one is generally the cheapest solution.
A serious error can be made if the number of anodes is simply calculated dividing
the total weight of the anodes (calculated on the basis of the lifetime) by the weight
of a single anode selected by a catalog without verifying its output capacity. In this
case, in fact, the total anode mass is sufficient for the expected duration of the
protection, but may not be able to provide the current required for the protection,
which depends on anode surface area rather than weight. In other words, it is
necessary to optimize the weight-to-surface area ratio of the anodes to ensure both
protection and duration.
Procedure steps for determining the anode number are based on the following
calculations:
• Protection current (total surface area times the protection current density)
• Anode weight (current times consumption times duration)
• Anode resistance of a selected anode (first choice) by applying empirical
equations reported in Table 19.6 (resistivity is the one of the electrolyte sur-
rounding the anode)
• Current output of an anode (driving voltage divided by anode resistance)
• Number of anodes (total weight divided by the weight of an anode)
• Minimum anode output (total current divided by the number of anodes)
• Compliance between anode output and minimum current requirement
• Acceptance of the solution or repetition with a second anode choice.
19.2.2 Impressed Current Cathodic Protection

Systems (ICCP)
CP by impressed current is primarily applied to buried and reinforced concrete

structures and also to water tanks, heat exchangers, desalinators and ships. For these
systems, a direct current is supplied by a DC feeder through an anode immersed or
embedded in the environment. Figure 19.6 illustrates the equivalent electrical cir-
cuit of an ICCP system.
Anode materials. Table 19.8 reports compositions, consumption rate and working
conditions of main used anodes of ICCP systems. The anodic reaction occurring on
anode surface depends on both anode material and environment. For example, for
carbon steel anodes, the anode reaction is iron dissolution; for inert or so-called
insoluble anodes, for example platinized or MMO (mixed metal oxide) activated
titanium, graphite and others, the anodic reaction is oxygen evolution or chlorine
DC Feeder
IRcables
IRi
Cathode Anode
Fig. 19.6 Equivalent electrical circuit for ICCP
evolution or both depending on the electrolyte, soil or seawater, and anodic current
density.
Feeding voltage. The first step for the design of an ICCP system is the calculation
of the minimum feeding voltage, Vmin, required. From electrical and electrochem-
ical considerations, it is the so-called cell voltage given by:
Vmin ¼ I Rtot þ w ð19:11Þ
where I is the total design protection current; Rtot is the total resistance of the circuit
(calculated or given) and w is the thermodynamic and kinetic contribution of
electrode reactions, which is the minimum feeding tension out of the ohmic drop. It
is negligible for dissolving iron anodes and 2–3 V for inert anodes.
Groundbeds. In seawater and inside equipment, the anodes work without backfill
as directly exposed to the electrolyte. Anode shape can be easily adapted as for the
shape of the cathodic surfaces and the mechanical requirements for the installation.
In soil applications, the need for a low anode resistance prevails on other
requirements. As a rule of thumb, resistance is often less than 2 X. Furthermore, for
safety reasons, the feeding voltage should not exceed 50 V in compliance with
standards. To achieve this goal a backfill is used to reduce the anode resistance.
Typical groundbeds for soil applications are of three types: horizontal, shallow
vertical, deep vertical.
Calculation scheme. The design of an ICCP system deals with type and sizes of
groundbed and feeder requirements. Often, adopted technical solutions are deter-
mined by external input, for example in urban areas vertical deep groundbeds are
mandatory for lack of suitable large areas or lack of usage permits.
The general calculation procedure consists of the following steps:
• Calculation of the protection current (product of the cathodic surface area times
the protection current density)
19.2
Table 19.8 Properties and characteristics of the main insoluble anodes

Material Description—composition Density Resistivity Consumption Anode current density (A/m2)
3 −8
CP Applications
Mg/m X m 10 UF kg/A year Soil Fresh Seawater Mud

water
Iron Scrap steel 7.1–7.8 12–55 0.5 10 5 NR (–) (–)
Graphite Graphite impregnated with oil, resins, 1.6 800–1500 0.6 1 2.5–10 2.5 20 2.5
wax (*)
Silicon iron Cast iron 14% Si, 0.75% Mn, 0.95 C 6.8–7.0 72 0.5 1 10 10 NR (–)
Cast iron 14% Si, 4.5% Cr, 0.75% Mn, 7.0 72 0.5 0.5 10 10 15 (–)
0.95 C
Lead Solid lead with 2% Ag 11.3 25 0.6 0.1 (–) (–) 32–65 (–)
Solid lead with 1% Ag, 6% Sb 10.9 25 0.6 0.2 (–) (–) 50–200 (–)
Magnetite Non stoichiometric Fe3O4 5.2 33,000 0.4 0.05 20 20 60 20
Pt (on Ti) Platinized titanium 4.5 48.2 0.85 10–4 100(*) 150 500 (–)
Pt (on Nb) Platinized niobium 8.5 15.2 10–4 100(*) 150 500 (–)
Plastic support Polyolephyne plastics with conductive 1 0.5 0.5 (–) (–)
anodes fillers (carbon)
Activated Titanium activated by mixed noble 4.5 48.2 0.95 10–4 50– 150 600 100
titanium metal oxides (Ir, Rh) 100 (*)
UF utilisation factor; (–) not recommended; (*) with calcined carbon coke backfill
397
• Choice of groundbed and calculation of anodic resistance, Ra, and cable resis-
tance, Rcable
• Calculation of the total resistance, Rtot ðRtot ¼ Ra þ Rcable Þ
• Calculation of feeding voltage Vmin ¼ I Rtot þ w , where w is thermodynamic
and kinetic constant, and I is the maximum protection current
• Check of anode life.
19.2.3 CP Monitoring
CP monitoring includes all operations aimed to check, directly or indirectly, the

protection condition of a structure, which is related to local conditions rather than to
global parameters. Therefore, protection conditions are not monitored by the total
protection current output or by the potential measured in a remote location; instead,
protection on a point of a structure is reached if the current density, at that point, is
equal to or greater than the protection value.
Measurement of potential. The measurement of potential is the criterion univer-
sally used to verify CP. The measurement follows the scheme shown in Fig. 19.7; a
reference electrode is placed in contact with the environment (as soil, water, con-
crete) and connected to the negative pole of an high impedance voltmeter (at least
greater than 10 MX for most used reference electrodes1), while the structure is
connected to the positive one. This simple and easy measurement needs however a
correct interpretation, as discussed in the following.
Interpretation of potential measurements. When measuring the potential by a
portable reference electrode (as shown in Fig. 19.7), there is an ohmic drop con-
tribution, IR, due to the current flowing in the electrolyte (protection current, stray
current, etc.). This contribution alters the potential reading, hence has to be elim-
inated. The measured value, E, is the sum of three contributions, as shown in
Fig. 19.8:
E ¼ Eeq þ g þ IR ð19:12Þ
1
The current flowing during measurement is given by the ratio of the potential difference and the
circuit resistance which practically coincides with the internal impedance of the voltmeter. If, for
example, the reference electrode has a surface area of 10 cm2 and the potential difference is 1 V
with a voltmeter impedance of 1 MX, current density exchanged on the reference electrode surface
is 1 mA/m2 which is less than the exchange current density of active metals like copper, zinc and
iron, but is greater by at least one order of magnitude than the passivity current density of Ti.
Therefore, when using a small size MMO activated Ti as reference electrode, to avoid its polar-
isation the voltmeter impedance must be greater than 10 MX for short measurements and higher
than 1 GX for continuous monitoring.
Offshore
platform
Reference
electrode Reference
electrode
Pipe
Fig. 19.7 Measurement of the potential of buried and immersed structures
Reference
Voltmeter electrode
E
Reference
electrode IR
I’
η
Eeq
Pipeline
I
Soil
(or electrolyte)
Fig. 19.8 Measurement of the potential of structures and the meaning of the measure
Fig. 19.9 Schematic E

indication of overvoltage
contribution and meaning of
potential measurement Anodic curve
Ecorr
Eeq 
EIR-free 
IR
E
log i
where Eeq is equilibrium potential defined by Nernst equation, η is overvoltage

related to the exchanged current measured with respect to the equilibrium potential
and IR is ohmic drop in the electrolyte. The sum (Eeq + η) is the so-called IR-free
potential, EIR-free, also referred to as “true potential”, which can be expressed
through the free corrosion potential, as shown in Fig. 19.9:
EIRfree ¼ E IR ¼ ðEeq þ gÞ ¼ ðEcorr þ wÞ ð19:13Þ
where w is the overvoltage measured with respect to the free corrosion potential,
Ecorr.
The ohmic contribution, IR, is the spurious term that contaminates the mea-
surement of potential. According to the second Ohm’s law, it depends on the
position of the reference electrode with respect to the monitored structure, the
resistivity of the electrolyte, and the flowing current density, i. Hence, the measured
potential is a function of the position of the reference electrode: it decreases when
the reference electrode is placed close to the structure, therefore, the simplest
technique to minimize it, consists in placing the reference electrode as close as
possible to the structure. Resistivity plays an important role: for example in sea-
water, where resistivity is low, even if current is high, the ohmic drop is often
negligible. On the contrary, in concrete and in soils, especially in the most resistive
ones, the ohmic drop is not negligible at all, even if a small current circulates.
Elimination of ohmic drop contribution from potential measurement
The two ways to eliminate the ohmic drop from potential measurement are based on
the following actions:
• Reduction of the distance reference electrode—structure
• Elimination of the circulating current.
In the first case, local (fixed) reference electrode or potential probes are used. The
elimination of the circulating current is achieved by the ON-OFF method.
Local reference electrode. If the reference electrode is placed close to the structure,
the IR drop contribution is reduced or even eliminated. In practice, this is done in
seawater, for example on offshore platforms, where it is easy to place the reference
electrode close to the jacket at the desired point. For buried structures, it is nec-
essary to make use of fixed reference electrodes buried very close to the structure,
up to a maximum of 0.2 m.
While this method is efficient for bare structures, it is questionable for coated
structures, since to know the IR-free potential at a coating holiday, the reference
electrode must be as close as possible to it. In other words, by simply installing a
reference electrode close to the coated structure, the potential measured is not
representative of the lower protection level established at holidays, unless the ref-
erence electrode is, by chance, close to the biggest one.
Potential probe. To overcome this problem, an artificial defect, called corrosion
coupon, is used in combination with a close reference electrode. This device is
called potential probe. The coupon is connected to the structure to simulate the
presence of a coating defect. Coupon surface is in the range 1–10 cm2, depending
on the insulation resistance of the pipe to which it is connected. Indeed, the coupon
shall be representative of a defect in the pipe coating or of any buried structure. The
potential probe represents an elegant and brilliant method to measure the protection
A E
Plastic case Steel coupon
Porous plug
Reference
electrode
Pipeline Potential
probe
Fig. 19.10 Fixed probe with built-in reference electrode
potential of the coupon because ohmic drop is eliminated physically by placing the
reference electrode in close proximity to the coupon (E = EIR-free). Figure 19.10
shows a potential probe, which consists of a coupon embedded with an incorpo-
rated reference electrode.
ON-OFF technique. This method is based on the experimental evidence that when
the protection current is interrupted, the IR drop disappears in a very short time, on
the order of 10−6 s. Therefore, by recording the potential reading shortly after
current interruption, the IR drop is no longer included. This technique is not valid in
presence of currents different from the protection current, as stray currents.
Obviously, by interrupting the protection current, overvoltage is also eliminated
but over a much longer period than IR drop, ranging from milliseconds for acti-
vation overvoltage (related to hydrogen evolution reaction) to seconds or even days
for concentration overvoltage (related to oxygen diffusion). The latter is the pre-
vailing one in CP. Figure 19.11 reports a typical potential recording obtained by
means of a high frequency acquisition voltmeter (at least 10 Hz sampling fre-
quency) where the so-called OFF potential, Eoff, is the potential value recorded
immediately (within 1 s according to international standards) after current inter-
ruption. Nevertheless, some typical situations should be carefully considered:
• Overprotection conditions. When measurement is taken on coated structures in
overprotection conditions, that is with hydrogen evolution, Eoff potential does
not correspond to the IR-free potential, since the activation overvoltage of
hydrogen evolution disappears very rapidly, in less than 1 ms, so that Eoff >
EIR-free. Therefore, by taking the OFF reading 0.1–1 s after current interruption,
Fig. 19.11 Example of E

potential recording in (V CSE)
ON-OFF technique –0.85
Overpotential
Eoff
–1.00
IR
Eon
–1.15
–100 ms 0 100 ms 10 s Time
error can be as high as 200–300 mV and overprotection condition can not be

recognized;
• Coated structures. When coating holidays of various sizes are present, two
problems arise. The first depends on the different polarisation level achieved by
each defect according to its size: smaller defects are more polarised than larger
ones. The resulting Eoff reading is difficult to interpret and can not be associated
to an isolated defect. The second problem is related to the fact that once the
protection current is interrupted, the more polarized holidays (the smaller ones)
become anodes, releasing some current to the less polarized holidays, acting as
cathodes. The result is the circulation of a so-called equalizing current, which
makes an apparent lower protection on the small holidays and an overestimated
protection on the larger ones;
• Grounded structure. If the ON-OFF technique is applied on a grounded structure
(for examples on a carbon steel pipeline with a copper-made earthing), when
current is OFF, galvanic corrosion between the two metals occurs and the mea-
sured potential is typically the potential of the wider surface, specifically the
grounding system. For this reason, the ON-OFF technique can not be applied
on grounded structures. To overcome this problem, the OFF reading should be
carried out on a buried corrosion coupon, without interrupting pipeline protection,
simply by disconnecting it from the pipeline. The drawback of this device is that an
IR drop contribution, due to the CP current of the pipeline, may still be present.
Close Interval Potential Profile. In case of a coated pipeline in cathodic protection
condition, the monitoring of CP, as well as the localisation of coating defects, can
be worked out by examining the potential profile along the pipeline, as schemati-
cally illustrated in Fig. 19.12. To obtain the profile, an electrical connection with
the pipeline is required and the measurement must be synchronised with the
operator’s movement. The ON potential, Eon, measured before the interruption of
the protection current by a portable reference electrode, may provide useful
information. However, because of IR drop, the Eoff potential profile has to be used.
Two distinct effects are recorded in correspondence with defects: a peak towards
more positive potential values of both Eon and Eoff (the polarisation is lower and
therefore the potential is more positive) and a decrease in ohmic drop measured as
the difference (Eon − Eoff).
Fig. 19.12 On-off potential profile along a pipeline with coating defects
CP of Marine Structures
The exploitation of offshore oil and gas fields developed special structures as
platforms and submerged wellheads with their ancillary components like
pipeline and risers. The most impressive of these structures are the platforms.
Used to locate new deposits or to exploit them, they are fixed or movable,
laying on the bottom by gravity or fixed with piling, designed to operate in
deep waters, depths exceeding 150 m, or semi-submersible or floating and
maintained in position with appropriate anchoring systems. Construction
materials are carbon-manganese steel for tubular structures and reinforced or
pre-compressed concrete for those operating by gravity. A few meters above
the waves area, all the equipment and crushing materials, sludge deposits and
various pumping systems, the power plant and the housing module are
installed on the work platform and sometimes a plant for a first crude treat-
ment. The collateral structures used for the production, transport and tem-
porary storage of crude oil are also of great importance, and must also be
cathodically protected. To name a few: floating tanks, mooring buoys, jets,
pipes that carry crude oil on the surface (risers) or on the bottom (seals), drill
pipes, casings. On the other hand, due to the need to exploit reservoirs in
deep water, early production systems are in use, including delicate parts, such
as well test or collecting groups (manifolds and so-called umbilicals) often
made of non-carbon material, e.g. stainless steel and monel, which are
cathodically protected.
CP is the corrosion protection technique for immersed zones.
ICCP is generally cheaper than GACP, nevertheless is used in practice
only for retrofitting purposes. Some concerns derived from the past
experience of ICCP which faced various failures of cable-anode connec-

tions and premature anode consumption, most likely because anodic current
density was too high. GACP is mandatory when no energy is available;
nevertheless it is mostly used because more reliable, assuring good current
distribution and no need for maintenance. Drawbacks of the method are high
investment cost, high weight and wave induced mechanical load especially
for large size anodes; furthermore, operating conditions are unchangeable.
Anodes normally used are aluminium-based.
Calcareous deposit
Before discussing the CP design in seawater, it is important to draw
attention to the formation of calcareous deposits promoted by the application
of CP, especially to its importance for a fruitful protection condition. As
mentioned in Sect. 19.1.5, the cathodic reaction causes on the cathodic sur-
face an increase in pH. For a protection current density equal to the oxygen
limiting current density, the measured pH is about 10.8–11, and for higher
current density where also hydrogen evolution takes place, pH reaches 11.5.
This pH increase moves the calcium carbonate-bicarbonate equilibrium to the
precipitation of calcium carbonate, CaCO3, as soon as the equilibrium pH,
around 8.7, is exceeded. In addition, magnesium hydroxide precipitates when
pH exceeds 10.
Protection potential
The exploitation of offshore oil and gas reservoirs started in the Gulf of
Mexico after World War II (more than 1000 platforms were present in 1960)
followed by the North Sea. The analysis of failures occurred in the 1950s and
1960s indicated two main reasons: plastic collapse due to overloading by
action of hurricanes on structures weakened by generalized corrosion and
generalized corrosion itself.
From this experience, a design philosophy developed and extended to all
other seas that consisted of a mechanical design to withstand the maximum
loads induced by so-called 100-year storm and the application of CP. The
experience demonstrated that a protection potential of −0.8 V Ag/AgCl was
sufficient to reduce generalized corrosion; indeed, it was proved that even
potential in the range −0.7 to −0.75 V Ag/AgCl could stop corrosion effi-
ciently, extending the life from 3 to 5 years without CP to more than 30–
40 years.
In practice, more negative potentials are recommended, on one hand to
allow the formation of beneficial calcareous deposits, and on the other hand
also to prevent MIC by SRB particularly at sea bottom. Hence, the recom-
mended protection potential is −0.9 V Ag/AgCl.
Protection current
By adopting a protection potential of –0.8 V Ag/AgCl, the cathodic pro-
cess is oxygen reduction under diffusion control, then approximating the
oxygen limiting current density. The build-up of the calcareous deposit
reduces the oxygen availability with time and accordingly the protection
current density. For example, based on local conditions, adopted protection
current density is 65 mA/m2 in Gulf of Mexico, 85 mA/m2 in Persian Gulf
and or West Coasts of United States, West Africa and Australia, 120 mA/m2
in Mediterranean Sea and 250 mA/m2 in the North Sea.
Typical protection current density values are given in Table 19.9.
Values in Table 19.9 or from standards are the initial ones, then after the
so-called polarization period, lasting about a few months where calcareous
deposit forms, protection current density drops by about 30–50%. Calcareous
deposit starts forming near galvanic anodes where current density is higher,
then spreading far away; according to this mechanism, an initial uneven
current distribution helps the polarization, hence galvanic anodes are more
suitable than impressed current by remote anodes.
Specific conditions affect protection current density, as vibrations or hot
surfaces, for example the so-called hot risers; for the latter, because strong
convection sets up, the oxygen limiting diffusion current density increases by
two or three times.
Finally, once again, it must be emphasised the importance of the build-up of
the calcareous deposit, which is affected by: hydrodynamic conditions, such as
strong turbulence associated with the abrasive action of suspended solids; the
first period of polarisation; the quality of calcareous deposit: low porosity, high
thickness, good adhesion and mechanical strength to resist turbulence and
abrasive actions. High initial current densities assure the best characteristics.
Current and Potential Distribution
Current output
As previously stated in Sect. 19.2.1, the current output depends on anode size
and seawater resistivity. As the latter is function of temperature, output varies
considerably from tropical to Arctic regions, as well as with seasons and
depth. For example, from the Persian Gulf to Gulf of Mexico and to the North
Sea (where the benefits of the Gulf Stream are present) to even colder seas,
Table 19.9 Protection Environment Protection current density (mA/m2)

current density for marine
structures Seamud 20–33
Stagnant seawater 50–110
Typical condition 60–140
Stormy seawater 130–550
Hot pipelines 120–600
for example in Alaska, water resistivity increases from 0.2 X m up to

0.5 X m; hence anode output decreases proportionally.
However, because in colder seas, with higher resistivity, the protection
density is also the highest, ohmic drop is not anymore localized on the anode
only. For example, in North sea with resistivity 0.3 X m or more, protection
current density exceeds 150 mA/m2, hence ohmic drop within 1 m in
cathodic region may also be 50 mV: consequently, driving voltage reduces
by about 20% and also current output.
Potential distribution
Once checked that the CP system can deliver the protection current, po-
tential distribution must be verified throughout the structure. As complexity
and size of the structure increase, the difficulty of this task also increases,
because for tubular jacket-like structures like platforms, neither few remote
external anodes nor insulating screens are suitable; instead, anodes inside the
structure are necessary.
Furthermore, potential distribution needs to take into account specific local
conditions, as for example, complex nodes for which ohmic drop is not neg-
ligible, so that potential ennobles by more than 100 mV compared to the one
far away from them. Besides nodes, under-protection conditions may occur at
numerous local situations as shadowed areas, recesses and shielded zones.
Overprotection
In GACP systems, anodes are installed preferably far from surface and not
directly in contact with the structures or on a shield. This reduces high anode
consumption, as well known in applications other than those of off-shore
structures, for example tanker tanks.
In ICCP systems risk of overprotection is much higher due to the higher
driving voltage. Adopted solutions are similar to those for galvanic anodes, as
distance from structure and use of shields. The availability of a variety of size
and shape of anodes in combination with their number helps avoid over-
protection conditions.
Current demand versus current availability
Anode current output and current requirement or protection current must
balance. For ICCP systems, this condition is easily achieved because current
can be changed manually or automatically; instead for GACP, in spite of an
intrinsic self-regulating current output capacity, the problem exists and is
difficult to solve if not properly considered in the design phase. In fact,
current output variation with time has to be forecast in design, by changing
shape, number and size of anodes, for example to obtain a high initial output
to facilitate the calcareous deposit buildup. In the past bi-anodes, zinc cored
with a magnesium shell were proposed for the same purpose.
Cyclic variations of protection current occur as environmental conditions

change (turbulence, temperatures, oxygen content) due to tides and seasons;
by damaging the calcareous deposit, storms provoke an increase of protection
current up to the maximum initial values.
Finally, protection current may increase with time simply because the
surface of the structure increases due to additional auxiliary structures as well
casings installed after platform installation.
A critical situation to be investigated in design is the one at the middle of
design lifetime when a depolarization occurs after an exceptional violent
storm, because there is the risk that anodes are no longer able to repolar-
ize the structure by rebuilding the calcareous deposit. Obviously, this is a
critical situation because the structure corrodes and anodes consume rapidly.
19.3 Anodic Protection (AP)
Anodic protection was first experienced by C. Edeleanu in 1954. It is applied to

active-passive metals for bringing the potential inside their passivity interval by
means of an anodic polarization, obtained, as shown in Fig. 19.13, by an electrical
circuit where the structure is the anode connected to the positive pole of a DC
Fig. 19.13 Schematic Potentiostat

representation of the anodic
protection of a stainless steel
tank containing sulphuric acid
Reference electrode
Cathode
(a) (b)
E E
Etr Etr
Ep Ep
Epp Epp
ip ic icorr ia icp log i ip icorr icp log i
Fig. 19.14 Anodic protection principle: a the metal remains passive after the anode current is
interrupted; b the metal returns under active conditions if the protection is interrupted
feeder and a cathode, connected to the negative pole, is immersed in the solution.
The potential is maintained in the passivity interval by a potentiostatic control.
Figure 19.14a illustrates the principle of the method. For instance, with reference
to a stainless steel in sulphuric acid, point ① represents the initial corrosion con-
dition as active behaviour. Starting from Ecorr (i.e., point ①), to achieve an anodic
polarization an increasing external current (ie = ia − ic) has to be supplied, which
initially causes an increase in the corrosion rate, expressed by ia; then, once reached
the primary passivation potential, Epp, the external current decreases sharply
because passive conditions are achieved (point ②). To reach this condition, the
external current must exceed the critical passivation current, icp. The potential
should be fixed to a value neither too high to avoid transpassivity conditions, nor
pitting potential if chlorides are present.
In general, there may be two cases: the first where passive conditions, once
established, persist even when the external current is interrupted (Fig. 19.14a); a
second case in which the protective action terminates as current stops (Fig. 19.14b).
19.3.1 Electrode Reactions
On the structure surface, the anodic reaction is the formation of passive film, as
follows:
xM þ yH2 O ! Mx Oy þ 2yH þ þ 2ye ð19:14Þ

19.3 Anodic Protection (AP) 409
with possible competing reaction of oxygen evolution:
2H2 O ! O2 þ 4H þ þ 4e ð19:15Þ
On the cathode in neutral or alkaline environments, cathodic reaction is the re-

duction of oxygen, while in acidic solutions, as in most of applications, hydrogen
evolution prevails.
In neutral or alkaline electrolytes, anodic reactions cause a slight acidification on
the metal surface; this effect is exploited in seawater for titanium components,
typically on submarines, because the decrease in pH inhibits the fouling growth.
19.3.2 AP Applications
The anodic protection has found various applications for reducing the corrosion rate
of passivating metals in highly aggressive electrolytes (acids, bases and saline
solutions) as shown in Table 19.10.
The most known application deals with the storage of concentrated sulphuric
acid in carbon steel tanks: AP reduces corrosion rate by two orders of magnitude as
well as iron ions contamination and the amount of hydrogen developed, hence
reducing the related hazards.
Again in concentrated sulphuric acid, AP is applied as prevention method of
corrosion-erosion of AISI 316L in heat exchanger tubes. Without AP, this attack is
particularly severe (with penetration rates of several mm/year) because the passive
film, enriched with iron, chromium and nickel sulphates, is mechanically unstable.
Conversely, AP converts that film into oxides that have better mechanical resis-
tance, hence able to withstand the turbulent regime even at high temperatures.
19.3.3 AP Versus Active-Passive Metals
The anodic characteristic, E − logi, of the active-passive metal determines whether

AP is possible, easy and effective, through the following parameters:
Table 19.10 Typical anodic protection applications

Metal Electrolyte
Carbon Oleum, sulphuric acid, phosphoric acid, ammonia in aqueous solution, aqueous
steel ammonium nitrate solutions, aqueous ammonia and ammonium nitrate
solutions, ammonium nitrate and urea
Stainless Sulphuric acid, sulphuric and nitric acid mixtures, phosphoric acid, aqueous
steel ammonium nitrate solutions, aluminium sulphate aqueous solutions, caustic
soda, sulphonic acids, oxalic acid, sulphamic acid
Titanium Sodium chloride solutions, rayon industry, chlorides of Cr2+ and Cr3+
• Critical passivation current density, icp, which determines the maximum current
needed (easiness, feasibility)
• Passivity current density, ip, which measures the residual metal dissolution rate
(effectiveness)
• Passivity interval, e.g. the difference between the primary passive potential and
the transpassive potential, which defines upper and lower limits of potential
range (possibility, feasibility, easiness).
Titanium, for example, passivates more easily than steel in the vast majority of
environments, because both icp and ip are small. Similarly, austenitic stainless steels,
particularly those containing molybdenum, are better than ferritic ones because of low icp.
Both the passivity current density, ip, and the critical passivation current density,
icp, depend on both metal and environment nature, composition and temperature
(Table 19.11).
Table 19.11 Operating variables for anodic protection of different materials in different
environmental conditions
Metal Environment Temperature Critical current Passivity current
(°C) density, icp (mA/m2) density, ip (mA/m2)
AISI 304 H3PO4 (115%) 24 0.15 1.5 10−3
H3PO4 82 0.31 1.5 10−3
H3PO4 177 650 22
HNO3 (80%) 24 25 0.31
HNO3 82 120 3.1
H2SO4 (67%) 24 50 103 1
H2SO4 82 46 2.9
NaOH (50%) 25 9 4.4 10−3
AISI 316 H3PO4 (75–80%) 104 – 140
H3PO4 121 – 350
H3PO4 135 – 440
H2SO4 (67%) 24 5 103 1
H2SO4 66 40 103 3
H2SO4 93 110 103 9
Carbon steel Oleum 25 1.1 4.4 104
H2SO4 (96%) 27 – 11
H2SO4 49 – 120
H2SO4 93 – 1.1 106
Alloy 20 H2SO4 (50%) 120 – 10
Titanium H2SO4 (40%) 60 200 0.2
Often, the presence of contaminants and impurities is important; for example,

a small content of chlorides in concentrated sulphuric acid can change by more than
one order of magnitude icp and ip for either carbon steel or stainless steels.
The upper limit of passivity range depends on metals; for example for titanium,
it is always in the order of several volts although it varies with environmental
conditions; for carbon steel in concentrated sulphuric acid, it varies from about 2 to
5 V when the concentration of acid increases from 67 to 96%.
The passivity interval of carbon steel and stainless steels does not generally
exceed 1 V and shortens considerably, especially at high temperatures or when
depassivating species such as chlorides are present.
19.3.4 Throwing Power of AP
The throwing power of AP is generally higher than that of CP, at least once met the
passive conditions, for the following reasons:
• Currents are small
• Electrolyte conductivity is high
• The resistance of passive films is high.
Table 19.12 shows the passivity current density, ip, and film resistivity in typical
applications. It appears that there is a relationship: as one grows the other decreases.
The throwing power of AP is so high that passivation is easily achieved even for
equipment with complex geometry, with uniform distribution of potential, although
primary distribution would be strongly uneven. For example, for carbon steel pipes
carrying concentrated sulphuric acid (although passivity current density, ip, is high
and oxide resistivity is low) cathode distance from tube inlet with diameters 25, 50
and 150 mm can be 3, 5 and 9 m, respectively.
For opposite reasons, the throwing power is not good in the initial phase
especially when critical passivation current density, icp, is high and in the presence
of interstices, where the achievement of AP may be critical. For example, com-
paring laminated against wrought stainless steel plate (AISI 304 vs. CF-8 type) the
Table 19.12 Passivity current density and resistivity of passive film in 67% sulphuric acid
applications
Metal Passivity current density, ip (mA/m2) Oxide film resistivity (kX m)
Carbon Steel 150 0.26
AISI 304 2 5
AISI 310 1.5 21
AISI 316 1 180
Titanium 0.8 180
Alloy 20 0.3 460
potential and current distribution inside a crevice by imposing different external

potentials would show strongly different behaviour because icp is different:
• The AISI 304 laminated plate, with low icp, passivates perfectly inside crevice
even with external potential +0.2 V SCE
• CF-8, with high icp, does neither passivate completely under the same condi-
tions, nor with an external potential as high as +0.8 V SCE, that is, the maxi-
mum potential before falling into transpassivity.
This is because the throwing power is low before current exceeds icp inside the
interstice, as two out of three necessary conditions are absent: high current density
and low oxide film resistance. In conclusion, in the presence of crevices, cracks or
interstices, AP is driven, besides the geometry and the external potential, by the
value of the critical passivation current density, icp. Accordingly, for metal/
environment couples with very high icp AP works satisfactorily only in the absence
of cracks or after passivation pretreatments carried out in suitable environments.
19.3.5 Potentiostatic Feeding
To apply AP a potentiostat is necessary. As mentioned in Chap. 29, the potentiostat

is an electronic device able to maintain a prefixed potential, by regulating auto-
matically the circulating current between the structure and a counter electrode (the
cathode). The potential, E, is measured by a reference electrode and compared with
the prefixed protection potential. The feeder uses the difference to vary dynamically
the current until the potential scatter zeros (Fig. 19.15).
ΔE = E - Ep
Ep
Anode Cathode
(structure)
Reference
electrode
Fig. 19.15 Operating scheme of a potentiostat

Power of the feeder. To set up the protection, a current proportional to icp is

necessary while the one to maintain passivity conditions is proportional to ip. These
two currents differ by orders of magnitude. For example, based on data shown in
Table 19.11, AP of a stainless steel AISI 304 tank containing concentrated sul-
phuric acid (67%) requires 5 A/m2 to reach passive conditions, while only 1 mA/m2
to maintain it. To avoid immobilizing an expensive high power feeder not neces-
sary once AP conditions are met, different strategies are used:
• Pre-passivation treatments by employing low icp electrolytes (for example, using
phosphoric acid which shows icp two or three orders of magnitude lower than
sulphuric acid)
• Addition of anodic inhibitors to reduce icp
• Lowering the temperature
• Step-by-step passivation obtained by a progressive partial filling operation.
Generally, the time needed to reach passive conditions is very short, in the order
of minutes; however in a few cases, longer times are required as for cast iron tank
containing boiling concentrated sulphuric acid (75–96% at 310 °C). In this case,
passivation starts with acid at 60 °C, then increasing temperature by steps of 20 °C
per hour. For example, with a tank surface of 20 m2, the initial current is 130 A,
after 24 h as target temperature is reached, current drops to 30 A, then to 5 A after a
week and finally to 3 A after one year.
Consequences of feeding current interruption. By interrupting the current, the
system goes back to free corrosion in active condition. This is not so harmful if AP
has the aim to reduce metal ion pollution when the metal itself resists enough
corrosion (for instance, in concentrated sulphuric acid tank applications); con-
versely, consequences can be catastrophic when free corrosion conditions match
with high corrosion rates (Fig. 19.14b): in this case, other prevention methods than
AP are necessary.
19.3.6 CP-AP Comparison
Table 19.13 reports and compares the main features of the two techniques. It is
worth mentioning that an imperfect CP is almost never more harmful than its
absence, instead an insufficient AP can result in disastrous attacks, even more
serious than without its application. Only a correct AP leads to a strong reduction of
corrosion rate.
It is also interesting to compare CP by passivity and CPrev and AP. For all of
them, passive conditions are set up: the first two by supplying a cathodic current,
while in the latter by an anodic current.
Table 19.13 Comparison between AP and CP

Anodic protection Cathodic protection
Metal Only active-passive All
Only bare Bare or coated
Attention to amphoteric and less noble
Environment From low to high Low to moderate aggressive
aggressive
Throwing power Relatively high Generally low
Good with coating or low protection
current density
Protection current Comparable to passivity Depends on environment
current Determined by the coating efficiency
Depends on metal
Design parameters Determined in lab From practice
Empirical
Cost per plant unit Medium Low
Cost of operating Very low Low to medium
Partial protection Harmful Always beneficial
conditions
• ASTM B 843—Standard Specification for Magnesium Alloy Anodes for

Cathodic Protection.
• ASTM F 1182—Standard Specification for Anodes, Sacrificial Zinc Alloy.
• DNV RP B401—Recommended practise for Cathodic Protection design in
seawater.
• EN 12495—Cathodic protection for fixed steel offshore structures.
• EN 12496—Galvanic anodes for cathodic protection in seawater.
• EN 12499—Internal cathodic protection of metallic structures.
• EN 12696—Cathodic protection of steel in concrete.
• EN 12954—Cathodic protection of buried or immersed metallic structures—
General principles and application for pipelines.
• EN 13509—Cathodic protection measurement techniques.
• EN 14505—Cathodic protection of complex structures.
• EN 15280—Evaluation of a.c. corrosion likelihood of buried pipelines appli-
cable to cathodically protected pipelines.
• ISO 12473—General principles of cathodic protection in seawater, International
• ISO 15257—Cathodic protection—Competence levels of cathodic protection
persons—Basis for certification scheme, International Organization for
Standardization, CH-1211 Geneva 20.
• ISO 15589-1—Petroleum, petrochemical and natural gas industries—Cathodic

protection of pipeline systems—Part 1: On-land pipelines, International
Organization for Standardization, CH-1211 Geneva 20.
• NACE SP0169, Recommended Practice: Control of External Corrosion on
Underground or Submerged Metallic Piping Systems, NACE Int., Houston, TX.
• NACE SP0675, Recommended Practice: Control of Corrosion on Offshore Steel
Pipelines, NACE Int., Houston, TX
• NACE SP0176, Control of Corrosion on Steel Fixed Offshore Platforms
Associated with Petroleum Production, NACE Int., Houston, TX.
• NORSOK M-503, Cathodic Protection, Lysaker, Norway.
19:1 Discuss by means of Evans diagram the three following cathodic protection
criteria: cathodic protection by immunity, by quasi-immunity and by passivity.
19:2 What is the protection criterion used for carbon steel in aerated soil? What is
the recommended potential range? Can the protection criterion by immunity
be applied to aluminium in pitting condition? Why?
19:3 What are the drawbacks of overprotection condition of a carbon steel coated
pipeline?
19:4 The cathodic protection potential of carbon steel in aerated soil is −0.85 V
CSE. Estimate the residual corrosion rate at the protection potential con-
sidering that in free corrosion condition (−0.65 V CSE), the corrosion
current density is about 0.1 A/m2. Consider the Tafel slope of steel disso-
lution reaction equal to 0.1 V/decade.
19:5 What are the main parameters that affect cathodic protection current density
in seawater? Estimate the cathodic protection current density in the fol-
lowing conditions: (a) seamud; (b) stagnant seawater; (c) cold stormy
seawater; (d) propeller zone in ships.
19:6 Demonstrate that the driving voltage of a cathodic protection employing a
Zn-based galvanic anode to protect a steel structure is 250 mV. Explain
why it is independent of the electrolyte.
19:7 What are the main constituents of an anode backfill of a galvanic anode for
cathodic protection application in soil? How does the backfill affect anode
current output?
19:8 What are the electrochemical reactions on an insoluble anode for ICCP
system in seawater? Which is the prevalent reaction? Discuss the effect on
anodic current density.
19:9 Demonstrate that the term W* which is the thermodynamic and kinetic
contribution of electrode reactions in an ICCP system is about 0 for steel
anodes and 2–3 V for inert ones. Show that for seawater applications it is
lower than in soil application.
19:10 Consider an ICCP system of the external bottom of a carbon steel tank in
soil, connected to a copper grounding network. A deep vertical anode is
used to supply the protection current. Which cathodic current would you
design for carbon steel bottom tank (10 m diameter) and for the grounding
network (8 copper nets, 1.5 m length and 30 mm diameter)? Which is the
power supply of the DC feeder you suggest?
19:11 Explain why a high impedance voltmeter is used to make accurate mea-
surement of pipe-to-soil potential. Why shall the internal impedance be
higher if a MMO-Ti reference electrode is used rather than a CSE reference
electrode?
19:12 Discuss the main drawbacks of the use of the ON-OFF technique for
cathodic protection assessment.
19:13 Consider the following potential measurements of a buried carbon steel
pipe: (a) E = −1.35 V CSE: measured by a potential probe with internal
reference electrode; (b) E = −1.75 V CSE measured by a portable CSE
reference electrode in ON condition; (c) E = −1.10 V CSE: measured by a
portable CSE reference electrode in OFF condition. Is the pipe in over-
protection condition? Calculate ohmic drop contribution in ON-OFF
technique.
19:14 Estimate the cathodic protection current density of carbon steel in neutral
fresh water and in acidic solution (pH 3) to polarize the metal to −1.2 V
CSE. Oxygen limiting current density is 0.1 A/m2 and Tafel slope of
hydrogen evolution 0.12 V/decade.
19:15 Determine the design parameters for anodic protection of an AISI-304 tank
to store 10 m3 of sulphuric acid 65% at 50 °C.
Humphry Davy, Alessandro Volta and the Cathodic Protection2

The Priority of Humphry Davy
In 1823, the British Admiralty commissioned Sir Humphry Davy to inves-
tigate the corrosion of copper sheathing of the hulls of wooden ships of that
time. The following year, before the Royal Society of which he was
President, he read a paper in which he announced the discovery of the method
to control metal corrosion nowadays called «cathodic protection».
«In the Bakerian Lecture for 1806, I have advanced the hypothesis [..] that
the chemical attractions may be exalted, modified or destroyed by changes in
electrical state of bodies; that substances will only combine when they are in
different electrical states; and that by bringing a body naturally positive
artificially into a negative state its usual powers of combination are alto-
gether destroyed. [..]
2
This paper is extracted from Pietro Pedeferri, Humphry Davy, Alessandro Volta and the cathodic
protection, Istituto Lombardo: Accademia di Scienze e Lettere, 2001.
It was in reasoning upon this general hypothesis likewise, that I was led to
the discovery. Copper is a metal only weakly positive in the electro-chemical
scale; and accordingly with my ideas it would only act upon sea water when
in the positive state; and, consequently if it could be rendered slightly neg-
ative the corroding action of sea water upon it would be null. [..] But how
was this could be to be effected? I at first thought of using a Voltaic battery;
but this could hardly be applicable in practise. I next thought of the contact of
the zinc, tin or iron. I resolved to try some experiments on the subject. I began
with an extreme case. I rendered sea water slightly acidulous by sulphuric
acid, and I plunged into it a polished piece of copper, to which a piece of tin
was soldered equal to about one twentieth of the surface of copper. Examined
after three days the copper remain perfectly clean whilst the tin was rapidly
corroded: though in the comparative experiment, when copper alone and the
same fluid mixture was used, there was a considerable corrosion of copper».
[1]
Meanwhile Davy had advised the Admiralty to utilise the new idea. Cast
iron and zinc plates were installed on three copper-sheeted ships in record
time. The iron anodes proved to work and halted the corrosive process but,
unfortunately, unforeseen side effects, such as the development of marine
fouling organisms on copper no longer hindered by the toxic action of its
corrosion products, made it unfeasible: fouling reduced the speed of ships
under sail and the Admiralty decided against the new protection technique.
The method’s failure greatly vexed Davy. He was, as he said, «burned out».
Nearly a century passed before the technique proposed by Davy would
regain credibility and be utilised with the name of cathodic protection to
prevent corrosion of buried structures, oil and gas pipelines, offshore plat-
forms, marine reinforced concrete constructions, ships, chemical reactors or
simply to prolong the service life of the electric water heaters in our homes.
The world of cathodic protection recognises that Davy first applied the
cathodic protection in 1824 and also first understood the principle which it is
based on. On the occasion of the second centennial celebration of invention
of the pile, I am happy to prove that the second priority belongs to Alessandro
Volta. Until now this fact has been overlooked.
The Priority of Alessandro Volta
Alessandro Volta in a paper to the editors of the Swiss magazine
«Bibliothècque Britannique» in 1802 [2]—and «lu par l’auteur a la Societé
de phisique e d’histoire naturelle de Geneve dan la séance du 27e ventose»
(March 18th) of that year—wrote (Fig. 19.16):
L’oxydation est en partie indépendante de l’action galvanique, ou pour mieux dire

électrique; car elle est l’effet chimique ou ordinaire de tel ou tel fluide, sur tel ou tel
métal; elle en dépend aussi en partie, en tant que le courant électrique modifie
singulièrement cette oxydation, en l’augmentant beaucoup dans le métal d’où le
courant sort pour passer dans l’eau ou tout autre liquide oxydant, et en le diminuant
ou supprimant tout à fait dans le métal où le courant électrique entre, et où le gaz
hydrogène se développe. Ainsi donc, le courant électrique exerce une action oxy-
dante et une désoxydante, suivant qu’il passe d’un métal dans un liquide o du liquide
dans le métal.
In these few lines, Volta makes three crucial statements:

• First of all, he explains that the oxidation rate of a metal which exchanges
current with a solution depends in part on the corrosive processes that take
place on the metal and in part on the current exchanged («Oxidation is
partially independent of galvanic or better electric action: because it is
the usual chemical effect of one or the other agent on this or that metal; it
is in part dependent on this action because the electric current modifies in
a singular manner this oxidation»)
• Second, he observes that the oxidation rate increases when the current
leaves the metal and passes into solution («The oxidation increases very
much on the metal from which the current goes out for entering in water or
any other oxidising liquid»). This occurs, for example, when a metal
immersed in an aqueous solution is coupled with a more noble one, and in
general when, as we say today, the metal is polarised in the anodic
direction.
• Finally, he points out that the rate of oxidation decreases if the current
passes from the solution to the metal even to the point of extinction where
hydrogen is evolved. («The oxidation decreases or entirely suppresses it
on metal in to which current enters and on which hydrogen is evolved».)
This occurs, for example, to a metal coupled with a less noble or when, as
we say today, the metal is cathodically polarised or when cathodic pro-
tection is applied to it.
First Point
As far as the first point is concerned, no one before Volta had ever described
what happens to a corroding metal when it exchanges galvanic current with
the solution in which it is immersed. Nobody had before explained the cor-
rosion phenomena and the corrosion rate in term of ‘local corrosion’ and
external polarisation so clearly and correctly.3
3
Piontelli wrote: «Volta’s attitude against the ‘chemical theories’ must be considered remembering
that the chemical phenomena considered at this epoch very often were ‘local processes’ at the
electrodes». [3] According to Piontelli many of the theories of the pile given after Volta where
affected by the confusion between local chemical phenomena at the metal surface/solution and the
chemical reaction connected with the current.
Obviously Volta, like Davy few years later, did not realise that corrosion
was an electrochemical phenomenon even if he stated that galvanic current
can stop corrosion. The belief that the mechanism of corrosion is electro-
chemical will be expressed by de la Rive only in 1830. It is worth underlining
how the concepts expressed by Volta in 1802 will have their complete
clarification more than one hundred years after, in the period between the two
world wars. In particular, the confusion between local ‘chemical’ phenomena
and the ones produced by galvanic current will end only in 1938 when Hoar,
Mears and Brown gave the basic electrochemical theory of cathodic protec-
tion and Wagner and Traud the one of mixed potentials.
Second Point
With regards to the second point, observations had already been made, even
before the invention of the pile, showing how the corrosion rate of a metal
increases when it is in contact with a more noble metal. This type of corro-
sion, which today we call galvanic or bimetallic, had firstly been described by
Giovanni Fabbroni in 1792 in a paper given to the Accademia dei Georgofili
of Florence in 1792 but printed only in 1799 [3].4
Immediately following the invention of the pile, there was a proliferation
of observations on the fact that corrosion increased in metals coupled with a
positive pole during the functioning of the pile (Nicholson, Davy, Wollaston).
Volta himself in a letter dated September 22nd, 1800 to Landriani [4] writes
that already in April 1800 he had shown to Brugnatelli not only the devel-
opment of hydrogen and oxygen but also the calcination of metals and par-
ticularly of zinc in the areas in contact with water. But until 1802 everybody
thought that the corrosion which took place on the metal «from which the
current goes out for entering in water or any other oxidising liquid» was due
only to the current exchanged, while this was a part of the oxidation process,
as correctly stated by Volta.
4
Fabbroni wrote: «J’avois observé aussi que l’alliage employé a la soudure des plaques de cuivre
qui couvrent le toit mobile de l’Observatoire de Florence, s’étoit promtement altéré, chargé
manifestement en oxide blanc à son conctact extreme avec ce métal. J’avoix appris [..], en
Angleterre, que le clous de fer dont on se servoit autrefois pour assujettir le feuilles de cuivre
employées au doublage des vaisseaux, les rongeoient tellement par leur conctact que bientôt le trou
étoit dilaté, jusqu’à surpasser la tête de clou qui le retenoit. Il me parut qui il n’en falloit pas
davantage pour reconnoître que les métaux exerçoient dans set cas un action réciproque, et que
c’etoit elle qu’on devoit attribuer le cause des phénomènes qui s’opéroient par leur réunion ou
contact». With observations like these Fabbroni laid the foundations both of the chemical theory of
galvanism and of the electrochemical theory of corrosion.
Third point
Finally with reference to the third point that regards the effects of cathodic
polarisation, Volta was the very first to state that if the metal is cathodically
polarised, the oxidation rate of a metal decreases even to the point of
extinction (Pourbaix after 150 years would have said immunity). Volta was
thus the first to understand the principles underlying cathodic protection and
to describe its effects including side effects such as the development of
hydrogen. Today every specialist in cathodic protection knows that when
steel—or any other more noble metal like tin, nickel or copper—is polarised
to the point that hydrogen develops on its surface, corrosion stops. Volta had
already grasped this point in 1802.
Conclusion
No doubt exists that Davy in 1824 was the first to apply cathodic protection
and that Volta in 1802 was the first to express the basic principles of this
technique.
References
[1] Davy H (1824) Phil. Transactions, 114, part 1.
[2] Volta A (1923) Bib. Brit., 274 e 339, 1802. Opere di Volta, Ed.
Nazionale Tomo II, 151, Milan, Italy.
[3] Piontelli R (1961) On the theory of electrochemical systems, C. R. 3e
Reunion CITCE, Milan, Italy, 357.
[4] Fabbroni G (1799) Journal de Physique, 49, 348.
Fig. 19.16 Excerpt from the letter «Aux rédacteurs de la Bibliothèque Britannique» (March 18th, c
1802), in which Volta illustrates the principles of cathodic protection. The letter is kept in the
«Cartellario Voltiano» at «Istituto Lombardo di Scienze e Lettere» in Milan, Italy: «…oxidation is
partially independent of galvanic or better electric action: because it is the usual chemical effect of
one or the other agent on this or that metal; it is in part dependent on this action because the electric
current modifies in a singular manner this oxidation. The oxidation increases very much on the
metal from which the current goes out for entering in water or any other oxidising liquid. The
oxidation decreases or entirely suppresses it on metal in to which current enters and on which
hydrogen is evolved. The electric current produces an oxidant or a reducing action as it passes
from the metal into the liquid or from the liquid into the metal…»
Bibliography
Bianchetti R (2001) Peabody’s control of pipeline corrosion, 2nd edn. Nace International, Houston
Ashworth V (1982) Cathodic protection theory and practice. The Present Status. In: 1st
international conference, Coventry, UK, 28–30 April 1982
Ashworth V (1989) Cathodic protection theory and practice. In: 2nd international conference,
Stratfordon-Avon, UK, 24–28 June 1989
Lazzari L, Pedeferri P (1981) Protezione catodica. CLUP, Milano, Italy
Lazzari L, Pedeferri P (2006) Cathodic protection. Polipress, Milan, Italy
Morgan JH (1992) Cathodic protection. Nace International, Houston
Peabody AW (1967) Control of pipeline corrosion. Nace International, Houston
von Baeckman W, Schwenk W, Prinz W (1997) Handbook of cathodic corrosion protection.
Theory and practice of electrochemical protection processes, 3rd edn. Gulf Publishing-Nace
International, Houston
Chapter 20
Corrosion in Waters
Water is smooth and spreads softly, but can corrode rocks

and also destroy rigid and hard things.
This is another paradox: what is soft is strong.
Lao-Tsu (600 b.c.).
Abstract All natural and industrial waters are corrosive toward common con-
struction metals if a cathodic process can occur. Oxygen reduction is the most typical
cathodic process, for about 95% of dealings, then followed by slightly acidic con-
ditions, the presence of oxidizing species as chlorine and more rarely by bacteria. An
important factor that reduces water corrosiveness is the tendency to form protective
scales. The main damages due to corrosion are alteration of water quality, especially
for drinking water requirements, reduction of components service life, due to wall
perforation or other localized corrosion forms, and obstruction inside small pipes due
to the high volume of corrosion products. The performance of most used metals are
reported with reference to their use in freshwater, brackish and seawater.

https://doi.org/10.1007/978-3-319-97625-9_20
424 20 Corrosion in Waters
20.1 Types of Water
Waters differs according to the chemical composition and physical properties, as

resistivity and pH. The most known types of water are:
• Distilled or demineralized water, with a very low amount of salts, and a re-
sistivity higher than 20,000 X m
• Freshwater, characterized by a low salinity level, less than 2 g/L. According to
its origin, freshwater is divided in rainwater, surface water and groundwater:
– Rainwater is the product of condensation of water vapour in atmosphere and,
in theory, should be chemically pure water. However, in industrial and
densely populated areas, rainfall dissolves a series of gases, in particular
nitrogen and sulphur oxides, which provide, together with CO2, an acidic
character to rain. Varying amounts of solids, organic substances and even
bacteria are also often present
– Surface waters (rivers, lakes, ponds) contain highly variable concentrations
of organic matter and minerals due to the contact with atmosphere and soil
and because of urban and industrial sewage. Salt content is function of
geology of soil and is usually between 50 and 1000 ppm; in Italian rivers it
varies between 150 and 300 ppm
– Groundwater percolating through the soil (water table, artesian springs)
undergoes a natural filtration process that removes suspended solids and
bacteria and dissolves the minerals composing soil and rocks, in a variable
amount that depends on the chemical nature. For example, in CO2 containing
water in contact with gypsum (CaSO4⋅2H2O) or limestone (CaCO3 and
MgCO3) there is an enrichment with Ca2+ and SO42− or Ca2+, Mg2+ and
CO32−, respectively
• Potable (drinking) water is the most important freshwater from the corrosion
viewpoint. Its origin can be groundwater (as in Italy) or obtained by
chemical-biological treatments of surface waters. Basic requirements for potable
water are the absence of bacteria, limitations of the content of chemical species
dangerous to health, maximum level of ions (chlorides and sulphates lower than
250 ppm, sodium lower than 200 ppm, resistivity higher than 4 X m, total
dissolved salts lower than 1.5 g/L. The European Directive 98/83/EEC lists all
the requirements for a water to be considered for human consumption
• Industrial waters, characterized by a wide range of chemical composition, with
a salinity varying from few ppm to some g/L. Some of the industrial waters are
treated with oxygen scavengers to reduce oxygen content, with biocides to kill
aggressive bacteria and with other compounds to control composition and above
all pH
• Brackish water and seawater. When salinity exceeds 2 g/L water is defined as
brackish. Seawater is the most abundant “brackish” water, with an average
salinity of 34–36 g/L
20.1 Types of Water 425
• Formation water is associated with oil or multiphase hydrocarbons, which are

extracted from the reservoir. It is characterized by a very high ionic content,
typically from 3 to 4 times that of seawater, and a slightly acidic pH. Formation
waters are practically oxygen free, but rich in CO2 and H2S: the main cathodic
process is hydrogen evolution. Corrosiveness of formation water is described in
Chap. 24.
20.2 Factors Influencing Corrosion Likelihood
According to the international standard EN 12502, corrosion of metals in water is

influenced by the following main factors: the cathodic reactant, mainly dissolved
oxygen, which is the responsible for corrosion rate, water hardness and scaling
power, pH, temperature, resistivity, presence of bacteria. On the other side, at a
fixed water aggressiveness, metal composition plays an important role in defining
type of corrosion and corrosion rate. In order to minimize corrosion damages,
special care should be taken during design, construction, commissioning and
operation.
20.2.1 Oxygen Content
Oxygen dissolved in water is the main cathodic reagent. It is always present in

natural waters in contact with the atmosphere: its solubility depends on temperature,
salinity and fluid dynamic regime. Oxygen content in seawater (salinity about 35 g/
L) varies from 9 mg/L at 0 °C, to 6 mg/L at 30 °C, 3 mg/L at 60 °C, to zero at
100 °C (at the pressure of 1 bar). As salinity increases, solubility decreases until
zero above 150 g/L; in the Dead Sea, which is salt saturated (more than 200 g/L),
there is no dissolved oxygen and therefore there is no life and no corrosion for iron.
In natural waters, photosynthesis and fouling may determine local conditions of
either over- or under-saturation or even anaerobic; the absence of oxygen, which
would be ideal to impede corrosion, instead favours microbiologically influenced
corrosion. Dissolved oxygen increases as water velocity increases, reaching a
maximum in turbulent condition.
20.2.2 Water Hardness
Water hardness is a relevant parameter, as it expresses the content of Ca2+ and Mg2+
ions, i.e. ions that contribute to the formation of calcareous deposits. There are three
types of hardness: total, temporary and permanent. Total hardness expresses the
Table 20.1 Classification of Hardness (°F) Classification

water as a function of
hardness 0–7 Soft
7–15 Slightly hard
15–22 Moderately hard
22–35 Hard
>35 Very hard
total content of Ca2+ and Mg2+; permanent hardness is that persisting after boiling
and filtering water; the temporary is the difference between the first two. Hardness
is usually measured in mg/L of equivalent CaCO3 (accounting for both Ca and Mg
contents). For example, if the sum of Ca2+ and Mg2+ equivalents in 1 L of water is
1.5, water hardness is 1.5 50 = 75 mg/L, where 50 is CaCO3 equivalent weight
(MW/z = 100/2). Natural waters have hardness from a few mg/L to hundreds of
mg/L. Hardness is often measured in French degrees (°F) where 1 °F corresponds to
10 mg/L of equivalent CaCO3. Table 20.1 shows the classification of fresh waters
according to hardness.
20.2.3 Scaling Tendency
Depending on composition and temperature, freshwater can form a scale made of

calcium carbonate on the metal surface (Fig. 20.1). This scaling tendency is governed
by the chemical equilibrium of carbonate/bicarbonate precipitation, because calcium
carbonate is insoluble (it is marble) while calcium bicarbonate is highly soluble.
Once formed, the calcareous deposit reduces the oxygen diffusion proportionally
to its thickness and porosity. These properties are summarized through two indexes,
whose meaning is reported in the box, namely:
• Langelier Saturation Index, LSI
• Ryznar Stability Index, RSI.
If the Langelier index is positive (corresponding Ryznar index lower than 6), i.e.
water has a pH higher than that of saturation, the water will have a tendency to
deposit calcium carbonate, then is said “scaling”. If the Langelier index is negative
(corresponding Ryznar index higher than 6), i.e., pH is lower than the saturation
one, water will have a tendency to dissolve any deposits present and is therefore
defined as “aggressive”. Figure 20.2 shows the map of scaling and non-scaling
water as a function of water hardness (expressed as equivalent mg/L of CaCO3 and
pH). Scaling waters, with high values of Langelier index, are typically less cor-
rosive. An aggressive water is corrosive only if a cathodic reactant, i.e., oxygen, is
present.
20.2 Factors Influencing Corrosion Likelihood 427
Fig. 20.2 Scaling and pH

non-scaling water as a
function of hardness and pH
10
Scaling water
8
7
Aggressive water
6
0 50 100 150 200 250 300 350
Alcalinity (ppm as CaCO 3)
Ryznar and Langelier Indexes

Wilfred Langelier1 in 1936 proposed and developed an index, called
Langelier Saturation Index (LSI). It is based on the equilibrium of precipi-
tation of calcium carbonate: Ca(HCO3)2 $ HCO3− + H+ + CaCO3 that is a
function of pH which is controlled by the amount of CO2. The Langelier
index is the positive or negative offset of the water pH from the equilibrium
pH, called saturation pH, pHs. Hence: LSI= pH − pHs.
The saturation pH, pHs, is calculated based on the equilibrium condition
according to the equation:

pHs ¼ logK 2 logK ps log Ca2 þ logA
where: K2 = second dissociation constant of H2CO3; Kps = solubility product

of CaCO3; [Ca2+] = concentration of calcium ions in g ions/L; A = total
alkalinity (alkM) in eq/L. The following relationships are used, depending on
temperature:
T\25 C
pHs = 12.65 − 0.0142(1.8T + 32) − log[Ca2+] − log(alkM) + 0.1log(TDS)
T [ 25 C
pHs = 12.27 − 0.00915(1.8T + 32) − log[Ca2+] − log(alkM) + 0.1log(TDS)
1
Wilfred F. Langelier (1886–1981) was an American chemist. From 1909 to 1916 he worked for
the Illinois State Water Survey. In 1916, Langelier accepted an assistant professorship in Sanitary
Engineering at the University of California, Berkeley, where he remained until his retirement in
1955.
where T is °C; [Ca2+] in mg/L; alkM in mg/L as CaCO3; TDS is total dis-
solved solids in mg/L.
If the index is positive, the water is scaling. If the index is negative, the
water will have a tendency to dissolve scales if present and is said aggressive.
In 1944 the Ryznar Stability Index (RSI) was introduced. It is defined by
the equation:
RSI ¼ 2pHs pH
Ryznar index 6.5 roughly equals Langelier index 0. This index provides a
qualitative and semi-quantitative assessment of either scaling or aggressive
tendency of water: when smaller than 6, water has a scaling tendency and,
conversely, for an index greater than 6 it is aggressive.
Alkalinity M and P
The alkalinity of water defines its ability to neutralize acidic solutions.
Hydroxide (OH−), carbonate (CO32−) and bicarbonate (HCO3−) ions which
are in equilibrium through the reaction:
HCO3 þ OH ¼ CO3 2 þ H2 O
define the alkalinity.

At pH greater than 8.3, only CO32− is present. HCO3− exists only at lower
pH.
Neutralization reactions are:
(1) OH þ H þ ¼ H2 O
(2) CO3 2 þ H þ ¼ HCO
3
(3) HCO3 þ H þ ¼ CO2 þ H2 O
Reaction (2) is complete at pH 8.3, while reaction (3) at pH 4.5.
Phenolphthalein and methyl orange dyes are used as indicators to check
the completion of above reactions after titration of water.
Methyl orange alkalinity (AlkM) is the number of equivalents of strong
acid needed to turn methyl orange colour (around pH 4.5).
Phenolphthalein alkalinity (AlkP) is the equivalents of strong acid needed
to turn phenolphthalein (around pH 9).
The alkalinity of water gives information on its buffering power, i.e. the
ability to receive additions of acidic substances without changing pH
significantly.
20.2 Factors Influencing Corrosion Likelihood 429
Acidity P
The acidity of water (named AcidP) is measured by titration with an alkaline
solution to turn phenolphthalein. It measures the amount of free CO2 present.
This parameter is used to determine the aggressiveness toward steel and zinc.
20.2.4 Water Resistivity
Resistivity has a strong influence on localized corrosion, either galvanic or by

differential aeration; it depends on total dissolved salinity (TDS) and temperature: as
rule of thumb, the following relation can be used:
30
qðX mÞ ffi ð20:1Þ
ð1 þ 0:02 DT Þ TDS
where TDS is in g/L and DT is T-25 °C.
20.2.5 Bacteria
Bacteria are often present in water, but not all of them cause corrosion. The
determination of the presence and quantity of bacteria is generally performed with
observations under an optical microscope or through biological cultures. The most
dangerous bacteria with regard to corrosion are the so-called sulphate-reducing
bacteria (SRB), which develop under anaerobic conditions in the presence of sul-
phate ions. The corrosive attack is characterized by the formation on the metal of a
black deposit of sulphide-containing corrosion products.
20.2.6 Other Cathodic Reactant
In oxygen-free water, other possible cathodic reactions are the reduction of chlorine
to chlorides, hydrogen gas evolution in acidic environments, reduction of highly
oxidizing compounds (Fe3+ ions, H2O2, O3, …). The presence of chromates, per-
manganates, molybdates or nitrites is dangerous only in the presence of chlorides,
which may trigger localized corrosion.
20.3 Uniform Corrosion Rate Evaluation
In the presence of oxygen and chlorine, the maximum uniform corrosion rate of
carbon steel, Crate, expressed in µm/year, is given by the following equation:
T25 pffiffiffi
Crate ffi 12 2 25 f½O2 þ 0:14 ½Cl2 g 1 þ v ð20:2Þ
where [O2] and [Cl2] are oxygen and chlorine contents in mg/L, T is temperature in
°C and v is water velocity in m/s.
As discussed in Chap. 8, corrosion rate equals oxygen availability in the case of
uniform corrosion or is proportional to it in case of localized attack, as in galvanic
and differential aeration corrosion mechanisms. Factors influencing corrosion rate
in freshwaters are:
• Oxygen availability
• Scaling tendency with precipitation on steel surface of a calcareous deposit
which works as a barrier to oxygen diffusion
• Resistivity that mainly affects localized corrosion.
For non scaling freshwaters, defined by a negative value of Langelier Index, LSI < 0,
corrosion rate is given by (chlorine not included):
pffiffiffi T25
Crate;LSI\0 ffi 12 ½O2 1 þ v 2 25 ð20:3Þ
For scaling fresh waters, LSI > 0, corrosion rate depends also on the permeability
or porosity, p, defined as fraction of bare metal surface (i.e., 1 − p is scaling
efficiency):
T25
Crate;LSI [ 0 ffi 12 ½O2 2 25 p ð20:4Þ
p ranges between 0 when scaling efficiency is unitary, i.e., no oxygen diffusion is

possible, to 1 when there is no scale formation. When a calcareous deposit is
present, water velocity has a negligible influence, because the layer diffusion
thickness in stagnant conditions practically coincides with the scale thickness.
Porosity, p, is a function of saturation index, LSI. As proposed by Lazzari
(2017), the following empirical equation can be used:
h i
10 ðLSI Þ2
pffi ð20:5Þ
10
Therefore, corrosion rate (mm/year) in aerated fresh water with scaling tendency is
given by:
20.3 Uniform Corrosion Rate Evaluation 431
T25
h i
Crate;LSI [ 0 ffi 1:2 ½O2 2 25 10 ðLSI Þ2 ð20:6Þ
hence it results as function of oxygen content, temperature and saturation index, LSI.
In the presence of a non-homogeneous scale, differential aeration may occurs.
The maximum corrosion rate is given by the macrocell current between anodic
corroding area and surrounding cathodic area, as seen in Chap. 9:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h i
Crate;MC [ 0 ffi 32 ½O2 ; ppm 2 10 ðLSI Þ2 TDSðg/lÞ ð1 þ 0:02DT Þ
T25
25
ð20:7Þ
where parameters and symbols are known.
Even Small Changes Have an Influence

Iron in distilled (or demineralised) water corrodes with formation of typical
brownish rust. The addition of 1 g/L of sodium chloride increases the cor-
rosion rate; corrosion rate increases even more if 1 g/L ferric chloride is
added. The addition of 2 g/L of sulphuric acid causes corrosion with
hydrogen evolution; the addition of 2 g/L of sodium bisulphite slows down
corrosion rate and a black film of magnetite forms on iron surface. The
addition of 1 g/L of caustic soda halts corrosion and preserves on iron surface
its natural colour; 1 g/L of sodium chromate causes the same effect, but, if
1 g/L of NaCl is also added, localized attack takes place. The addition of
0.2 g/L of permanganate reduces corrosion rate, while 2 g/L stops corrosion;
by adding 0.3 g/L of hydrogen peroxide corrosion rate reduces and stops
when 3 g/L is added. When calcium or magnesium salts are added to give the
same composition of tap water—if you prefer, bring tap water directly—iron
corrodes if water is stagnant and does not if stirred.
(from M. Pourbaix, “Lectures on Electrochemical Corrosion”, Plenum
Press, New York, 1973)
20.4 Metals for Freshwater
Pipelines used to transport freshwater are made with cast iron, reinforced concrete,
carbon steel, galvanized steel, polyethylene and PVC. The choice of material
depends not only on economic considerations, but also on engineering factors, as
diameter, pressure and flow rate. For example, pre-stressed cylinder concrete pipes
(PCCP) are used for large diameter, low pressure and little change in load; cast iron
for pressures not exceeding 20 bars. For high operating pressure, steel and
galvanized steel are used. In civil works and in in-house installations, copper,
copper alloys, mainly brass, galvanized steel and stainless steel are used.
For each class of metals, standard EN 12502 highlights the influencing factors
related to corrosion issues.
20.4.1 Steel and Cast Iron
Ferrous materials in contact with aerated water are susceptible to both uniform and
localized corrosion. In neutral, oxygen-free waters, corrosion is almost negligible.
Oxygen concentration thresholds are 0.1 and 0.02 ppm in cold and hot water,
respectively.
Corrosion rate decreases in time as a stable scale starts forming composed of
corrosion products and calcareous deposit due to the local increase in alkalinity.
Oxygen diffusion is controlled by the scale porosity and thickness. Figure 20.3
shows schematically the typical trend of corrosion rate in aerated scaling fresh
water.
If the forming scale is porous, not adherent, localised corrosion takes place. This
is the most frequent corrosion form on steels and cast irons in water distribution and
storage systems. It occurs in the form of galvanic coupling, tubercles or shallow
pits, differential aeration, when surface deposits are only partially protective or
insufficient.2 It happens mainly at the welds and heat affected zones in waters with
high levels of chlorides and sulfates and low total alkalinity. The rationalization of
the experience gained in Europe in the field of drinking water has led to the
identification of criteria for estimating the probability of corrosion based on the
characteristics of drinking water (Table 20.2).
Localised corrosion can be enhanced by microbial activity, which can take place
in anaerobic conditions, especially under debris.
Carbon steel is also used for industrial waters such as, for example, in boilers,
where water pH and oxygen content are adjusted to reduce corrosion rate, or in
cooling waters formed by the condensation of steam from process gas containing
small amounts of acids or organic acids. In both cases, pH adjustment should be
carried out, completed by addition of corrosion inhibitors, in particular zinc salts in
the case of cooling water, film-forming inhibitors in the case of acidic condensates
process, or oxygen scavengers in the case of boilers. These treatments substantially
decrease the aggressiveness of the liquid phase and therefore allow to use carbon
steel even with good reliability.
2
When water velocity is high, protective deposits are removed mechanically and corrosion mor-
phology is corrosion-erosion. The erosion resistance of surface deposits is lower in slightly aerated
water, and corrosion-erosion occurs in waters with low oxygen content. The areas of removal of
deposits behave as anodic areas and corrosion rate is accelerated by the effect of turbulence
induced in the area of the attack.
20.4 Metals for Freshwater 433
100
Corrosion rate (μm/y) 75
50
25
5 10
Time (years)
Fig. 20.3 Corrosion rate trend in time
Table 20.2 Conditions for acceptable corrosion rate of carbon and galvanized steel
Parameter—index Carbon steel Galvanized steel
pH >7 >7
AlkM (mEq/L) >2 >2
Acidity P (mEq/L) <0.05 <0.7
[Ca2+] (mg/L) >20 >20
O2 (mg/L) <0.02 <0.1
HCO3−/(SO42− + Cl−) (mEq/L) >1.5 >1
(2SO42− + Cl−)/AlkM (mEq/L) <5 <1
The effect of pH on carbon steel corrosion rate is clearly depicted in Fig. 20.4. In
almost neutral condition (5 < pH < 10) corrosion rate is constant and it depends on
oxygen availability. At more acidic pH, the main cathodic reaction is hydrogen
evolution, no corrosion products deposit form and the corrosion rate increases
Fig. 20.4 Carbon steel 1.0

Corrosion penetration (mm/year)
corrosion rate in aerated fresh

water as a function of pH
0.75
Limited by
oxygen
diffusion
0.5 H 2 evolution
begins
Passivation
0.25
0
14 13 12 11 10 9 8 7 6 5 4 3 2
pH
exponentially at reducing pH. In alkaline condition, pH > 10, carbon steel passi-
vates according to Pourbaix diagram. Consequently, corrosion rate reduces to
negligible values, lower than 1 µm/year. Only the presence of activating agents,
chloride ions for instance, may promote severe localised corrosion in the form of
pitting.
Water Treatment for Boilers

Before World War II, cooling water in power plants underwent a physical
deoxygenation followed by a chemical treatment with sodium bisulphite and
sodium hydroxide. At that time, carbon steel plates were riveted and not
welded, then suffering frequent caustic cracking. Around the 1950s, the
availability of ion exchange resins for deionization allowed the use of
ultra-pure water which was deoxygenated, as in the past, with added a
mixture of phosphates (so-called coordinated phosphate treatment). Above
100 °C steel reacts with water to form magnetite according to the reaction:
3Fe þ 4H2 O ! Fe3 O4 þ 4H2
In the 1970s, as operating conditions became more severe, a new treatment

was introduced called AVT (All Volatile Treatment) consisting of physical
de-aeration followed by hydrazine treatment as oxygen scavenger and
injection of ammonia as alkalizer. Hydrazine reacts at temperatures above
100 °C to give nitrogen:
N2 H4 þ O2 ! N2 þ H2 O
In the temperature range 150–200 °C hydrazine tends to decompose into NH3

and N2.
Unfortunately, the layer of magnetite, which forms with this treatment,
tends to grow hindering heat transfer, so periodic acid cleaning is necessary.
The choice of pH between 10 and 10.5 allows to limit these drawbacks.
Currently, for its toxicity, hydrazine is replaced by other oxygen scavengers,
which, however, may decompose giving rise to carbon dioxide or organic
acids.
At the end of the 1970s a new treatment was introduced in parallel to the
previous one, called Combined Water Treatment (CWT) with dosages of
100 ppb of oxygen and addition of ammonia to bring pH in the range 8.3–8.5.
By this treatment, large magnetite crystals, covered with finer hematite
crystals, form on the steel surface and grow more slowly, then reducing acid
cleaning frequency.
(from P. V. Scolari, Corrosion in power plants, AIM Conference, Milan,
Italy, 2006).
20.4.2 Galvanized Steel
Hot-dip galvanized steel pipes are used in particular in civil buildings as the resis-
tance to corrosion of zinc is higher than steel. The thickness of zinc and the corrosion
rate determine the operational life. The lower corrosion rate of zinc depends on the
formation of protective corrosion products that is favoured by the presence of
bicarbonates, phosphates, silicates, aluminium ions and organic molecules. Attention
should be paid to the temperature because above 50 °C a dangerous polarity inver-
sion between steel and zinc may take place, for which zinc becomes cathodic.
When different metals are present, in particular copper, copper alloys and
stainless steel, zinc coating suffers galvanic corrosion in correspondence of junc-
tions; the severity of the attack increases with water conductivity and pipe diameter.
Moreover, zinc may locally corrode due to the deposition of copper.
Table 20.2 shows the characteristics of water that make the likelihood of cor-
rosion of carbon steel and galvanized steel minimum, according to EN 12502.
20.4.3 Copper
Copper is the most used metal for water pipes in buildings, due to its high corrosion
resistance. Uniform corrosion is rare and if occurring would give as side effect an
unwanted release of copper ions in water. Uniform corrosion is prevented by the
formation of protective corrosion products, as basic carbonate, Cu2(OH)2CO3. Its
solubility increases as pH decreases and concentration of carbonic and bi-carbonic
ions increases. Uniform corrosion rate is negligible if the following requirements
are fulfilled: AcidP < 1.5 mEq/L and AlkM > 1 mEq/L. The more typical corro-
sion morphology is pitting that happens in situations of altered state of tube surface,
in particular for the presence of carbon particles originated during drawing as
a result of cracking of lubricants. The weak point of pure copper is the very low
resistance to corrosion-erosion. As soon as the water velocity exceed 2 m/s, copper
pipes suffer severe localized attack at corrosion-erosion rates as high as 2–5 mm/
year. To overcome the problem, copper alloys (brass, Cu–Ni) must be used: their
critical velocity increase up to 3 m/s.
Brass with Zn content higher than 15% suffers dezincification.
Pitting on Copper Pipes for Drinking Water

Copper for drinking water pipes works satisfactorily, showing sometimes a
few perforations within one year after installation. For pipes conveying cold
water, pitting is classified according to two types: type I, where pit is triggered
by the presence of carbonaceous particles present on the metal surface; type
II, which occurs when a protective film does not form due to unfavourable
environmental conditions.
Type I. Carbon debris, which trigger pitting, may have different origins:
cracking decomposition of lubricants (oils or grease) used in drawing or of
waxes, fats or oils present on surfaces subjected to welding, or decomposition
of soldering fillers. Regulations are nowadays very strict on requirements for
proper cleaning (chemical etching) after manufacturing to remove any
contaminants.
Type II. Pitting is associated to the formation of copper protoxide, Cu2O,
which appears shiny after cleaning. It forms in the presence of a number of
interrelated factors that are not easy to predict. For example: water compo-
sition, flow conditions, presence of deposits, for example corrosion products
of iron, exposure (the bottom of pipes is more risky). As far as water com-
position is concerned, influencing parameters are: pH (as it increases, pitting
susceptibility decreases), bicarbonates, sulphates and chlorides, which are
beneficial, while conversely iron, sodium, manganese and aluminium ions
have a detrimental effect; stagnant conditions are much worse than flowing
ones. Since pitting takes place especially within a few months from operating
start-up, initial conditions are particularly important (chemical composition
and hydrodynamics). The influence of copper metallurgy seems poor,
although literature reports that copper containing oxygen seems to be more
susceptible than deoxidized copper and that the addition of small amounts
(1%) of tin or aluminium is beneficial (Fig. 20.5).
Fig. 20.5 Localised corrosion on a copper pipe transporting fresh water

20.4.4 Stainless Steel
Stainless steels are used for transportation and distribution of water and as con-
struction materials in food and pharmaceutic industry, where no kind of metallic
contamination is allowed. Most common stainless steel types are austenitic (AISI
304 and AISI 316), the most used, and austenitic-ferritic ones (22Cr5Ni3Mo).
Among austenitic types, the choice between AISI 304 and AISI 316 depends on
working conditions, namely: level of chlorides, stagnant or flowing regime, the
presence of cracks or deposits and the presence of welds (Fig. 20.6).
As described in Chaps. 11 and 12, in selecting the proper stainless steel, PREN
index and chloride content must be primarily considered. As rule of thumb:
• Stainless steels with a PREN lower than 18 are recommended in the presence of
low chloride content or under special conditions as discontinuous operation,
absence of oxygen and other oxidants, cathodic protection or favourable gal-
vanic coupling or at high pH as in concrete
• In flowing water, without cracks and welds, it is possible to use AISI 304 up to
200 ppm of chlorides
• Molybdenum containing stainless steels, as AISI 316 type, with PREN 24–28,
can be used for brackish waters with chlorides content up to 1 g/L, not acidic, at
temperature not exceeding 30–40 °C
• Stainless steels with PREN 35–40 or higher, resist pitting attack in seawater,
provided there are no harmful galvanic coupling conditions as for instance with
carbonaceous materials and titanium
Fig. 20.6 Corrosion of AISI 316 stainless steel in the presence of bacteria in water containing
tank
• The best performance, even in presence of chlorine, is achieved using stainless

steel with PREN greater than 45 (as superaustenitic steels or superduplex: alloys
with 6% molybdenum)
• In case of water containing bacteria, especially of the oxidizing type gallionella
and manganese oxidizing strain, attacks have occurred even at levels of chlo-
rides lower than those reported.
Stainless steels for potable water and foodstuffs or for devices possibly in contact
with food must be sufficiently inert to exclude any transfer of metals to water and
food in quantities that endanger human health, change water composition unac-
ceptably, or deteriorate its organoleptic characteristics. To comply with these
requirements, steels must be tested at conditions in accordance with standards.
20.5 Brackish Water and Seawater
When salinity exceeds 2 g/L water is defined as brackish. Seawater is the most
abundant “brackish” water, with an average total salinity of 34–36 g/L with a few
exceptions such as Baltic Sea (about 9 g/L), Caspian Sea (average 12 g/L) and
Dead Sea (practical at saturation, around 34% by weight, water density 1.240 g/L).
Table 20.3 shows the synthetic seawater composition, according to ASTM D1141,
with a salinity 35 g/L and density 1.023 g/L at 25 °C.
Oxygen (as well as nitrogen and carbon dioxide) dissolves from the atmosphere
and in addition is produced and consumed by photosynthesis and microbiological
processes, respectively. The amount of dissolved oxygen can change according to
temperature, local turbulence and salinity, as already mentioned in Sect. 20.2.1. The
high salinity of seawater influences the carbonate/bicarbonate equilibrium so
strongly to determine the seawater as non-scaling water.
Table 20.3 Concentration of Ion or molecule Concentration

the main chemical species in
(mM/L) (g/kg)
seawater
Na+ 468.5 10.77
K+ 10.21 0.399
Mg2+ 53.08 1.29
Ca2+ 10.28 0.412
Sr2+ 0.09 0.0079
Cl− 545.9 19.354
Br− 0.842 0.0673
F− 0.068 0.0013
HCO3− 2.3 0.14
SO42− 28.23 2.712
B(OH)3 0.416 0.0257
20.5 Brackish Water and Seawater 439
Seawater has a slightly alkaline pH, around 8.3, and buffering properties (i.e.,
ability to maintain constant pH although small quantities of acids or bases are
added) through a complex series of chemical equilibria between dissolved carbon
dioxide and carbonates.
Another important factor is fouling, which consists of micro and macro organ-
isms, growing on submerged structures and even inside plants. Fouling can be
either beneficial or detrimental. In a few cases, it protects the metal beneath as an
oxygen barrier; instead, most likely it creates anaerobic conditions, which allow
MIC by sulphate-reducing bacteria.
The salinity of seawater is derived from chlorinity, which represents the total
content of halogens (chlorides, iodides, bromides) expressed as weight of chlorides
in a kilogram of water, or in parts per thousand (‰) obtained by titration with silver
nitrate. The following empirical relationship is used:
salinityð&Þ ¼ 0:03 þ 1:805 chlorinityð&Þ ð20:8Þ
The content of ionic species in solution determines the electrical conductivity (r),
which is about 100–200 times higher than that of fresh water. The conductivity can
be calculated as function of salinity (or chlorinity) and temperature as follows:
r ¼ 1=q ¼ ð0:15 þ 0:005 TÞ chlorinity ð&Þ ð20:9Þ
where r is expressed in S/m, resistivity q in X m and chlorinity in g/L.
20.5.1 Corrosion Zones in Seawater
Among natural environments, seawater is the most corrosive towards carbon steel,
due to high conductivity, oxygen availability and formation of porous corrosion
products. Localized corrosion may occur on passive metals. Microbiologically
influenced corrosion (MIC) is also a concern for localized corrosion attack pro-
moted by SRB (i.e., sulphate-reducing bacteria).
For the classification of corrosion, hydrodynamics and oxygen availability
condition determine four different zones as follows.
Atmospheric zone. It is the zone exposed to the atmosphere, free from seawater
spray. Relative humidity and pollutants (chloride and sulphate) govern the intensity
of the attack, so it varies with the geographical site. Affecting factors are direction
and speed of wind, temperature, solar radiation, rainfall, pollution and dust. In this
zone, corrosion takes place with the mechanism of atmospheric corrosion. Painting
is the most used corrosion prevention method for carbon and low alloy steels.
Splash and tidal zone. It is the zone exposed to alternating immersion and
emersion (the tidal width is determined by the geographical site) and includes the
zone exposed to a continuous water spray. Corrosion rate is high, almost an order of
magnitude higher than that in continuous immersion, due to the continuous wetting
and the high oxygen availability. Corrosion prevention is achieved by the use of
thick and strong protective coatings, either organic or metallic, as for example,
copper-nickel alloys or fibre reinforced epoxy coatings.
Submerged zone. In this zone, the metallic structure is permanently immersed in
seawater. The corrosion behaviour depends on temperature and turbulence, which
are highly variable from site to site. In stagnant condition, corrosion rate decreases
with time because corrosion products mixed with calcareous deposit (i.e., calcium
carbonate) contribute to reduce oxygen availability, although not forming a tough
scale. In summary, the following equations can be used to estimate uniform cor-
rosion rate (lm/year):
12 ½O2
Crate;seawater;stagnant ffi pffi ð20:10Þ
t
pffiffiffi
Crate;seawater;flowing ffi 12 ½O2 1 þ v ð20:11Þ
where t is time (y) for t > 1. In stagnant conditions, affecting parameters are oxygen
content, temperature and exposure time; yet, temperature is already accounted for in
the variation of oxygen content in the different seas—for instance, the North Sea
contains roughly 15–20 ppm O2 (oversaturation) while this decreases to 8–10 ppm
in tropical seas. In turbulent conditions, the main parameters are oxygen content
and water velocity. In this zone, corrosion prevention is achieved by cathodic
protection.
Mud zone. It is the zone placed below the seabed, where oxygen content is very low,
almost close to zero, hence corrosion rate significantly reduces below 20 lm/year.
Anaerobic condition may trigger SRB corrosion, with corrosion rate as high as
1 mm/year. Also in this zone cathodic protection is adopted.
Figure 20.7 shows the relative thickness loss for a carbon steel structure, as an
offshore platform, operating in the different corrosion zones.
20.5.2 Materials for Seawater
Two main categories are used: corrosion resistant alloys (CRA) and active metals
properly protected by cathodic protection and coatings, as described in dedicated
chapters. Corrosion resistant alloys, in particular copper, copper alloys, nickel
alloys and stainless steels are described in the following.
Copper and copper alloys. In principle, copper suffers oxygen-related corrosion,
therefore it is expected to corrode in seawater; nevertheless, long experience has
shown that copper and copper alloys resist corrosion in seawater and are considered
20.5 Brackish Water and Seawater 441
Fig. 20.7 Relative thickness Zone 1 atmospheric

loss for a carbon steel corrosion
structure operating in the
different corrosion Zone 2 splash zone
above high tide
zones (adapted from Humble
Mean high tide
1949)
Zone 3 tidal Mean low tide
Zone 4 continuously
submerged
Mud line
Zone 5 subsea
Relative loss in metal thickness
as ideal for marine applications. The reason is that copper passivates in the presence
of chlorides by forming cupric oxi-chloride, Cu2(OH)2Cl2. This corrosion product
leads to a passivation of copper and copper alloys, not as strong as stainless steel
passivity, nevertheless sufficient to reduce corrosion rate to negligible values from
an engineering point of view. Because of passivation and not passivity, this pro-
tective layer cannot resist corrosion-erosion; typically, when shear velocity exceeds
2 m/s corrosion erosion takes place. Copper-nickel alloys (typically, 90-10 and
70-30) and Ni-Al bronze are most used in applications when erosion-corrosion is a
concern. For heat exchangers, brass (i.e., copper-zinc alloy) is often used.
Stainless steels. On the contrary to copper alloys, stainless steels suffer localized
corrosion because of the presence of chlorides. PREN is the key for selection of the
corrosion resistant stainless steels. Most often, additional preventative measures are
adopted, typically cathodic prevention. For safe and reliable use, PREN must
exceed 40, therefore the use of Mo-containing stainless steels becomes mandatory.
Common stainless steels such as AISI 304 and AISI 316 are often successfully used
provided cathodic protection is applied (more appropriately, cathodic prevention
when applied since the installation). In seawater, crevice conditions should be
avoided. For stress corrosion cracking and corrosion fatigue behaviour, reference is
made to the dedicated chapters.
Nickel and nickel alloys. Nickel-based alloys offer excellent corrosion resistance to
a wide range of corrosive media in energy, power, chemical and petrochemical
industries, for applications in seawater and reducing electrolytes. They are also
successfully used in nuclear submarines. Some commercially important
nickel-copper alloys include so-called Monel as: Alloy 400 (66% Ni, 33% Cu),
Alloy R-405, Alloy K-500, which combine formability, mechanical properties and
high corrosion resistance, and so-called nickel-based super-alloys. These latter are
employed in high temperature applications due to their high mechanical strength
and oxidation resistance. Their composition is carefully balanced by additions of
chromium, cobalt, aluminium, titanium and other elements. Hastelloy is the trade
name of the most known super-alloy family, based on Ni-Mo and Ni-Mo-Cr alloys.
Hastelloy B is known for its resistance to HCl. Hastelloy C resists active oxidizing
agents such as wet chlorine, hypochlorite bleach, iron chloride and HNO3.
Hastelloy C-276 (17% Mo plus 3.7% W) resists seawater, pitting, stress corrosion,
cracking and reducing atmospheres. Alloy 625 (9% Mo plus 3% Nb) offers
high-temperature resistance as well as pitting and crevice corrosion resistance.
20.6 Applicable Standard
• ASTM D1141, Standard Practice for the Preparation of Substitute Ocean Water,
ASTM International, 100 Barr Harbor Drive, PO Box C700, West
Conshohocken, PA 19428-2959, United States.
• ASTM G52, Standard Practice for Exposing and Evaluating Metals and Alloys
in Surface Seawater, ASTM International, 100 Barr Harbor Drive, PO
Box C700, West Conshohocken, PA 19428-2959, United States.
• Directive 98/83/EEC of the European Community and the Council of 3
November 1998 on the quality of water intended for human consumption. (O.
J. EC L 330, 05.12.1998, p. 32–54).
• EN 12502-1, Protection of metallic materials against corrosion—Guidance on
the assessment of corrosion likelihood in water distribution and storage systems
—Part 1: General, European Committee for Standardization, rue de Stassart, 36
B-1050 Brussels.
the assessment of corrosion likelihood in water distribution and storage sys-
tems–Part 2: Influencing factors for copper and copper alloys, European
Committee for Standardization, rue de Stassart, 36 B-1050 Brussels.
—Part 3: Influencing factors for hot dip galvanised ferrous materials, European
Committee for Standardization, rue de Stassart, 36 B-1050 Brussels.
—Part 4: Influencing factors for stainless steels, European Committee for
Standardization, rue de Stassart, 36 B-1050 Brussels.
—Part 5: Influencing factors for cast iron, unalloyed and low alloyed steels,
European Committee for Standardization, rue de Stassart, 36 B-1050 Brussels.
20:1 Discuss the effect of pH and water hardness on the scaling tendency. Which
are the indexes used to define the scaling tendency? Make examples of water
with different indexes.
20:2 What is the effect of water resistivity on corrosion rate of carbon steel in a
non scaling freshwater? And in the presence of a non-homogeneous scale?
20:3 A carbon steel fire-system plant suffered localized corrosion after 4 year. The
thickness of the pipe is 4 mm; pipe diameter is 2″. During visual inspection,
a corroded area 1 cm2 wide was found. Deposits were detected on the
internal side of the pipe. Water composition is as follows: hardness 2 °F,
oxygen 2 ppm, chlorides 50 ppm, sulphates 80 ppm, pH 7.5, T = 15–20 °C,
conductivity 500 mS/cm. Make a corrosion assessment.
20:4 Estimate the corrosion rate of carbon steel in seawater in the following
conditions: oxygen 6 mg/L, stagnant condition, laminar regime (v = 0.3 m/
s), turbulent regime (v = 4 m/s).
20:5 Consider the following conditions:
• Stagnant fresh water, pH 6.5, T = 18 °C, 50 mg/L chlorides, 6 mg/L
oxygen
• Deaerated fresh water, pH 6.5, T = 20 °C, water velocity 2 m/s, 500 mg/
L chlorides
• Brackish water, 2 g/L chlorides, T = 40 °C; 5 mg/L oxygen
• Seawater.
For each condition, propose a stainless steel material selection based on
PREN index.
20:6 An AISI 304 stainless steel tank (18–8 CrNi) contains stagnant seawater at
15 °C. In few months, corrosion has penetrated a 4 mm thick plate in the
bottom. What is the cause of corrosion? How can corrosion prevention be
improved?
20:7 The same steel (AISI 304) is used in a pipeline carrying water to which ferric
chloride (FeCl3) is added to such an extent that the free potential is about
600 mV SCE. The temperature is 50 °C. Explain what will happen. Propose
alternative material selections.
20:8 A carbon steel platform is designed to work in the Adriatic Sea. Indicate the
corrosion zones. For each section, list the influencing parameters, estimate
the expected corrosion rate and suggest a possible protection technique.
20:9 The same carbon steel platform has to work in the Nordic Sea. Which are the
main differences in the corrosion rate evaluation?
20:10 Explain why in the Dead Sea, aluminium and magnesium alloys corrode,
while carbon steel does not.
20:11 What are the chemical treatments adopted to reduce the corrosion rate of
carbon steel boilers?
20:12 According to Fig. 20.7, carbon steel corrosion rate in tidal zone is lower than
in seamud zone. Explain the reason of this behaviour.
20:13 A water injection plant is used to inject at high pressure huge quantities of
water, suitably treated, into the hydrocarbon reservoir in order to increase oil
recovery in a petrochemical plant. In principle, it consists of the following
five components: water supply pump (so-called lifting pump); a flow-line
from supply well area to injection area (even some km long); a booster pump
to increase pressure; a distribution system (manifold); injection wells.
• Please indicate corrosion-related problems for each plant unit, comparing
the use of carbon steel and stainless steel, for the following three different
waters: (a) low salinity water; (b) high salinity water, such as formation or
brine separated from hydrocarbons (TDS > 250 g/L as NaCl); seawater
(TDS 35 g/L as NaCl)
• Suggest treatments for the use of carbon steel for all plant units. Possible
treatments are biocides, oxygen removal, inhibitors, filters, corrosion
allowance. [Hint: separate the plant into homogeneous zone from a cor-
rosion viewpoint, for instance aerated zones, de-aerated zones].
Giuseppe Bianchi
Giuseppe Bianchi (1919-96) graduated from Politecnico di Milano (Milan,
Italy), first in chemical engineering and then in electrical engineering, and there
began his teaching and scientific career in 1943. In 1959 he was called to the
University of Milan where he held the chair of Electrochemistry for more than
thirty years and gave life to the Institute of Electrochemistry and Metallurgy to
make it one of the main European research centres in the field of electro-
chemistry and corrosion. He was a man of high culture and moral stature, a
great researcher and a talented technician of anti-corrosion, indeed he was the
first true Italian corrosionist. It is an aptitude that is always present in its
activity, but becomes prominent since the 1980s when he first tackled the issue
of reliability of plants in relation to the risk of corrosion, and then that of
transferring the corrosion experience gained in the field to the emerging expert
systems. He was also a great teacher. With his lessons he fascinated genera-
tions of students, researchers and technicians. His great teaching ability also
transpires from his book of corrosion (written with Francesco Mazza) and his
splendid monographs: from the one on cathodic protection awarded by the
Ministry of Industry in 1954, to those on corrosion and protection in cooling
circuits of thermal and nuclear power stations, published in early 1970s. In
these works, the perfect knowledge of electrochemistry and of the behaviour of
materials in use allowed him to rationalize very complex corrosion processes
and to be able to predict and control them.
.
Bibliography 445
Bibliography
LaQue FL (1975) Marine corrosion. Causes and prevention. Wiley, New York
Corrosion (EFC) Series, vol 68. Woodhead Publishing, London
Humble HA (1949) Cathodic Protection of Steel Piling In Sea Water. Corrosion 5(9):292–302
Chapter 21
Corrosion in Soil
I see that water, nay, I see that fire and air and earth, and all
their mixtures become corrupt, and but a little while endure.
Dante, Paradise Canto 7
Abstract Soil can be defined as a complex agglomeration composed of an aqueous

solution with solid particles dispersed in, originated from the fragmentation of rock.
Its pores entrap either water or air as competitors: these situations determine dif-
ferent corrosion mechanisms, related to the presence (or absence) of oxygen. In this
Chapter, the corrosion forms in soil will be described, divided in three main groups:
oxygen-related corrosion (general and localized, differential aeration), microbio-
logically influenced corrosion (MIC) and stray current corrosion, by DC and AC.
For these last conditions, acceptance criteria of interference are highlighted.

https://doi.org/10.1007/978-3-319-97625-9_21
448 21 Corrosion in Soil
21.1 Soil Classification
The main constituents of soils are coarse particles, sand, clay and silt; typically, an
agricultural soil contains sand, clay and silt in comparable quantities. Table 21.1
lists the geological classification of soils, according to AASTHO Soil Classification
System (US code). Dry soil is not corrosive, instead corrosion can take place in the
presence of water. Water in soil may be available as:
• Underground water, with salinity varying from 80 to 1500 ppm
• Meteoric (rain) water, collected from atmospheric precipitation and available
only for a short period unless retained by clayey soils where it may be held back
longer
• Capillary water, that is, low salinity water retained in capillaries of clayey soil
or lime.
Soil entraps either water or air in pores as competitors: dry soil is aerated (aerobic
conditions) while wet soil is oxygen-free (anaerobic conditions) since the presence
of water impedes oxygen diffusion through the pores. The capacity of a soil to
retain water increases as the average particle size decreases; accordingly, the
presence of coarse particles provides the soil with a high drainage capacity and
therefore a low degree of water retention, as typical for sandy and coarse soils. On
the contrary, lime and clay have a high capacity to retain water with poor draining
capacity, therefore establishing anaerobic conditions. These two situations deter-
mine different corrosion mechanisms, which are related to the presence (or absence)
of oxygen.
As regards the chemical composition of soil, key factors are the presence of
soluble salts, mainly chlorides and sulphates, the presence of bicarbonates able to
form calcium carbonate deposits, pH that is usually between 6.5 and 7 but, in
extreme conditions, reaches 3 in acidic soils and 9.5 in alkaline soils. Temperature
can vary by several tens of degrees above and below zero depending on the season
and geographical location. When temperature drops below zero and the water
contained in the pores ices, corrosion stops.
The corrosion forms in soil can be divided in three main groups in accordance
with corrosion mechanisms involved: oxygen-related corrosion, microbiologically
influenced corrosion, MIC, particularly by sulphate-reducing bacteria under
anaerobic conditions, and stray current corrosion (Fig. 21.1).
Table 21.1 Classification of Class Definition Diameter of particles (average)

soils based on particles size
(AASTHO soil classification 1 Stones–Gravel 20–2 mm
system) 2 Sand 2–0.2 mm
3 Fine sand 0.2–0.02 mm
4 Silt 20–2 lm
5 Clay <2 lm
21.2 Corrosion in Aerated Soils 449
21.2 Corrosion in Aerated Soils
Oxygen in soils as well as in water is the most important factor determining

corrosion in the absence of bacterial activity. In certain acidic soils, even the
hydrogen evolution reaction is important. The amount of oxygen reduced in the
corrosion process is that arriving through diffusion, hence regulated by Fick’s law
(i.e., corrosion process is under cathodic control of oxygen transportation). The
forms of the oxygen-related corrosion are uniform corrosion in homogeneous
aerated soils with low conductivity and in acidic soils, localized corrosion with
formation of pustules in the presence of chlorides and sulphates, differential aer-
ation corrosion in the presence of non-uniform distribution of oxygen, corrosion by
galvanic coupling due to the contact with noble metals. As discussed in previous
chapters, corrosion rate equals oxygen availability in the case of uniform corrosion
or is proportional to it in case of localized attack, as in galvanic and differential
aeration mechanisms.
Although uniform corrosion is very rare in soils, except in some acidic and high
resistivity soils, it is useful to consider its theoretical aspects, especially concerning
oxygen related corrosion. In the presence of oxygen, the maximum uniform cor-
rosion rate is given by the following equation:
T25
Crate ffi 12 2 25 ½O2 ð21:1Þ
where Crate is expressed in lm/year, [O2] is the oxygen content in mg/L (ppm)
and T is the temperature (°C). In soil, since turbulence conditions are absent, the
oxygen limiting current density is only slightly variable, generally between 10 and
100 mA/m2, and the corresponding uniform corrosion rate is limited in the range
10–150 lm/year. In practice, the corrosion rate differs from these values, as it is an
order of magnitude lower due to the formation of protective corrosion products after
the oxidation of ferrous ions to ferric ions.
NBS long term testing results. After extensive experimentation carried out in
the United States, the National Bureau of Standards (NBS) through a statistical
approach derived an equation that correlates the metal thickness loss (X, lm) of
different metals to the period of exposure and soil resistivity:
X ¼ k tn ð21:2Þ
where t is exposure time in years, and k and n are two constants that depend on
metal, soil resistivity and aeration. Corrosion rate is worked out by derivation from
Eq. 21.2:
0
Crate ¼ k tn1 ð21:3Þ
The value of n for carbon steel, extrapolated from the results obtained by NBS,
ranges from 0.1 (good soil aeration) to 0.8 (poor soil aeration). In well-aerated soil,
corrosion rate, although initially great, falls off rapidly with time because the pre-
cipitation of ferric hydroxide occurs in the presence of oxygen and this scale on the
surface reduces corrosion rate. On the other hand, in poorly aerated soils, corrosion
rate decreases slowly with time. As a general consideration, corrosion rate
decreases with time, especially for low values of n. k values are inversely pro-
portional to soil resistivity.
The presence of a high content of chloride and sulphate ions influences the cor-
rosion rate through the tendency to depassivate and form soluble corrosion products
with scarce protective properties and promotes conditions for localized corrosion
attacks.
In particular, the corrosion attack localizes beneath corrosion products or
deposits, forming so-called pustules or tubercles, where oxygen can not be replaced,
while the surrounding surface works as cathode, according to the macrocell mech-
anism described in Chap. 9. Inside the tubercle, which works as a pit (Fig. 21.2), the
oxidation and hydrolysis reactions produce Fe3O4 and Fe2O3, increasing the acidity
(the pH drops below 4) due to the poor diffusion towards the outer zones. At the
same time, sulphates and chlorides enter inside the tubercle transported by the
macrocell current, creating an aggressive local environment. If the cathodic area is
sufficiently large, the corrosion rate may exceed a millimetre per year.
Cl-
SO42-
Tubercle Fe3O4
(black or green)
Protective layer Fe3+ Fe2O3 (reddish)
Cl-
H+
SO42-
Fe2+
Pit
Carbon steel
Fig. 21.2 Corrosion of carbon steel with formation of pustules due to the presence of chlorides
and sulphates
According to laboratory data and extensive field experimentation (Jailloux

1989), the corrosion rate becomes high, that is, greater than 100 lm/year, when
threshold values of 200 ppm of chlorides and 1000 ppm of sulphates are exceeded.
With a chloride content less than 200 ppm, a sulphate content less than 1000 ppm,
and a resistivity higher than 10 X m, the constants k and n of Eq. 21.2 are k = 25
and n = 0.65. When contents exceed the limits indicated, the constants k and n are
calculated as follows:
kCl ¼ 0:21 ½Cl0:86 nCl ¼ 1 ð21:4Þ
kSO4 ¼ 2:74 ½SO4 0:32 nSO4 ¼ 0:65 ð21:5Þ
When both chlorides and sulphates are present, an additional property applies for
k:
h i
k ¼ kCl þ kSO4 ¼ 0:21 ½Cl0:86 þ 2:74 ½SO4 0:32 n ¼ 0:65 ð21:6Þ
21.2.3 Corrosion Index
As reported in Harris and Eyre (1994), DVGW (the German Gas and Water Works
Engineer Association) developed an index in 1960s to evaluate soil corrosiveness.
Trabanelli et al. (1972) and later other researchers (Elsener et al. 1988) revised the
model. Soil corrosiveness is evaluated by the use of indices associated with cor-
rosion factors such as resistivity, redox potential, pH, humidity, chlorides, sulphates
and sulphides content (Table 21.2).
21.2.4 Differential Aeration Corrosion
Differential aeration corrosion takes place in all those conditions where a

non-homogeneous oxygen distribution exists, as in the presence of corrosion
products or deposit, which limits the oxygen diffusion.
In soil, differential aeration corrosion takes place when the soil surrounding the
structure is not homogeneous and shows variable oxygen permeability. A typical
case study is the presence of both a clayey layer and a sandy layer (Fig. 21.3). The
metal surface in contact with clay, which is not permeable to oxygen, becomes
anodic and metal dissolution takes place (Fe ! Fe2+ + 2e−). On the other hand, the
metal surface in contact with sand, which is highly permeable to oxygen, becomes
cathodic and oxygen reduction takes place (O2 + H2O + 4e− ! 4OH−). Therefore,
a macrocell sets up, where cathodic and anodic surface areas are separated.
Corrosion rate is given by the cathodic process rate, equal to the oxygen diffusion
Table 21.2 Index for corrosion rate estimation

Resistivity Eredox pH Humidity
Xm Index mV SHE Index pH Index % wt Index
>120 0 >400 +2 >5 0 <20 0
120–50 −1 400–200 0 <5 −1 >20 −1
50–20 −2 200–0 −2
<20 −4 <0 −4
Chlorides Sulphates Sulphides
ppm Index ppm Index ppm Index
<100 0 <200 0 Absent 0
100–1000 −1 200–300 −1 <0.5 −2
>1000 −4 >300 −2 >0.5 −4
Index sum Expected corrosion Corrosion rate (mm/year)
0 Nil <0.1
−1 to −8 Low 0.1–0.2
−8 to −10 Moderate 0.2–0.5
<-10 Severe >0.5
limiting current density multiplied by the cathodic-to-anodic surface area ratio. For
example, with an oxygen limiting current density of 100 mA/m2 (possible in
well-aerated zones) and a cathodic-to-anodic surface area ratio of 5, which is a
common ratio based on a soil resistivity around 20 X m, the corrosion rate is about
0.5 mm/year.
Figure 21.4 shows the electrochemical interpretation of differential aeration
corrosion of Fig. 21.3 by means of Evans diagram: in well-aerated soil, the cathodic
reaction (i.e., oxygen reduction) forms corrosion products which passivate the steel,
then ennobling the potential, while the anodic zone (oxygen-free) remains active.
The established macrocell shows a maximum driving voltage of about 200 mV.
Figure 21.5 shows a typical example of corrosion by differential aeration on a
coated pipeline with a bituminous, i.e., rather porous coating.
21.2.5 Galvanic Corrosion
The presence of two metals showing different nobilities may lead to galvanic
corrosion. The less noble metal, which has a lower potential in the natural envi-
ronment, behaves as anode and the more noble one shows prevalent cathodic
behaviour. The mechanism and influencing factors of corrosion due to galvanic
coupling are described in Chap. 10. Galvanic corrosion is favoured in low resis-
tivity soils: the lower the resistivity, the greater the corrosion effects. Although soil
is an environment with medium to high resistivity, especially if compared to sea-
water, where bimetallic corrosion is dreaded, galvanic corrosion is not negligible
O2 O2
Clay Fe2+ Sand

O2
Anodic reaction Cathodic reaction
Clay Sand
Fig. 21.3 Example of differential aeration corrosion
Pipeline in sandy soil
Eeq Pipeline in clayey soil
i0 log i
Fig. 21.4 Electrochemical interpretation by means of Evans diagram of differential aeration

corrosion
because of an extended electric field geometry (typical cathodic-to-anodic surface

area ratio is more than double that the one establishing by the differential aeration
mechanism).
To predict galvanic corrosion, the free corrosion potential of concerned metals,
as shown in Table 21.3, must be considered. Corrosion rate is high when a small
anodic zone is coupled to an extensive cathodic one as it happens in the case of
coupling with copper grounding net and buried steel structures. Figures 21.6 and
21.7 show some typical examples for tank bottoms and coated pipelines. So far,
cathodic protection has demonstrated to be the best prevention method to stop
corrosion. Other prevention measures, such as the application of a coating to the
cathodic surface, can only reduce the corrosion rate, but never stops it.
Fig. 21.5 Corrosion by differential aeration on a pipe with a bituminous coating
Table 21.3 Potential series of metals in soil and concrete

Metals Potentials (V CSE)
Stainless steel (passive) 0
Aluminium (passive) 0
Copper −0.2
Steel in concrete
– Active (carbonated concrete) −0.55/−0.30
– Active (chloride contaminated concrete) −0.55/−0.30
– Passive (aerated) −0.25/+0.20
Carbon steel
– Bare steel −0.55
– Coated steel −0.70/−0.55
Steel in concrete
– Passive (oxygen free) −0.80
Galvanised steel −0.95/−0.80
Zinc anode −1.04/−0.95
Magnesium anode −1.70/−1.55
Copper grounding net
Coating defect
Macrocell current
Fig. 21.6 Example of galvanic corrosion in soil between a carbon steel pipe (anode) and a copper
grounding net (cathode)
Tank
Corrosion
Copper Copper
grounding grounding
net net
Fig. 21.7 Example of galvanic corrosion of the bottom of a carbon steel tank because of the
coupling with a copper grounding net
Resistivity Measurement
The measurement of soil resistivity serves two purposes: evaluate soil cor-
rosiveness and, in CP application, calculate the groundbed resistance. The
Wenner method is the most widely used for measuring soil resistivity. It is
also referred to as the four-pin method. The method is easy to use and to
interpret when soil is assumed homogeneous in the zone under investigation.
Measurements are taken with four electrodes, usually made of copper or
stainless steel, aligned along the soil surface and equidistant by a length, d. A
direct or half-wave rectified current, I, is circulated between the two external
electrodes while the ohmic drop, ΔV, between the two internal electrodes is
measured. In the case DC is used, the measurement is repeated, inverting the

direction of the current. In homogeneous soil, the electric field generated by
the circulating current has a semi-spherical shape, as schematically shown in
the figure, and the ohmic drop, ΔV, is worked out by solving the electric field
equation: DV ¼ q I=ð2pd Þ, from which the resistivity is obtaibed.
If the soil is not homogeneous and, for example, made up of two parallel
layers with different resistivity, the electric field is distorted with respect to a
homogeneous condition. The resistivity value worked out from the equation
indicated above, suitable for homogeneous layers, represents the so-called
apparent resistivity and may vary considerably from the true value. In con-
clusion, the Wenner method is appealing because of its directness and sim-
plicity but often provides an approximate resistivity value. Moreover, it does
not provide information on soil stratigraphy.
To overcome the limits of the Wenner’s method, Schlumberger proposed
an improvement that consists of a series of measurements taken as in
Wenner’s method, with the difference that the external electrodes are spaced
successively, while the spacing of internal electrodes is kept constant. Each
measurement provides a value of the apparent resistivity, which in a sim-
plified way may be considered equal to the average resistivity of layers
crossed by the current. By increasing external electrode spacing, the depth the
current may reach increases and the apparent resistivity measured at each
spacing is closer to the resistivity value of the deepest, most influential soil
layer (Fig. 21.8).
V
A M d N d B
d
Electric field
lines
Fig. 21.8 Measurements of soil resistivity by Wenner method

21.2.6 Effect of Soil Resistivity
When considering the macrocell mechanism, as in differential aeration corrosion or

galvanic coupling, the corrosion rate depends on macrocell circuit resistance and
therefore on soil resistivity. A qualitative empirical model can be based on the
empirical correlation with resistivity: the greater the resistivity, the smaller the
macrocell current and therefore the lower the corrosion rate (Table 21.4). This
model is often unreliable and conflicting when one considers that the low resistivity
of a soil is due to its high water content, as in the case of clayey soil. However, a
water-saturated soil does not allow oxygen diffusion, hence it should be concluded
that despite its low resistivity, oxygen corrosion is nil.
Nevertheless, in the absence of oxygen, SRB corrosion may develop without a
direct and clear relation to resistivity, although water is necessary for bacteria to
thrive. Moreover, high resistivity denotes a dry soil, which permits high oxygen
diffusion rate, thus favouring differential aeration corrosion and a high corrosion
rate. Therefore, high resistivity soils such as those in desert zones may experience a
Table 21.4 Empirical Soil resistivity (X m) Corrosiveness

correlation between soil
corrosiveness and soil <5 Very severe
resistivity 5–10 Severe
10–30 Moderate
30–100 Light
100–250 Poor
>250 Negligible
Table 21.5 Influence of resistivity on corrosion in soil

Resistivity (X m)
Factors Low High
q < 10 q > 100
Water content High Low
Composition
– silt/clay High Low
– sand/stones Low High
– salt content High Low
Water drainage Low High
Oxygen diffusion Low High
Anodic overvoltage Low High
Electrochemical control Cathodic Anodic
Free corrosion potential Less noble More noble
Tendency to uniform corrosion High Low
Tendency to differential aeration corrosion Low High
Likelihood to microbial corrosion High Low
104
Resistivity (Ω m)
103
Sandy soil
102
Agricultural soil
10
Clayey soil
1
0 10 20 30 40
Humidity (%)
Fig. 21.9 Variation of resistivity with water content (schematic trend). This plot was presented by
Mario Arpaia in a cathodic protection course held at Politecnico di Milano, Italy
high localised corrosion rate. Table 21.5 lists the factors that directly or indirectly
influence resistivity. The relationship between resistivity and water content is
schematically illustrated in Fig. 21.9.
21.3 Microbial Corrosion
Trabanelli et al. (1972) reported that about half of the corrosion attacks on buried
pipelines can be attributed to bacterial and microbiological corrosion (MIC,
Microbiologically Influenced Corrosion). It has been observed that this takes place
mainly in neutral or alkaline soils, enriched in organic matter, and is absent in acidic
or neutral soils with a high salt content. The most damaging family of these
microorganisms is the sulphate-reducing bacteria (SRB) that develop and live in
anaerobic environments (Figs. 21.10 and 21.11). The properties of clayey soils,
which are neutral and oxygen-free, appear ideal for excluding corrosion from an
electrochemical perspective, yet they actually provide conditions that most favour
the growth of these bacteria and thus provide the worst outcome from a corrosion
point of view. Literature data agree on a corrosion rate even above 1 mm/year. SRB
are highly adaptable and are generally able to resist a temperature of 60 °C. Certain
families of bacteria resist even up to 80 °C and a pressure of 400 bars, which are
conditions encountered in oil and gas reservoirs. Although they are not active in
aerobic conditions, they survive and are ready to resume growth as soon as micro
and macro anaerobic environments are settled.
Chapter 7 reports a unified model of MIC for active and active-passive metals.
For localized corrosion of active metals, typically carbon and low alloy steels in
anaerobic environments, the cathodic process is the reduction of sulphate ion to
21.3 Microbial Corrosion 459
Fig. 21.10 Corrosion attack by sulphate-reducing bacteria on a carbon steel pipeline beneath a
welding joint sleeve
sulphide. This cathodic reaction, although as noble as oxygen reduction in neutral

solutions, cannot take place spontaneously, if not catalysed, because of its slow
kinetics. The most known catalyser is given by SRB metabolism, as proposed by
Von Wolzogen and Van der Vlugt (1934). Through an enzyme, the hydrogenase,
bacteria make use of hydrogen produced at the cathode to reduce sulphate ions
through the following reactions:
4Fe ! 4Fe2 þ þ 8e ð21:7Þ
8H þ þ 8e ! 8H
4 þ 8H ! S
SO2 þ 4H2 O
2
Fe2 þ þ S2 ! FeS
3Fe2 þ þ 6OH ! 3FeðOHÞ2
The reduction of sulphate to sulphide occurs also in nature, in anaerobic,

sulphate-enriched environments, where the oxidation reaction is carbon to carbon
dioxide or methane; if SRB find metallic iron available, the thermodynamically
preferred reaction becomes iron oxidation.
Redox potential measurements with a platinum electrode make it possible to
establish if a soil is prone to the development of SRB (Table 21.6). In fact, once the
pH is fixed, the redox potential measures the oxygen concentration, so that noble
redox potentials are characteristic of aerobic conditions. In order to compare
Table 21.6 Relationship EH (mV SHE) EH (mV CSE) SRB corrosion

between redox potential and probability
probability of corrosion
<100 < -200 High
100–200 −200 to −100 Moderate
200–400 −100 to 100 Limited
>400 >100 Nil
measurements of potentials obtained at different pH values, it is necessary to bring

them to scale at pH 7 through the following equation:
EH ¼ Ep þ ER þ 0:059 ðpH 7Þ ð21:8Þ
where EP is the potential measured versus a reference electrode, ER is the potential

of the reference electrode versus standard hydrogen electrode (SHE) and pH is the
measured soil pH. For example, if the measured potential, EH, is −20 mV, the soil
Fig. 21.11 Pipeline for

methane transportation (48″ in
diameter) affected by SRB
corrosion. The attack took
place beneath disbonded
polythene tape where cathodic
protection could not
penetrate, while providing
conditions for bacterial
growth
21.3 Microbial Corrosion 461
is prone to SRB corrosion. However, this does not mean that bacteria are present.
On the other hand, soil with a measured potential, EH, equal to +400 mV, therefore
well aerated, can not sustain bacterial growth.
21.4 Corrosion by Stray Currents
Interference corrosion greatly worries owners of buried structures, because of the

severe damage it causes. It occurs when a DC electric field influences a buried
metallic structure, determining the onset of cathodic and anodic surface areas. The
latter may suffer severe corrosion called stray current corrosion. Interference can be
stationary and non-stationary.
Stationary interference takes place when the structure is immersed in a sta-
tionary electric field generated, for example, by a cathodic protection system, and
the effect is greater as the structure is closer to the groundbed (GB). Figures 21.12
and 21.13 illustrate two general case studies; in the first case, the interfered pipeline
crosses the protected one and the zone close to the GB tends to gather current from
the soil (cathodic zone), which is released at the crossing point, causing corrosion
(anodic zone). In the second one, the two pipelines are almost parallel and the
current is released more extensively, typically in zones exposed to a soil with low
resistivity. In both cases, if the interfered structure is provided with an integral
coating, interference cannot take place, but when the coating has a number of faults,
corrosion is very severe since current concentrates in them.
Non-stationary interference occurs when the electric field is variable, as in the
typical case of stray currents dispersed by DC traction systems, illustrated in
Fig. 21.14. Interference takes place only during the trains transit, and often, in spite
of the limited duration, a few minutes, the effects may be severe due to high
circulating current. The corrosion mechanism is simple: the DC traction system
Interfered pipeline
Groundbed
Interference current
Corrosion
Fig. 21.12 Scheme of stationary interference between two crossing pipelines

Low
resistivity
Groundbed soil
Interference current
Interfered pipeline Corrosion
Fig. 21.13 Scheme of stationary interference between two almost parallel pipelines
Substation
Cathodic zone Anodic zone
Ecorr
Time
Fig. 21.14 Scheme of non-stationary interference caused by stray current dispersed by a DC

transit system
has an aerial conductor as a positive and the track as a negative, so that the current
return path is through both track and soil. If a pipeline is close to the track,
interference takes place and corrosion occurs where the current leaves the structure
near the substation.
In both cases, corrosion attacks are localized and very severe, with corrosion
rates even higher than 1 mm/year, depending on current densities reached locally
(Fig. 21.15).
21.4 Corrosion by Stray Currents 463
Fig. 21.15 Corrosion by stray currents on a coated carbon steel pipe
21.4.1 Electrochemical Reactions on the Interfered

Structure
Stray currents influence potentials of both anodic and cathodic zones: the former
become more positive and the latter more negative than the free corrosion potential,
as Fig. 21.14 shows. On cathodic zones, which receive current from soil, reactions
are oxygen reduction first and hydrogen evolution when sufficiently negative
potentials are reached, according to the following reactions:
O2 þ 2H2 O þ 4e ! 4OH ð21:9Þ
2H2 O þ 2e ! H2 þ 2OH
On anodic zones, which release current to the soil, the reaction is metal disso-
lution when the metal is active, for instance in case of active steel:
Fe ! Fe2 þ þ 2e ð21:10Þ
When the metal is passive, the anodic reaction depends on the type of metal and
environment. For example, in alkaline media, such as pristine concrete where
carbon steel is passive, for an initial period the anodic reaction is oxygen evolution,
by the following reaction:
2H2 O ! O2 þ 2H þ þ 4e ð21:11Þ
Then, because acidity is produced, passivity may be destroyed, provoking metal

dissolution. This also happens on stainless steel, which is rapidly depassivated,
so the corrosion reaction is metal dissolution with same harmful corrosion effects as
for carbon steel. According to Faraday law, the amount of metal that dissolves by
reaction (21.10) is directly proportional to current and time. A flow of 1 A dissolves
about 9 kg/year of iron and a current density of 1 A/m2 produces a thickness loss at
a rate of 1.17 mm/year.
21.4.2 Interference Current
Stationary interference. An evaluation of the interference current is obtained by

solving the electric field equation. In practice, the interference current can be
estimated from the balance of electrical tensions, as for example shown in
Fig. 21.16 for stationary interference. Path 1 is the current path of cathodic pro-
tection, where the current leaves the anode and enters the pipeline through the soil.
Path 2 is the one of the interference current and sums different contributions: (a) in
soil from the anode to the interfered structure; (b) within the structure; (c) in soil
from the interfered structure to the protected one. Ignoring the overvoltage at the
anode, common to both paths, path 1 is characterised by an IR drop in soil and a
cathodic polarisation contribution, Wc1; path 2 includes IR drop in soil and struc-
ture, cathodic and anodic overvoltage on the interfered structure (Wc2 and Wa2) and
the cathodic polarisation contribution, Wc1*. W indicates the overvoltage with
respect to the free corrosion potential (W = E − Ecorr) localised at anode (Wa) and
cathode (Wc). The balance of electrical tensions is the following:
Z Z Z
@L @L @L
q I1 þ Wc1 ¼ q I2 þ Wc2 þ qstr I2 þ Wa2
S S S
1 2 3
Z ð21:12Þ
@L
þ q I2 þ Wc1
S
4
By ignoring the structure ohmic drop and assuming constant cathodic overvoltage
(Wc1 Wc1*, although it depends on the effective local current density), the elec-
trical balance is:
2 0 13
Z Z Z
@L @ @L @LA5
DE ¼ Wc2 þ Wa2 ¼ q4 I1 I2 þ I2 ð21:13Þ
S S S
1 2 4
2
I2
A
I1
1
IRsoil
IRsoil IRpipe IRsoil
Fig. 21.16 Electrical scheme of stationary interference
where q is environment resistivity. DE is the resulting driving voltage imposed by

the interference system, which drives the interference current and represents the
“ohmic drop saving” in soil.
As general approach, the interference current density on the anodic zone (iint),
corresponding to the corrosion rate, is expressed by Tafel equation for active
metals:
Wa
iint ¼ icorr 10 b ð21:14Þ
where b (V/decade) is anodic Tafel slope and icorr (A/m2) is corrosion rate in free
corrosion condition.
Non-stationary interference. Cell balance for interference current evaluation is
based on the electrical scheme shown in Fig. 21.17, where current I is the current
that passes through the rail (estimated to be about 50% of the total current) and I* is
interference current:
I Rr
I ¼ ð21:15Þ
R1 þ Rpipe þ R2
where overvoltage is discarded and Rr and Rpipe are respectively rail and pipe
resistance, R1 and R2 are ground resistance. Corrosion damage, quantified through
I*, decrease as the rail resistance, Rr, decreases and the parallel soil path resistance
increases.
Rail Substation
i I Rr
i
Pipe
i Rpipe
Fig. 21.17 Electrical scheme of non-stationary interference
21.4.3 Interference assessment
Stray current corrosion is assessed through potential measurements; indeed, the

interference current cannot be measured. Different criteria apply for stationary and
non-stationary interference, as follows:
• For stationary interference, the so-called ON and OFF potentials on the inter-
fered structure are checked by switching the interference source on and off. The
potential shift, Eon − Eoff, quantifies the interference: positive at anodic zones
and negative at cathodic ones. As reported in Fig. 21.18, on interfered structure,
in the absence of CP, the OFF potential matches the free corrosion potential and
the ON potential gives the sign of the anodic or cathodic interference
Corrosion zone
Protected zone
Anodic interference
(V CSE)
Eon > Eoff

Eoff = Ecorr
Eon
Eon < Eoff
Cathodic interference
Distance
Fig. 21.18 Potential profile in case of interference

• Non-stationary interference, generated by DC traction systems, is checked and

monitored through a 24-h potential recording. Interference is present if potential
changes with time in either anodic (positive) or cathodic (negative) direction, as
depicted in Fig. 21.14. However, it is often difficult to ascertain corrosion
conditions from the potential recording, because there is a high IR drop con-
tribution caused by stray current circulation in soil. For evaluating the true
potential in the presence of stray currents, according to standards the use of
coupons or potential probes is recommended.
21.4.4 Criteria for Interference Acceptance
The effect of stray current corrosion depends on interference current, which, as said,
is not measurable. To assess interference conditions, the definition of an acceptable
corrosion rate, generally agreed on the threshold rate of 10 lm/year, is based on the
measurement of potential.
20 mV anodic potential shift criterion. Let’s consider an interfered structure. On
anodic zones the potential ennobles (more positive) and conversely on cathodic
zones it becomes more negative than the free corrosion potential, Ecorr, as shown in
Figs. 21.19 and 21.20 for an active metal and a passive one in an ideal case study
for which anodic and cathodic surface areas, Sa Sc, are of comparable size.
Figure 21.21 illustrates the most common and dangerous case, when the cathodic
surface area is much greater than the anodic one (Sa Sc) and cathodic polar-
ization becomes practically negligible.
For active metals, the increase in current density (and therefore in corrosion rate)
can be estimated by measuring Wa (Eq. 21.14). Assuming an anodic Tafel slope, b,
of 50–100 mV/decade, an increase in potential of 50–100 mV corresponds to an
increase in corrosion rate by one order of magnitude (for example, from 100 to
1000 µm/year). Accordingly, since the potential-current dependence is exponential,
it is reasonable to consider 20 mV as maximum allowed potential increase. This is
E Cathodic zone E
Anodic zone
ic log i ia log i
Fig. 21.19 Potential variation on anodic and cathodic zones for active material
E Cathodic zone E Anodic zone
ic log i ia log i
Fig. 21.20 Potential variation on anodic and cathodic zones for passive material
E E
ic log i ialog i
Fig. 21.21 Potential variation on anodic and cathodic zones for active materials when Sc Sa
Table 21.7 Values of Wa and Wc in some practical cases (Lazzari and Pedeferri 2006)
Type of structure Wa (mV) Wc (mV) Wa + Wc (mV)
Bare steel 20 0 20
Coated steel 20 300 320
Steel in concrete (passive) 500–800 0 500–800
Steel in concrete (active) 20 0 20
the meaning of the 20 mV anodic potential shift criterion. Table 21.7 reports values
of Wa and Wc for different practical cases.
Driving voltage criterion for concrete structures. Steel reinforcement of concrete
structures resists corrosion because in passive condition due to the alkalinity
(pH > 13) of the cement paste. Corrosion occurs when passivity is destroyed by
acid attack, for example due to carbonation, or when chloride content exceeds a
critical concentration (refer to Chap. 23) or to stray currents.
In the latter event, on passive steel, interference current can flow only if a driving
voltage (DE) higher than 0.8 V for Sa ≅ Sc is available (refer to Fig. 21.20) which
reduces to 0.5 V if cathodic surface area is large (Sc Sa). So a high driving
voltage is required because the anodic reaction is oxygen evolution, which occurs at
a noble potential of +0.5 V CSE.
When interference is stationary, the continuous oxygen evolution breakdowns
passivity due to the strong local acidification, then steel starts corroding as active
metal. Non-stationary interference is generally not harmful because there is a suf-
ficient time to neutralise the produced acidity during the short interference period.
Once steel is active, the 20 mV anodic potential shift criterion applies. Table 21.7
summarizes the practical conditions.
21.4.5 Prevention and Control of Stray Current Corrosion
Depending on the type, different approaches are used to prevent and control
interference. The main strategies are the following.
Stationary interference. Prevention methods of stationary interference follow two
basic principles: the elimination of driving voltage and the increase in current path
resistance. Driving voltage, ΔE, typically zeros by inserting a drainage, which is the
most common, effective and economic method used for crossing pipelines. It
consists of an electrical connection between the pipelines at the crossing point so
that both pipelines are cathodically protected. A calibrated resistance (Fig. 21.22) is
used when pipelines have different coatings, hence requiring different protection
current density. Driving voltage can be reduced by installing galvanic anodes at the
crossing, so most of the interference current leaves anodes and not steel, reducing
corrosion rate. The resistance of the current interference path is increased by the use
of insulating joints and coatings (Fig. 21.23). Insulating joints show best perfor-
mance where the potential gradient in soil is low or minimum that is, generally far
Interfered pipeline
Drainage by
Groundbed calibrated resistance
Fig. 21.22 Drainage at pipeline crossing

Interfered pipeline
Coating
Groundbed
Insulating joint
Fig. 21.23 Example of the use of insulating joint and coatings
away from both the crossing point and the interfering groundbed. Coatings are best
effective when applied to cathodic zones.
Non-stationary interference. It is more difficult to prevent or reduce because
changing in time. A general prevention measure is the adoption for rails of welded
joints to reduce the ohmic drop within the metallic rails within below 1 mV/m. On
the interfered structure, the reduction of interference current is achieved by
increasing the pipeline resistance by means of insulating coatings on cathodic zones
and by inserting insulating joints. Cathodic protection is an effective control method
if operated by means of the so-called constant potential setting of the feeding
system, with the aim to annihilate automatically interference effects; a reference
electrode placed at the anodic zone is used to drive potential control.
Insulating Joint Interference

When protected pipelines convey electrolytes, particular attention should be
paid to internal interference occurring at insulating joints. Figure 21.4 shows
a typical case study, where cathodic protection current flows through the
electrolyte, thus bypassing the joint and provoking an internal corrosion
attack. Interference current (path 2) is the competing path of protection
current (path 1).
Side effects of this inevitable interference are reduced by increasing
resistance on the interference current path; this is achieved by installing an
insulating spool, or by applying an internal coating for a suitable length on
the protected side.
Insulating joint
Internal corrosion
Fig. 21.24 Schematization of insulating joint interference
Substation
Drainage
Insulating joints Interfered pipeline
Fig. 21.25 Example of drainage and insulating joint insertion to mitigate non-stationary
interference
An elegant method, alternative to CP, is the drainage, shown in Fig. 21.25,

which consists of an electrical connection between the structure and the substation
rail to drive the interference current through a metallic path. In order to avoid
dangerous current inversion, as in the case of a temporary substation shutdown, the
drainage must include a diode. Most often, drainage is provided by an ICCP system
connected to the rail as groundbed and operated at constant potential.
21.4.6 Alternating Current Interference
Alternating current (AC) can cause corrosion attacks by an interference mechanism

on buried metallic pipelines that run parallel to an AC interference source, as
high-voltage transmission lines (HVTL) or tracks of AC railway traction systems.

Interference mechanisms are as follows:
• Interference by conduction. It happens if AC current is spread in soil as typically
from grounding networks of AC transmission lines and AC traction systems. AC
currents may affect nearby buried metallic structures such as pipelines and tanks;
• Interference by induction. It takes place when a buried, well-coated pipeline
with a high insulating coating, like extruded polyethylene or polypropylene, is
parallel to a high voltage transmission line, typically 130 kV or higher. The
alternating unbalanced magnetic flux established between cables and soil
induces an AC in the coated pipeline (auto-transformer effect, which is not
possible if HVTL is buried).
In both cases, the buried structure exchanges AC through coating defects or
holidays. Nowadays, it is agreed that AC-induced corrosion happens in two specific
conditions: freely corroding and overprotected conditions (i.e., pipeline potential
below −1.2 V CSE) with AC density exceeding a threshold.
Influencing factors. The AC voltage, VAC, on a pipeline is the driving force for the
AC corrosion processes taking place on the steel surface at coating defects, so it
must be reduced to avoid AC interference. AC voltage is easily measured between a
metallic structure and a reference electrode placed in a remote position, i.e. where
no further variations of the AC voltage are measured increasing the distance
between the reference electrode and the structure. Moreover, corrosion damage
depends on AC current density on a coating defect and on the level of DC polar-
ization (IR-free potential and protection current density). However, in contrast to
the AC voltage measurement, current density can be measured only through ded-
icated coupons simulating a coating defect with a known surface (1 cm2) or it can
be estimated based on measuring parameters, as remote voltage and soil resistivity.
The spread resistance of a coating defect is given by the following equation:
q
R¼ ð21:16Þ
2p/
where R (X) is spread resistance, q (X m) is soil resistivity and / (m) is coating

defect size. The current density, iAC, exchanged on the defect is given by:
VAC 8p/VAC 8VAC

iAC ¼ ¼ ¼ ð21:17Þ
RA qp/2 q/
where iAC (A/m2) is current density, VAC is remote voltage and other symbols are
known.
According to international standard ISO 18086, the remote voltage on the
pipeline, VAC, and AC current density, iAC, should be maintained lower than 15 V
and 30 A/m2, respectively, on a 1 cm2 coating defect. By inputting the current
density threshold of 30 A/m2, the maximum allowable remote voltage of 15 V, and
an average resistivity of 50 X m, the minimum coating defect diameter results about

10 cm. It follows that the main control method to decrease AC current density on
smaller coating defects of a coated pipe is the grounding, which increases the
exposed surface to soil.
Acceptable AC interference levels. In the last years, an extensive effort has been
performed to provide acceptable criteria to evaluate AC corrosion likelihood. The
recent international standard ISO 18086 reports that in the presence of AC inter-
ference the criteria given by ISO 15589-1 (i.e. the −0.850 V CSE criterion) are not
sufficient to demonstrate that steel is protected against corrosion. The standard
provides the following acceptable interference levels, measured as an average over
a representative period of time (e.g. 24 h):
• As a first step, the AC voltage on the pipeline should be decreased to 15 V R.M.
S. or less;
• As a second step, effective AC corrosion mitigation can be achieved by meeting
the cathodic protection potentials defined in ISO 15589-1, and:
– Maintaining AC density, iAC, lower than 30 A/m2 on a 1 cm2 coupon or
probe, or
– Maintaining the average cathodic current density lower than 1 A/m2 on a
1 cm2 coupon or probe if AC current density is more than 30 A/m2, or
– Maintaining the ratio between AC current density, iAC, and DC current
density, iDC, less than 3.
In other words, while no AC density restrictions are defined for DC densities lower
than 1 A/m2, AC density is restricted to values lower than 30 A/m2 with DC density
in the range from 1 to 10 A/m2. In a recent work by Brenna et al. (2015), a more
conservative criterion has been proposed based on experimental tests on carbon
steel under cathodic protection condition and in presence of AC stationary inter-
ference. Laboratory tests showed that in overprotection condition, i.e., potential
more negative than −1.2 V CSE, only a few A/m2 of AC density could cause
corrosion of overprotected carbon steel. Results showed that cathodic current
densities lower than 1 A/m2 in combination with AC density higher than 30 A/m2
can lead to AC corrosion, as well as DC density higher than 1 A/m2 in combination
with AC density higher than 10 A/m2.
AC Corrosion Mechanism
Various hypotheses about the mechanism by which AC produces and
enhances corrosion of carbon steel (even in CP condition) have been pro-
posed. Most interpretations are based on electrical equivalent circuits repre-
senting the impedances existing between pipe and remote earth, on
electrochemical and mathematical models considering the anodic semi-period
effect of the AC signal, and on the effect of AC on the formation of passive
layer on steel under cathodic protection condition.
Recent works by Goidanich et al. (2010a, b) and by Brenna et al. (2015,

2016) suggest a corrosion mechanism in which the effect of AC is twofold.
A “mixed corrosion mechanism” was initially hypothesized, with a general
decrease in both anodic and cathodic overvoltage and an increase in exchange
current density of different metals (carbon steel, galvanized steel, zinc, and
copper) in various environments (e.g., soil-simulating solution, artificial
seawater) in the presence of AC. Generally, AC pushes the potential of
carbon steel under cathodic protection toward more noble values, and reduces
overvoltage contributions.
On the other hand, a two-step AC corrosion mechanism has been proposed
(Brenna et al. 2015). In the first step, AC causes the weakening of the passive
film formed under cathodic protection, due to electromechanical stresses.
Electrostriction appears to be a convincing explanation of the passive film
breakdown mechanism, because of the presence of high alternating electric
field (of the order of 106V/cm) across the passive film. After film breakdown,
high-pH chemical corrosion (i.e. potential independent) occurs in overpro-
tection condition because of the high cathodic current density supplied to the
metal.
21.4.7 Typical Cases of Improbable Interference
There is a tendency to attribute unexpected corrosion attacks to stray currents.

Generally, this happens because of ignorance of corrosion principles or someone
wants to avoid taking any responsibility and says: it is nobody’s fault, it is just
caused by stray currents! The following case studies are typical (for more details see
Lazzari and Pedeferri 2006).
Corrosion in water piping and heaters. The perforation of water piping, heaters
and heat exchangers in plants is sometimes attributed to stray currents and internal
corrosion, for instance because of inadequate water treatment, is not taken into
account. If stray currents were responsible for this damage, one should first identify
their source. Often, stray currents are present in soil because of electric transit
systems or ICCP systems, hence a question arises, that is, how they can affect the
piping. Looking at this system, stray currents from rail or groundbed may be picked
up by the grounding, then circulate in copper cables and eventually return to the
soil, that is, to the transit substation or CP feeder. Such a current path (soil-
grounding-copper-grounding-soil) can only produce corrosion of grounding rods
where current leaves the metal to the soil. Other current paths are not possible.
A hypothetical one, consisting of: soil-grounding-copper-pipe-water-pipe-copper
grounding-soil, which potentially could produce corrosion, is not consistent since
the internal path “copper-pipe-water-pipe-copper” cannot occur because the metal is
equipotential. The conclusion is that the cause of corrosion is corrosion, and not
stray current interference.
Corrosion of piping in buildings. Often in buildings, piping embedded in concrete
suffers corrosion, causing trouble, high repair costs and litigation when the builder
claims stray current effects, hence discarding responsibility. In this case, corrosion
comes from the external surface so that stray current interference might seem to be
responsible. Nevertheless, again, it is not. As in the previous case, stray currents
may be present in the ground, and the grounding system may pick up some current.
An alternative path is possible, such as: soil-grounding-pipe-concrete-soil, thus
causing corrosion at the “pipe-concrete” interface, but this path is much more
resistant by several orders of magnitude than metal paths, because bricks and
concrete have a much higher resistivity. Therefore, some current approximately
nano-amperes can leave bare pipe surfaces, but with no practical effects.
• AASHTO Soil Classification System, American Association of State Highway

and Transportation Officials.
• ASTM G 51, Standard test method for measuring pH of soil for use in corrosion
testing, American Society for Testing of Materials, West Conshohocken, PA.
• ASTM G 57, Standard test method for Field Measurement of Soil Resistivity
Using the Wenner Four-Electrode Method, American Society for Testing of
Materials, West Conshohocken, PA.
• ASTM G 187, Standard test method for Measurement of Soil Resistivity Using
the Two-Electrode Soil Box Method, American Society for Testing of Materials,
• EN 12501-1, Protection of metallic materials against corrosion—Corrosion
likelihood in soil. Part 1: general, European Committee for Standardization,
Brussels.
• EN 12501-2, Protection of metallic materials against corrosion—Corrosion
likelihood in soil. Part 1: low alloyed and non-alloyed ferrous materials,
European Committee for Standardization, Brussels.
• EN 50162, Protection against corrosion by stray current from DC systems,
European Committee for Standardization, Brussels.
• ISO 11048, Soil quality. Determination of water-soluble and acid soluble sul-
phate, International Standard Organization, Geneva, Switzerland.
• ISO 15589-1, Petroleum, petrochemical and natural gas industries—Cathodic
protection of pipeline systems—Part 1: On-land pipelines, International
• ISO 18086, Corrosion of metals and alloys—Determination of AC corrosion—
Protection criteria, International Standard Organization, Geneva, Switzerland.
• ISO 21809, Petroleum and natural gas industries—External coatings for buried
or submerged pipelines used in pipeline transportation systems, International
• NACE TM0106, Detection, testing, and evaluation of microbiologically influ-
enced corrosion (MIC) on external surfaces of buried pipelines, NACE
International, Houston, TX.
21:1 Explain why in well-aerated soil corrosion rate of carbon steel decreases
with time more rapidly than in case of poor aerated soil.
21:2 Consider Eq. 21.3 for the calculation of carbon steel corrosion rate in soil.
Calculate corrosion rate after 1, 10 and 20 years in the following conditions:
(a) chlorides 100 mg/L, sulphates 500 mg/L; (b) chlorides 1000 mg/L,
sulphates 1000 mg/L.
21:3 Demonstrate by means of Evans diagram that the maximum driving voltage
in differential aeration of carbon steel in soil is about 200 mV. [Hint:
suppose that the Tafel slope of the anodic process is 100 mV/decade and
200 mV/decade in poor-aerated soil and well-aerated soil, respectively].
21:4 Consider the replacement of a pipe section in a sandy soil by a new spool.
Make a corrosion assessment.
21:5 In free corrosion condition, carbon steel corrosion rate decreases with time.
However, in the case of carbon steel corrosion due to galvanic coupling (for
example with a grounding copper net), corrosion rate of carbon steel does
not decrease with time. Which are the causes of this behaviour?
21:6 In a gas station, a double wall underground tank is connected to a copper
grounding system. The tank external surface is coated with 1 mm thick
polyester reinforced coating. Estimate the time of perforation of the outer
wall (3.5 mm thick) in the presence of a small defect. Estimate oxygen
content as a function of soil type and consider a surface area ratio of 30.
21:7 In a fuel station, three underground structures are electrically connected: a
carbon steel tank coated with reinforced polyester (1 mm thick), a copper
grounding network and a reinforced concrete foundation. Make a corrosion
assessment. Explain why carbon steel reinforcements (that have the more
negative free corrosion potential) do not undergo corrosion. Is the use of
magnesium galvanic anodes effective?
21:8 How does an electrical drainage for interference prevention work?
21:9 A coated carbon steel pipe in soil (6 mg/L of oxygen) is interfered by a DC
non-stationary source. What are the electrochemical reactions correspond-
ing to the anodic and cathodic zones? Corresponding to the anodic zone, a
positive potential shift of 50 mV with respect to the free corrosion potential
has been measured. Calculate the corrosion rate in the anodic zone.
21:10 Consider the following interference conditions measured on a carbon steel

corrosion coupon (1 cm2), not in cathodic protection condition: (a) station-
ary interference (1.5 A/m2 for 24 h); (b) non-stationary interference (10 A/
m2 for 5 min every hour). Which criterion would you use to compare the
two cases? Calculate corrosion rate.
Bibliography
Brenna A, Lazzari L, Ormellese M (2015) AC corrosion of cathodically protected buried pipelines:

critical interference values and protection criteria. In: Proceedings international conference
corrosion/15, Paper N. 5753, ISSN 03614409, NACE International, Houston, TX
Brenna A, Ormellese M, Lazzari L (2016) Electromechanical breakdown mechanism of passive
film in alternating current-related corrosion of carbon steel under cathodic protection condition.
Corrosion 72(8):1055–1063
Elsener G, Jansch-Kaiser G, Sharp DH (1988) Soil (underground corrosion), vol 2. Dechema
Corrosion Handbook. Frankfurt Am Main, FRG
Goidanich S, Lazzari L, Ormellese M (2010a) AC corrosion. Part 1: effects on overpotentials of
anodic and cathodic processes. Corros Sci 52:491–497
Goidanich S, Lazzari L, Ormellese M (2010b) AC corrosion. Part 2: parameters influencing
corrosion rate. Corros Sci 52:916–922
Harris JO, Eyre D (1994) Soil in the corrosion process. In: Shreir LL, Jarman RA, Burstein GT
(eds) Corrosion Vol. I—metal/environment reactions, 3rd edn. Butterworth Edition, London,
UK
Jailloux JM (1989) Durability of materials in soil reinforcement applications. In: Proceedings 8th
Eurocorr conference, Vol. 1, Paper No. TR-086, Utrecht
Lazzari L, Pedeferri P (2006) Cathodic protection, ed. Polipress, Milan, Italy
Romanoff M (1986) Underground corrosion. Nat Bur Stand—Circular 579, U.S. Department of
Commerce, Washington, 1957, NACE Int. Edition, Houston, TX
Trabanelli G, Gullini G, Lucci GC (1972) Sur la determination de l’agréssivité du sol. Ann Univ di
Ferrara NS Sez V, III, (4), 43
Von Wolzogen Kuhr CAV, Van der Vlugt SS (1934) Graphitization of cast iron as an
electrochemical process in anaerobic soil. Water (Den Haag) 18:147–165
Chapter 22
Atmospheric Corrosion
Keep up your bright swords, for the dew will rust them.
W. Shakespeare, Otello, I, 11
Abstract Metallic structures exposed to the atmosphere undergo corrosion when a

thin liquid film forms at their surface. The extent of corrosion depends on
chemical-physical properties of this film, hence on the parameters they are determined
by, such as relative atmospheric humidity, temperature, composition as well as time of
wetness. Many of these factors are difficult to quantify, and often have complex,
contrasting effects on the corrosion process: this is the case of rain, wind and temper-
ature. All of these factors are discussed in the chapter, together with the classification of
atmospheric environments according to the ISO standards. The characteristics of most
used metals are also reported with reference to their use in atmosphere.
Fig. 22.1 Case study at the PoliLaPP corrosion museum of Politecnico di Milano

https://doi.org/10.1007/978-3-319-97625-9_22
480 22 Atmospheric Corrosion
22.1 Liquid Film
Electrochemical reactions only onset in the presence of a liquid film at the metal
surface. The thickness of this film depends on the chemical and physical charac-
teristics of the metal surface, including roughness and chemical contamination. On
a clean surface, it would not exceed 1 lm when exposed to a relative humidity
lower than 100%; when conditions are close to saturation it grows to thicknesses
ranging from 1 to 10 lm, reaching some tens or hundreds lm in presence of
condensation, and finally exceeds 500 lm in case of rain.
Considering thin films, oxygen diffusion in the electrolyte is not a
rate-controlling step to determine corrosion rate. This is controlled by the scarce
water presence when humidity drops below 80%, or by the diffusion of aggressive
species (oxygen, water, chlorides) through corrosion products that cover the metal
surface. Conversely, considering thick films, oxygen diffusion may control corro-
sion rate, as it happens in corrosion on immersed metals.
The worst conditions are found in presence of thin films, which do not obstacle
oxygen supply, but thick enough to make anodic and cathodic processes easy
(Fig. 22.1). Only for galvanic coupling, thick liquid films represent the worst conditions.
Film forms by condensation according to different chemical-physical phenom-
ena, which can be summarized to four mechanisms:
• Physical condensation: it consists of water passing from vapour to liquid state at
the metal surface, due to a decrease of the atmospheric temperature or because
metal is colder than the surrounding atmosphere; film thickness is in the order of
fractions of millimetre, and its composition is pure water
• Adsorption condensation: it is a purely physical phenomenon, caused by
attraction forces between metal and water molecules. It produces pure water
films with thickness ranging from few to hundreds of molecular layers at low
relative humidity to 100% humidity, respectively
• Chemical condensation: it takes place in the presence of hygroscopic species at
the metal surface, which dissolve in the water film creating highly conductive
solutions. In many cases, for instance in presence of calcium or ammonium
chloride—typical of marine environments—even very low values of atmo-
spheric humidity can be sufficient to produce this type of condensation
• Capillary condensation: it is typical of rough surfaces, or coated by porous patinas.
22.2 Factors Affecting Corrosion
22.2.1 Relative Humidity
Corrosion rate rapidly increases with relative humidity when it exceeds a threshold
defined as critical relative humidity, as shown in Fig. 22.2 for steel and copper.
22.2 Factors Affecting Corrosion 481
(a) (b)
4.0
100 Fe Cu
Weight increase (mg/dm2)
Weight increase (mg/dm2)

0.1 ppm SO2 0.1 ppm SO2
55 days 3.0 30 days
60 2.0
1.0
Without SO2 Without SO2
20
0
20 60 100 50 60 70 80 90 100
Relative Humidity (%) Relative Humidity (%)
Fig. 22.2 Weight gain as a function of relative humidity in atmosphere containing 0.1 ppm of
SO2: a carbon steel after 55 days; b copper after 30 days
Table 22.1 Relative humidity producing condensation on salt contaminated surfaces

Salt Relative humidity (%)
Na2SO4 93
(NH4)2SO4 81
NaCl 78
CaCl2 35
FeCl3 12H2O 10
Critical relative humidity varies with the metal composition and surface finishing
(for instance, shiny or opaque) and with the composition of corrosion products and
contaminants present on the metal surface. In case of the presence of hygroscopic
salts, as chlorides, critical relative humidity is very low1 (Table 22.1); with very
hygroscopic salts, surface wetting may result practically continuous.
22.2.2 Time of Wetness
Corrosion only happens if water is present at the metal surface,2 therefore its rate
depends on the time during which the surface remains wet, which is called time of
wetness, s. Time of wetness is correlated with the presence of high atmospheric
1
It coincides with the value of relative humidity giving a vapour tension equal to that of a saturated
solution of the same salts.
2
Dry corrosion practically never happens at room temperature, excluding cases of slight oxidation
or surface sulphuration, such as silver tarnishing (darkening) produced by traces of H2S even in
very low humidity conditions.
Table 22.2 Classification of time of wetness following ISO 9223

Category Time of wetness Examples
(hours in a year) (% in a year)
s1 s 10 s 0.1 Internal microclimates with climate
conditioning
s2 10 < s 250 0.1 < s 3 Internal microclimates without climate
conditioning, excluding humid climates
s3 250 < s 2500 3 < s < 30 External atmospheres in cold and dry
climates and part of temperate climates:
shielded and correctly aerated areas in
temperate climates
s4 2500 < s < 5500 30 < s 60 External atmospheres in all climates
(excluding cold and dry areas); shielded
and aerated humid areas; non-aerated
temperate climates
s5 5500 < s 60 < s Some zones of damp climates: shielded,
non-aerated humid areas
relative humidity levels. In order to have a statistical evaluation on a sufficiently

long period, typically over one year, it is used the time by which humidity exceeds a
given value (80% according to ISO standard 9223). Table 22.2 reports the classi-
fication of time of wetness proposed by ISO 9223.
22.2.3 Temperature
Temperature plays a complex role on atmospheric corrosion. As it increases, the

rate of electrochemical reactions increases; yet, at same water content relative
humidity decreases, hence, jeopardizing the presence of the liquid film at the metal
surface. Moreover, protective properties of corrosion products may change. If water
freezes3 corrosion stops because it loses its electrolytic properties.
Available data on tests performed at different European sites indicate an increase
of the corrosion rate of carbon steel by approximately 1 lm/year per Celsius degree
of mean annual temperature increase.
Table 22.3 reports estimated times of wetness of climatic zones characterised by
different temperature and humidity.
3
In contaminated atmospheres or inside pores, freezing is achieved some degrees below 0 °C.
Table 22.3 Estimated times of wetness of climatic zones characterised by different temperature
and humidity [ISO 9223]
Climate Min and max Max temperature with Time of wetness Category
temperature (°C) RH > 95% (h/year)
Very cold −65/+32 +20 0–100 s1
Cold −50/+32 +20 150–2.500 s2
Temperate −33/+34 +23 2500–4200 s3
Temperate, +25
hot
Hot, dry −20/+40 +27 2500–5500 s4
Very hot, +3/+55 +27
dry
Hot, humid +5/+40 +31 4200–6000 s5
22.2.4 Atmosphere Composition
The composition of atmosphere is reported in Table 22.4. The concentration of

main components (N2, O2) slightly varies from one region to another; conversely,
that of minor components can vary consistently from one site to another, even daily
or seasonally. For instance, the concentration of carbon dioxide is on average
380 ppm4 but it may be higher inside highway tunnels, in poorly aerated parking or
in particular environments, such as in crop silos, where it may reach 1%.
22.2.5 Contaminants
Table 22.5 reports annual releases of some contaminants in typical atmospheres.

Pollutants have different origins as volcanic, from metabolism of vegetation and
animals, from sea spray or dust carried by the wind, from exhausts of combustion of
fossil fuels (carbon, oil, gas), from industrial emissions (for instance, chemical,
metallurgical, cement industries). Finally, some substances are the result of reaction
between pollutants and the atmosphere, triggered by ozone or ultraviolet radiation.
Contaminants can accumulate on surfaces as dry deposits (which contribute to 70%
of the total, approximately) or as liquid phase (small droplets of rain or fog, making
up the remaining 30%).
Acid rains. This expression refers to all deposits (dry or humid) that cause an
acidification of the metal surface. It is worth reminding that even in the absence of
pollutants (SO2, NOX, HCl) rain is slightly acid due to the presence of carbon
4
In the last thousands years and until two centuries ago, CO2 concentration, estimated through the
analysis of gas trapped in polar ice, was constant and equal to 270 ppm. Since the beginning of the
industrial revolution it has been growing, first slowly, then faster, until reaching the current
accumulation rate, equal to approximately 1 ppm per year.
Table 22.4 Average composition of natural atmospheres

Nitrogen (N2) 78.1% Hydrogen (H2) 0.5 ppm
Oxygen (O2) 20.9% Nitrogen monoxide (NO) 0.3 ppm
Water vapour 0–5% Ammonia (NH3) <0.1 ppm
Argon 0.93% Sulphur dioxide (SO2) 10−3 ppm
Carbon dioxide (CO2) 380 ppm Nitrogen oxides (NOx) 10−3 ppm
Other rare gases 30 ppm Hydrogen sulphide (H2S) 10−3 ppm
Hydrocarbons (CH4) 2 ppm
Table 22.5 Indicative Pollutant Atmosphere

concentrations of some
Industrial Urban Rural
contaminants
SO2 (µg/m3) 100–200 30–80 5–20
NOx (µg/m3) 100–200 20–40 <10
HCl (µg/m3) 10–20 1–5 <1
Fumes and ashes (µg/m3) 100– 20–50 <20
1000
Continental Sea spray (mg/m2 d) 30 Continental
1000 Coastal
Other dusts (mg/m2 d) 0.1–50
dioxide in the atmosphere, with a pH of 5.5.5 Taking into account the presence—
even if minimal—of SO2 and NOx, even in non-polluted atmospheres, pH drops to
five. Hence, the term acid rain refers to any deposit that causes a decrease in pH
below five. In some periods of the year, the pH on metallic surfaces in industrial
areas is between 4 and 4.5. It can be even lower in highly polluted areas.
Sulphur oxides. Among polluting substances, sulphur oxides (sulphur dioxide,

SO2, and sulphuric anhydride, SO3) are the most dangerous. They can be present in
large quantities in urban and industrial areas because of the use of sulphur con-
taining fuels. When emitted, SO3 content is generally 1–5% with respect to SO2.
The latter gradually oxidises to SO3 with a permanence time in the atmosphere of
2–4 days. Sulphur oxides are the main responsible of acid rains. Just 100 lg/m3 of
SO2 is enough to increase remarkably the corrosion rate of carbon steel. Such
concentrations are found in industrial areas, especially in winter, and accelerate the
deterioration of protective coatings such as painting and metallic coatings like
galvanizing. Nowadays, SO2 emissions in industrial countries are controlled and
5
Carbon dioxide reacts with water in the following way: CO2 þ H2 O ! H þ þ HCO3 . The
equilibrium constant of this reactions is: K ¼ ½H þ ½HCO3 =½CO2 ¼ 107:6 . Since
½H þ ¼ ½HCO3 , then ½H þ ¼ 107:6 ½CO2 . For a CO2 concentration of 380 ppm:
2
þ 2 11 þ 5:5
½H ¼ 10 ; then ½H ¼ 10 ; pH is then 5.5.
there has been a sensible decrease in emissions in the last three decades. Anyway,
they still represent the most important corrosion issue in urban and industrial areas.
Chlorides. Chlorides accelerate atmospheric corrosion processes both because they
produce hygroscopic salts, which increase time of wetness, and because they make
corrosion products less protective. Chlorides are present mostly in coastal areas.
The mass of chlorides depositing on exposed surfaces decreases with distance from
the coast. The parameters that play a role are not only the distance from the sea, but
also wind speed and direction, surface orientation with respect to wind and to the
ground, and height of surfaces. The Italian coastal situation is generally less
aggressive than the average European one, due to the absence of strong permanent
winds coming from the sea to the mainland, and consequently the influence of
chlorides does not exceed a few hundred metres from the coast. Yet, in some areas
affected by mistral winds—in particular west Sardinia and east Sicily—chlorides
may be present in significant quantities also at higher distances. Chlorides are also
present when de-icing salts, as sodium chloride, are used.
Solid particles. Air is also characterized by the presence of very small solid par-
ticles of different origin. Inorganic particles are lifted in air by the wind, for instance
silica sand; vegetal organic particles, microorganisms and other organic substances;
combustion by-products and ashes from industrial plants, domestic heating and
combustion engines. The presence of these particles on the surface of metals can
accelerate corrosion by favouring the time of wetness by capillary condensation or
by chemical condensation in the presence of hygroscopic salts. They may also exert
a depassivating action, as in the case of salts like (NH4)2SO4 and NaCl, which
dissolve in the liquid film and impede the formation of protective corrosion
products. The effect of the presence of carbon powders is twofold: enhances gal-
vanic corrosion (due to its electrical conductivity) and favours the absorption of
corrosive gases as SO2.
22.3 Classification of Environments
Factors that influence atmospheric corrosion of metals change consistently as a

function of climatic zone, latitude, rainy or dry weather, rural or urban areas and
proximity to the sea. To classify the corrosion behaviour in different geographical
areas, the following four environments are generally considered:
• Rural environment: basically not polluted, far from industrial atmospheric
exhaust releases and from coastal areas
• Urban environment: residential or commercial areas with light or moderate
pollution, due for instance to car traffic or light industrial activities
• Industrial environment: characterized by relevant pollution, due to the presence
of heavy industrial activities, mainly chemical and metallurgical ones
• Marine environment: areas close to the seaside.
Table 22.6 Classification of pollution levels based on SO2 and chloride deposition as reported in
ISO 9223 standard
Sulphur dioxide Chlorides
SO2 Deposition Concentration (µg/ Chlorides Deposition
class rate (mg/m2 d) m3) class rate (mg/m2 d)
P0 <4 <5 S0 <3
P1 4–24 5–30 S1 3–60
P2 24–80 30–90 S2 60–300
P3 80–200 90–250 S3 300–1500
1000
Industrial severe
Industrial marine
Industrial
100
[SO2] (μg/m3)
Urban Urban marine
10
Rural Marine
1
1 10 100 1000
[Cl-] (mg/m2d)
Fig. 22.3 Classification map for atmospheric corrosion environments according to ISO 9223
ISO 9223 standard classifies pollution levels as a function of SO2 and chlorides
deposition rate, following the scheme reported in Table 22.6. Figure 22.3 shows the
map of corrosive atmosphere.
22.3.1 Microenvironments
The above reported definition of environments helps perform a first assessment of

corrosion behaviour, but what really matters is the microenvironment. For instance,
in areas close to chimneys or industrial exhausts, especially in conditions of thermal
22.3 Classification of Environments 487
inversion, the concentration of pollutants and dusts is higher; conversely, if wind is

present, leeward areas with respect to the emissions location—or coast position—
are completely different from windward ones. Even between central and suburban
areas of large cities, or between indoor and outdoor environments, or within one
same building, the situation may change consistently.
22.3.2 Classification of Atmospheric Corrosiveness
ISO 9223, ISO 9224, ISO 9225 and ISO 9226 standards propose a classification of
corrosiveness and a methodology to evaluate corrosion rate. Specifically, ISO 9223
defines six exposure classes: C1, C2, C3, C4, C5 and CX as a function of the
increasing environment corrosiveness, and indicates for each class the intervals of
corrosion rate values expected after one year of exposure of different metals. The
methodology to evaluate corrosion rate in the first year of exposure is reported in
ISO 9226, together with composition limits for considered metals (carbon steel,
zinc, copper and aluminium).
Table 22.7 reports, for different classes of exposure, examples of corresponding
outdoor environments (from ISO 9223 Annex) and corrosion rates in the first year
of exposure in the specific environment for carbon steel and zinc.
When experimental data on corrosion rate are missing, a second approach
proposed by standards allows estimating corrosion rate for the first year of exposure
based on environment data. In this case, calculations are performed with dose-effect
type equations and evaluations are based on the description of exposure conditions:
relative humidity, SO2 and chlorides deposition (Pd and Sd parameters, already
described in Table 22.6 and evaluated based on ISO 9225). This method involves
higher uncertainties in predictions.
Once the corrosion rate for the first year is known, it is then possible to estimate
service life following ISO 9224 by applying the following equation:
s ¼ C rate;1 tb ð22:1Þ
where s is the penetration of the corrosive attack, t the exposure time (years) and b a
constant that depends on metal composition (on average, 0.5 for carbon steel and
0.8 for zinc, as reported in the standard) which underlines that these values were
calculated on the basis of well-defined chemical compositions. In particular, for
steel corrective factors are proposed as a function of alloying elements and their
content. The standard suggests considering a validity of this equation up to a
maximum of 20 years of service life, afterwards corrosion rate stabilizes and suc-
cessive variations of corrosion penetration follow a linear trend.
Figure 22.4 shows corrosion penetration values calculated after 20 years of
service life with both approaches suggested by the standard: values proposed for
classes C1–CX are compared with values calculated with the dose-effect equation
Table 22.7 Classification of atmospheric environments based on first year corrosion rate in lm/
year (according to ISO 9223)
Corrosiveness Outdoor environment Carbon Zinc
category steel
C1 Very Dry or cold zone, environment with very low pollution 1.3 0.1
low and time of wetness, for instance desert and Antarctic
areas
C2 Low Temperate zones, low polluted environments, e.g. rural 1.3–25 0.1–0.7
areas, small towns
Dry or cold zones atmospheric environments with short
time of wetness, e.g., deserts, subarctic areas
C3 Medium Temperate zones, environments with medium levels of 25–50 0.7–2.1
pollution e.g. urban areas, coastal areas with low
deposition of chlorides
Subtropical and tropical zones, atmospheres with low
pollution
C4 High Temperate zones, environments with high pollution or 50–80 2.1–4.2
substantial effects of chlorides, e.g. polluted urban areas,
industrial areas, coastal areas without spray or salt water
or exposure to strong effects of de-icing salts
C5 Very Temperate or subtropical zones, heavily polluted and/or 80–200 4.2–8.4
high with significant effects of chlorides, e.g. industrial areas,
coastal areas, sheltered positions on coastline
CX Extreme Subtropical or tropical zones (very high time of wetness), 200– 8.4–25
environments with very high pollution and/or strong 700
effects of chlorides, e.g. extreme industrial areas, coastal
and offshore areas, occasional contact with salt spray
method. For P0–P2 and S0–S2 classes, the maximum values of pollutant concen-
tration in each class were considered for P3 and S3 classes the maximum pollutant
concentration used in the dose-effect correlation was considered.
22.3.3 Indoor Atmosphere
Most of the experimental data referred to atmospheric corrosion are related to

outdoor exposure. The conditions of indoors exposure are different, because the
metal is not exposed to rain and direct sunlight. Rusting depends on the conden-
sation of the moisture, which may evaporate from the surface much more slowly in
enclosed conditions; moreover, the corrosion products tend to remain on the surface
and may build up in time to a thick layer.
According to the ISO 9223 standard, the indoor microclimates are included
mainly in the category s1 and s2, as far as the time of wetness is concerned. In
indoor atmospheres without conditioning, the categories s3 to s5 may apply if
22.3 Classification of Environments 489
1500
T 20°C, RH 80%, 20 years
Corrosion thickness (μm)
1000
Carbon steel
Zinc
500
0
C1 P0 C2 P1 P2 C3 S1 P3 C4 S2 C5 S3 CX
Corrosivity category
Fig. 22.4 Corrosion penetration values calculated after 20 years of service life: comparison
between classes C1–CX and values calculated with the dose-effect equation method
sources of water vapor are present or in humid condition. Combining the values of
time of wetness by that of pollution, the relevant corrosive classes can be defined.
ISO 11844 classifies five categories of indoor atmospheres:
• IC 1—Very low indoor corrosivity
• IC 2—Low indoor corrosivity
• IC 3—Medium indoor corrosivity
• IC 4—High indoor corrosivity
• IC 5—Very high indoor corrosivity.
The upper limit of categories IC3 and IC5 correspond roughly to the upper limit
of category C1 and C2, as per ISO 9223.
The corrosiveness of indoor atmospheres increases with the relative humidity,
type and levels of pollution. Frequency of relative humidity and temperature
variation, and frequency and time of condensation are also important. Accordingly,
the time of wetness defined in ISO 9223 is not exactly applicable to indoor cor-
rosiveness. Pollutant concentration are generally lower or similar in indoor envi-
ronments, depending on the sheltering (i.e. filtration, conditioning) except for cases
of internal sources of pollution.
22.4 Corrosion Behaviour of Most Used Metals
22.4.1 Carbon Steels
Carbon steels do not exhibit good atmospheric corrosion behaviour because rust,
which forms on their surface, consists of a porous, non-protective layer.
The attack generally takes place as uniform corrosion, with a corrosion rate
ranging from 20 lm/year in rural environments to 40–50 lm/year in urban envi-
ronments, 60–100 lm/year in urban-industrial or marine ones and eventually 100–
200 lm/year in industrial areas, and even higher in humid tropical marine climates.
Hence, carbon steel structures must be protected. Painting cycles or zinc coatings
are used for this purpose.
Painting cycles. The use of paints is the most common practice to protect carbon steel
structures exposed to the atmosphere. The general aspects of this technique are
described in Chap. 17. Here only maintenance issues will be briefly considered.
Except for extremely low aggressiveness conditions, a painting cycle is generally not
able to ensure a duration sufficient to protect carbon steel for the whole service life
(50 years for civil structures, 20–30 years for industrial plants). It is then necessary to
proceed with periodical re-applications, which require the removal of the old paint and
rust before applying the new coat, therefore these interventions are rather expensive.
It is common practice to plan a preventative maintenance, which helps avoid
expensive total painting replacements. A maintenance intervention consists of
periodical repair of the damaged coating, whose frequency depends on environment
aggressiveness, operation costs and inspections results (Fig. 22.5; Table 22.8).
Ideal Cycle
0 5 10 15 20 25 30
Time
(years)
Initial Spot touch-up Maintenance

Full Repaint
painting 3-5% Repaint
Practical Cycle
0 5 10 15 20 25 30
Time
(years)
Initial Spot touch-up Maintenance

Full repaint
painting 10% Repaint
Fig. 22.5 Maintenance cycles for painted structures (from Brevoort and Roebuck 1993)
22.4 Corrosion Behaviour of Most Used Metals 491
Table 22.8 Initial expected lifetime for some painting cycles in marine and urban environments
Cycle Surface Minimum Marine Urban
preparation thickness (lm) environment (years) environment (years)
HB ST epoxy/ SP6 300 12 (16) 14 (21)
HB ST epoxy/
polyester
urethane
Zn urethane/HB SP10 250 12 (16) 14 (21)
acrylic-urethane/
acrylic-urethane
Zn inorganic/HB SP10 280 12 (16) 15 (22.5)
epoxy/HB epoxy
acrylic urethane
epoxy/polyester
urethane
Zn inorganic/HB SP10 225 12 (16) 14 (21)
epoxy/HB epoxy
Zn epoxy/HB SP10 280 12 (16) 14 (21)
epoxy/HB epoxy
Zn organic/HB SP10 280 12 (16) 15 (22.5)
acrylic urethane/
HB acrylic
urethane
Zn epoxy/HB SP10 225 12 (16) 14 (21)
epoxy/polyester
urethane
vinylic/HB
vinylic
Zn inorganic SP10 75 (15) (17)
Zn organic SP10 75 (6) (5)
Values refer to an ideal maintenance cycle, or to a practical one (in brackets) (from Brevoort and
Roebuck 1993)
HB high build (high thickness), ST surface tolerant, SP6 commerical blast, SP10 white metal
sandblasting
These interventions are undoubtedly the cheapest way to extend the coating life.
Yet, they are more delicate than the initial application, since a good adherence
between old and new paint is often difficult to achieve. It is therefore recommended,
when choosing the painting cycle in the design stage, to take into account the
feasibility of maintenance operations.
Zinc coatings. Zinc coatings are the most widespread metallic coatings to protect
carbon steel. Zinc corrosion rate, even in industrial and marine environments, is
generally 10–30 times lower than that of carbon steel, since it tends to form a
protective film, which is stable in the pH range of 6–12.5. Initially, zinc corrosion
200
T 20°C CX
RH 80%
C5
150
Corrosion thickness (μm)
C4
100
C3
50
C2
C1
0
0 5 10 15 20 25 30 35 40 45 50
Time (years)
Fig. 22.6 Duration of the zinc coating in different environmental conditions
causes the formation of a hydroxide, which reacts with acid species present in the
atmosphere (in particular, CO2) and forms a protective film of basic zinc carbonate.
In polluted areas, acid pollutants—first sulphur dioxide—produce a basic zinc
sulphate, which is more soluble than carbonate, forming less protective corrosion
products. An analogous situation can be found in marine areas, where a basic zinc
chloride forms, which is more soluble as well. Consequently, zinc corrosion rate
can vary significantly and increase even by one order of magnitude when passing
from rural environments to those polluted by sulphur dioxide or to marine envi-
ronments. Zinc corrosion rate depends on the environment, but it is almost constant
in time (Fig. 22.6). Hence, the duration of the protection offered to steel depends on
the environment and on coating thickness.
The protective characteristics of the coating are lost in case of scratches larger
than some tenth of millimetre. A frequent damage is that caused by welding, as
shown in Fig. 22.7.
The New Delhi Pillar

In New Delhi, India, there is a cast iron column, dating back to the IV century
A.D. (the so-called New Delhi Pillar, Fig. 22.8), which has raised the
curiosity of corrosionists. Its top part is perfectly conserved, showing no
traces of rust, instead it appears coated with a bronze-bluish coloured oxide
layer. Clearly, favourable environmental conditions (absence of chlorides and
sulphur compounds) and the absence of sulphur and phosphorus in the metal
Fig. 22.7 Corrosion at a

damaged zone of zinc coating
caused by welding
allowed the formation and conservation of a compact, protective layer (maybe

magnetite) instead of the typical porous, non-adherent rust. In its sixteen
centuries of service life, the periodic exposure to high temperatures has
favoured the growth of this film, which has reached a considerable thickness.
The good behaviour of the New Delhi Pillar cannot be used to support the
widespread opinion that steels used in Medieval ages or in ancient times were
more resistant than contemporary ones. The good conservation status of many
iron inserts in medieval buildings should be ascribed mainly to the fact that
they operated for centuries in presence of low amounts of water and no
pollution, and only to a limited extent to the fact that the steel produced with
wood carbon did not contain sulphur.
It is curious to notice that also in ancient times steel handcrafts were
compared with older ones, saying that older steels were more resistant. As
Pliny writes: “It is said that in a city close to the Euphrate river, called
Fig. 22.8 The New Delhi

Pillar
Zeugma, there is a chain that Alexander the Great had used to build a bridge.
Some rings of the chain were substituted. These ones corroded in short time,
while the original ones remained intact.”
22.4.2 Weathering Steels (Cor-Ten)
Since the first decades of last century, it was known that by adding 0.2–0.3% of
copper to a carbon steel, corrosion rate halves in atmospheric exposure conditions.
In 1933 the U.S. Steel company launched a new low alloy steel containing 0.2–
0.5% copper, 0.5–1.5% chromium and 0.1–0.2% phosphorus which doubled the
atmospheric corrosion resistance compared with the known copper-alloyed steel;
also the yield strength improved. In the following years, the composition was
adjusted by introducing 0.4% nickel to minimise the damaging induced on the steel
by hot working, and phosphorus was reduced to a content lower than 0.04% to
avoid the formation of welding cracks. Small quantities of other elements (V, Zr,
Mo) were also added to improve mechanical resistance, so that yield strength
increased from 350 to 490 MPa.
These steels were called weathering steels or Cor-ten (corrosion tensile resis-
tance steel). Initially, they were used with the addition of protective coatings.
Applications like cargo carriages, trucks, farm machines, beams for bridges,
showed service lives from 1.5 to 4 times higher than the same components made of
carbon steel with the same protective coatings.
The first important application in the civil sector dates back 1964. It opened the
way to several others, including the Chicago Civic Center, in the central square of
Chicago, fronting the Picasso statue La capra (made of a mix of Cor-ten and
stainless steel, Fig. 22.9), or the Italian Centro Sperimentale Metallurgico, close to
Rome, which is also made of both Cor-ten and stainless steel. The most recent
important applications are beams and scaffoldings of highway bridges (Fig. 22.10).
Weathering steels are self-protecting in many exposure conditions by the for-
mation—in a period of 1 to 4 years—of a pleasant rusty patina, characterized by an
outer porous layer and an inner thin film, amorphous and impermeable, rich in
copper, chromium and phosphorus, which enhances corrosion resistance. During its
formation, affecting parameters are wet-dry cycles, sunlight exposure (which
probably exert a photocatalytic action), degree and type of pollution, therefore
depending on geographical location, distance from the sea, and its shape. The
importance of wet-dry cycles lies on the evidence that the patina does not form on
permanently wet zones. Therefore, critical conditions are met at lower parts of
structures in contact with soil and where stagnant water is formed.
In the presence of high chlorides concentration, as in marine environments or
where de-icing salts are used, the patina can form in a non-correct way. Similarly,
Fig. 22.9 Picasso statue

behind the Chicago Civic
Center, made partially of
Cor-ten, 1960
Fig. 22.10 Viaducts beams

made of Cor-ten
high concentrations of SO2 associated with high humidity conditions, as typical in

industrial and marine-industrial areas in the years 1960s–1970s, lead to a
non-protective patina as experienced in some unsuccessful applications observed in
the 1970s.
Figure 22.11 compares the corrosion behaviour of carbon steel and weathering
steel in industrial and marine environments. As the protective patina is formed,
Industrial environment Marine environment

300 300
Service life (years)
Service life (years)

Carbon steel
200 200 Carbon steel
Weathering steel
100 Weathering steel 100
0 0
5 10 5 10
Exposure time (year) Exposure time (year)
Fig. 22.11 Atmospheric corrosion trend of carbon steel and weathering steel
thickness loss is maximum after few years, then corrosion rate becomes negligible.
In marine exposure, with continuous wetting by salty water, corrosion behaviour is
similar to carbon steel.
22.4.3 Stainless Steels
Stainless steels offer an excellent behaviour in atmosphere if correctly selected.

However, some concerns may arise, dealing with:
• Surface staining or pinning, in marine and industrial zones, especially in
Mo-free stainless steels
• Crevice corrosion when gaps or dead spaces are present, favouring the
entrapping of electrolyte
• Galvanic coupling, which affects less noble metals as carbon steel, aluminium
and zinc coupled with stainless steels. In humid atmosphere and in the presence
of condensation, insulation is recommended. Figure 22.12 shows an example of
a galvanic corrosion in an atmospherically exposed galvanic coupling.
Figure 22.13 reports a guidance map for the choice of stainless steel based on
environmental conditions as pollutants concentration.
Ferritic stainless steels. The classical 12 and 17% chromium stainless steels (AISI
410 and 430) as well as martensitic grades are the worst corrosion resistant stainless
steels in atmosphere. In particular 12%Cr grade may show pinning and staining
after a few years of exposure especially when a rough surface finishing is present.
A regular cleaning of the metal surface can help avoiding these alterations, which
anyway do not compromise mechanical resistance. These steels are not recom-
mended in urban-industrial or marine environments, but they can be used in less
aggressive conditions.
Fig. 22.12 Galvanic coupling: stainless steel screws on aluminium plate
1000
Alloys 20 High alloy steels
100 AISI 316

[SO2] (μg/m3)
Alloys 20
AISI 304
10
AISI 430
1
1 10 100 1000
[Cl-] (mg/m2d)
Fig. 22.13 Selection map of stainless steels in atmospheres based on pollutant concentration
Stainless steels without molybdenum. AISI 304 and related grades for welded
structures, AISI 304L and AISI 321, are definitely the most used stainless steels.
They do not undergo corrosion in rural or urban areas (Fig. 22.14). In the latter
ones, after several years a slight opacification and some pinning can be noticed in
Fig. 22.14 Chrysler Building

(New York), made in AISI
304 stainless steel, 1930
areas shielded from rain. Conversely, in heavily polluted industrial and marine
atmosphere they suffer localised corrosion, usually of shallow type. Hence, these
steels can be adopted in rural, urban and low polluted industrial areas regardless the
surface finishing. In polluted areas, a low roughness finishing is recommended.
Stainless steels with molybdenum. AISI 316 and related grades for welded
structures, 316L and 316Ti, containing Mo show good performance also in polluted
and marine atmosphere (Figs. 22.15 and 22.16). Nevertheless, it is still necessary to
avoid geometries and exposure conditions or surface finishing that may favour
water stagnation or formation of any deposit on the surfaces, or create gaps and
crevices (as may happen, for instance, in the case of nets, badly performed welding
or mechanical junctions). They suffer corrosion only in heavily polluted marine
atmosphere due to the presence of chemical or metallurgical industries, or inside
highway tunnels, where antifreeze salts carried by vehicles and high levels of SO2
are simultaneously present. They also undergo corrosion if intermittent or contin-
uous contact with brackish water or seawater takes place. In these cases,
high-alloyed steels should be used. In the atmosphere that generates inside swim-
ming pools, where water is maintained at temperatures higher than 30 °C and is
treated with chlorine, also AISI 316 steels may present unacceptable corrosion
attacks.
Fig. 22.15 Petronas Towers

(Kuala Lumpur), made in
AISI 316 stainless steel, 2000
Fig. 22.16 The “Bean”

(Chicago), made in AISI 316
stainless steel, 2006
Austeno-ferritic (duplex) stainless steels. As far as pitting or crevice corrosion

forms are concerned, the corrosion behaviour of these steels is similar to that of
austenitic steels with same PREN index. On the other hand, they are much more
resistant to SCC.
Corrosion of Stainless Steels in Swimming Pools

Stainless steels are largely employed in swimming pools: stepladders,
handrails, aeration and ventilation pipes, trampolines, tie beams. In the last
20 years an increase in corrosion phenomena on these elements was regis-
tered: surface attacks with formation of rust (staining), localised spots (pin-
ning), perforating corrosion (pitting) and even SCC with catastrophic
consequences. In these acid conditions, SCC may take place on stainless
steels at temperatures lower than 50 °C and close to room temperatures.
For instance, in 1985 the reinforced concrete false ceiling of a swimming
pool in Zurich (built in 1972) collapsed, killing 12 people and injuring many
others. The collapse was caused by the SCC-related failure of AISI 304 tie
beams supporting the 200-ton false ceiling to the swimming pool roof. More
recently, for the same reason, several other cases occurred, fortunately
without tragic consequences; in fact, in 2001 and 2003 the suspended ceilings
of two swimming pools collapsed, in Netherlands and Finland, respectively.
SCC occurs on aerial surfaces exposed to swimming pool atmospheres,
but does not on surfaces that are immersed or continuously rinsed by the pool
water. This occurs because of the formation of chloride containing acidic
condensates.
When chlorine, which is normally used as sanitizing agent in swimming
pools, is added to water, it dismutes and produces hypo-chloric acid and
hydrochloric acid. The residual content of gaseous chlorine in water decreases
to 1–2 ppm. At a temperature of 28–29 °C, this concentration usually gen-
erates a very low vapour pressure, hence a low chlorine content in the at-
mosphere, in the range 3–6 mg/m3. This does not justify the high chloride
contents observed on metallic surfaces where corrosion onsets: the mecha-
nism is therefore more complex. Chlorine reacts both with water and with
nitrogen and ammonia compounds present in water, released for instance by
human perspiration or urine. The reaction causes the formation of chlo-
ramines (mono-chloramine NH2Cl; di-chloramine NHCl2; tri-chloramine
NCl3). These substances are highly volatile. Their evaporation and conden-
sation on cold metallic surfaces explain the chloride-enrichment mechanism
on aerial surfaces.
In the last 15–20 years a worse trend of failures has been recorded: the
main reason is recognized on the increase of water temperature, which raised
from 24 to 26–30 °C. Truly, the assessment of the incident occurred at the
abovementioned Zurich pool revealed that the water temperature was raised
to 37 °C three days a week as required and reserved for disabled people.
To prevent the SCC occurrence here described it is necessary to: limit water
temperature; maintain relative humidity in the range 50–70%; clean stainless
steel surfaces; avoid the use of AISI 304 or 316; choose SCC-resistant stainless
steels as duplex (25–07) (with 3% Mo, PREN 35), AISI 904L (4.5% Mo,
PREN 36), or alloys with 6% Mo (254 SMO, PREN 41).
22.4.4 Copper and Copper-Alloys
Copper and, in general, its alloys (bronze, brass) present a good atmospheric cor-
rosion resistance. After a time that varies between few years and several years they
become covered by a green patina (noble patina) mainly consisting of a mixture of
Cu2CO3(OH)2, Cu3(CO3)2(OH)2 and Cu4SO4(OH)6, which strongly reduces cor-
rosion rates (Fig. 22.17). In the presence of a protective patina, in rural areas
corrosion rate is lower than 1 µm/year, in industrial and marine environments
corrosion rate is a few µm/year. Corrosion attacks are possible only in presence of
high pollutants concentration or stagnant water.
In civil building, copper is largely used for roofs and for rainwater drainage
systems. After 1–2 years exposure to atmosphere, copper assumes a uniform dark
colour, indicating the formation of a stable protective patina. In urban and industrial
atmospheres, having a moderate content of sulphur dioxide, and in marine atmo-
spheres, a green patina (based on copper hydroxyl-sulphate or copper
hydroxy-chloride) forms in about 5–7 years. The green patina forms more slowly
on vertical surfaces than horizontal or leaning surfaces, because the latter remain
wet longer. In the presence of acidic water, as in industrial atmospheres near
chimneys, the patina of hydroxyl-sulphate does not form; in these cases, the water
drained from copper surfaces has a high copper ions content and gives rise to the
blue colour of the wet surfaces. The same water, due to the reduction of the copper
ions, can give rise to corrosion of steel and aluminium.
22.4.5 Aluminium
In a pH interval between 4.5 and 8.5, in environments with low pollution, a natural
protective oxide film covers aluminium, thus preventing excellently corrosion with
a corrosion rate lower than 1 µm/year. The protection properties of the passive film
Fig. 22.17 Parliament

buildings (Ottawa), mansard
roofs made in copper
Fig. 22.18 Warsaw

residential building in painted
anodized aluminium (Poland)
lower in the presence of SO2, carbon particles and chlorides (marine environments)
then triggering localised corrosion. To strengthen corrosion resistance, anodizing is
used, which produces a thicker and robust film. Figures 22.18 and 22.19 show some
use of anodized aluminium in polluted environments.
Aluminium is widely used for window frames and roofs. For these applications,
anodised aluminium is normally installed. The use of pre-painted semi-finished
products is also common. The most used paints are alkyd-melamine, polyester and
polyvinyl-fluoride. Concrete, due to the high pH of water present in its pores, is
highly corrosive for aluminium: when preparing mortars and concrete it is advisable
to avoid splashes of wet cement on aluminium surfaces, since they cause stains.
A good practice is to protect aluminium surface with removable plastic sheets.
22.4.6 Other Metallic Materials
Lead. The protection mechanism is similar to that of zinc, leading to the formation
of a basic carbonate more resistant than the one that forms on zinc (Fig. 22.20).
Titanium. The appealing aspect of titanium and its resistance to atmospheric agents
opened the way to applications of this metal in architecture for envelopes, external
and internal coatings of relevant buildings. Titanium is used both in its natural grey
Fig. 22.19 Pirelli tower

(Milan), building envelope in
anodized aluminium, 1959
Fig. 22.20 Auditorium

(Rome), Renzo Piano, lead,
1996
colour and with anodic colours. To overcome cost related issues, it is used in very
thin sheets, often applied on polymeric supports.
A Catchy “Mono-Chromatism” Effect

Large grey titanium surfaces, at least in some finishing conditions, give
coloured glares whose hues change with observation angle and type of
Fig. 22.21 Guggenheim museum, Bilbao, F.O. Gehry, titanium, 1998
illuminant. This behaviour is well embodied by the Guggenheim Museum of

Bilbao, opened in 1998. Architect Frank O. Gehry has realized an amazing
titanium envelope: “a sort of big metallic stripe, as François Burkhardt writes,
which wraps the different ‘boxes’ the museum is made of and ensure its unity
forming an incredible ‘landscape’ that—given the multitude of inclined or
rounded planes—transports light, arising a different color in each single
point, until it forms a catchy monochromatism effect that goes from gold to
blue, and from pink to white”.
To be true, the aspect of ‘natural’ titanium can vary with surface finishing
—drawing, sandblasting, etching or passivation. As Gehry writes: “The
rolling of the material is very delicate. It can lead to a dead surface or a
wonderful light-receptive one.” Whatever the treatment, the resistance to
atmospheric agents remains very high. It is again Gehry who writes: “The
titanium is thinner than stainless steel would have been; it is a third of a
millimetre thick. […] It’s ironic that the stability given by stone is false,
because stone deteriorates in the pollution of our cities whereas a third of a
millimetre of titanium is a hundred-year guarantee against city pollution. We

have to rethink what represents stability (Fig. 22.21).”
22.5 Corrosion and Protection of Metallic Cultural

Heritage
The atmospheric corrosion of cultural heritage surfaces is highly influenced by the

history of the metal and in particular by the presence of corrosion layers. Many
statues and architectural elements, such as claddings and roofing, are originally
designed to be exposed outdoor and are typically characterised by the presence of
natural and/or artificial patina. Both natural and artificial patinas have a relevant
historical and artistically value (see box “The noble patina”). The protection of
outdoor objects is frequently obtained by the use of protective treatments. It has to
be considered that there are specific requirements to be fulfilled by a product to be
applied in the field of Cultural Heritage such as good protective efficacy, good
optical properties, that is negligible modification of the appearance of the surface in
terms of colour and gloss, chemical and photochemical stability and inertness
towards the substrate. Moreover, retreatability of a material is an important
requirement since protective treatments need to be maintained and, if necessary, to
be removed and reapplied without altering the surface of the material.
In addition, there is a huge variety of objects that have remained underground or
under the sea for centuries; a great variety of salts and corrosion products over the
surface may be present. Unfortunately, it is not always possible to completely
remove salts and destabilising species without irremediably damaging the object
and therefore specific conservation strategies have to be considered since the
presence of highly hygroscopic salts may favour condensation of water over the
surface. It may happen, then, that atmospheric corrosion is active even at relative
humilities that are normally considered safe. Environmental control and the used of
closed showcases are frequent approaches for the preservation of archaeological
objects. The closed environment of the showcases may present some issues, since
different materials may constitute the objects (metal and wood for instance). They
may require different environmental condition to be preserved. In the presence of
hygroscopic salts, the metal may require a quite low relative humidity, which may
result detrimental for the wood. In addition, wood may release substances, such as
acetic or formic acid, which would cumulate into the showcase causing an accel-
eration of corrosion processes of bronze artefacts.
The Noble Patina

The term noble patina is reserved to the green patina that forms as corrosion
product of copper or bronze. Some of the most ancient observations and
considerations on corrosion phenomena actually deal with this patina. In De

Pythiae Oraculis Plutarch describes a statue at the entrance of the Apollo
sanctuary, in Delphi. Although some centuries old, it appears covered with a
brilliant patina of uniform colour; and he wonders whether it has been pro-
duced by ancient sculptor masters with special manufacturing, or by the
action of atmosphere, which penetrate bronze and push corrosion out; or,
eventually, if it is bronze itself that produce it by ageing.
In the Greek and Roman world, bronze works were preferred to show a
finishing that helped the natural metal colour stand out, hence the problem
was to avoid the formation of rust (aerugo, bronze rust) with periodical
maintenance involving cleaning and oiling. Yet, sometimes artists broke with
tradition and searched for the corrosion attack, instead of avoiding it. For
instance, in San Marco horses in Venice, Italy, the mane gilding is engraved
to weaken the brightness of gold with the colour of bronze appearing
underneath, or better, of its corrosion products. In some cases, the corrosion
product is not used to give a finishing to a complete work, but even to express
feelings and moods. Pliny tells that the sculptor Aristonides, when repre-
senting Athamas shocked after having thrown his son Learchus from a cliff,
used a copper-iron alloy, so that iron would rust inside the shiny copper
surface and express the shame and dismay of the man.
In the Renaissance, the art of bronze melting finds new life and artificial
patina is born. As Vasari writes in his treatise on sculpture: “In time, bronze
takes by itself a colour that turns to black, not to red as it happens when it is
worked. Some make it black with oil, some make it green with vinegar, some
give the black colour with paints, so that everyone changes it the way it
pleases him most”. The diffusion of artificial patina on large scale dates to the
beginning of the 20th century. Even if treatments and recipes increase, and
with them the colours obtained, patina-making keeps being an art that relies
on the skills and creativity of the artists that perform it, rather than on
technical knowledge. Indeed, the artists themselves often realize it.
Even now, this treatment does not provide predictable and repeatable
results: indeed, even a sculptor like Henry Moore defined it in 1967 as a very
exciting intervention, but with very uncertain results. In fact, he writes:
“Bronze naturally in the open air (particularly near the sea) will turn with
time and the action of the atmosphere to a beautiful green. But sometimes one
can’t wait for nature to have its go at the bronze, and you can speed it up by
treating the bronze with different acids which will produce different effects.
Some will turn the bronze black, others will turn it green, others will turn it
red. Usually, when I prepare the cast I have an idea of the bronze finishing I
want, dark or clear, and of the colour I want to obtain. When the cast comes
back from the foundry, I give the patina, and sometimes it comes out good,
but sometimes you cannot repeat what you have already done in other
occasions. It is very exciting but poorly reproducible, this operation of bronze
22.5 Corrosion and Protection of Metallic Cultural Heritage 507
patination.” (H. Moore, Henry Moore on Sculpture, 140, Philip James, New
York, 1967)
• ASTM G 50, Standard practice for conducting atmospheric corrosion tests on

metals, American Society for Testing of Materials, West Conshohocken, PA.
• ISO 8565, Metals and alloys—Atmospheric corrosion testing—General
requirements, International Standard Organization, Geneva, Switzerland.
• ISO 9223, Corrosion of metals and alloys—Corrosivity of atmospheres—
Classification, determination and estimation, International Standard
Guiding values for the corrosivity categories, International Standard
Measurement of environmental parameters affecting corrosivity of atmospheres,
Determination of corrosion rate of standard specimens for the evaluation of
corrosivity, International Standard Organization, Geneva, Switzerland.
• ISO 11844, Corrosion of metals and alloys—Classification of low corrosivity of
indoor atmospheres, International Standard Organization, Geneva, Switzerland.
22:1. Compare the atmospheric corrosion behaviour of stainless steel type AISI
316 (18% Cr, 8–10% Ni, 2–3% Mo) and titanium in the following condi-
tions: rural environment, industrial environment (very polluted).
22:2. Compare the atmospheric corrosion behaviour of stainless steel type AISI 304
(18% Cr, 8–10% Ni) and galvanised steel (Zn thickness 80 lm) in the following
conditions: urban environment, industrial environment (medium pollution).
22:3. Compare the atmospheric corrosion behaviour of “weathering” steel and Al–
Si–Mg alloy (series 6xxx) in the following conditions: urban environment,
marine environment.
22:4. Evaluate atmospheric corrosion behaviour for carbon steel in urban areas
(temperate zones); select a suitable value of the corrosion rate in the first year
(Crate,1) and exponent b (Eq. 22.1) and evaluate the thickness loss after 20
and 50 years. To guarantee the minimum service life 50 years, with corro-
sion allowance 0.4 mm, is necessary to protect the steel? If yes, which
protection method is suggested?
22:5. Repeat the Exercise 22.4 considering coastal areas in subtropical zones and
rural areas in temperate zones.
22:6. Evaluate atmospheric corrosion behaviour for galvanised steel in industrial
areas, medium pollution (temperate zones); select a suitable value of the
corrosion rate in the first year (Crate,1) and exponent b (Eq. 22.1) and evaluate
the thickness loss after 20 and 50 years; which is the minimum zinc thick-
ness able to guarantee the service life (50 years) without corrosion?
22:7. Repeat the Exercise 22.6 considering environment with low pollution (rural)
and coastal areas in temperate zones.
22:8. A zinc layer is applied on carbon steel to protect it from atmospheric cor-
rosion. Which is the influence of a defect in the zinc layer on steel corrosion
behaviour? The effect would be the same if copper was used instead of zinc?
22:9. Why the performance of weathering steels is not satisfactory in case of
immersion or continuous exposure to very high humidity (near to
saturation)?
22:10. Explain the rationale behind the Fig. 22.13 (selection of stainless steels in
atmospheric exposure).
22:11. Which is the main difference between the corrosion product formed in at-
mosphere by copper (and their alloys) and stainless steels? Is there any effect
of this difference on the corrosion of the two metallic materials?
Bibliography
Brevoort GH, Roebuck AH (1993) A review and update of the paint and coatings cost and
selection guide. Mater Perform 4:31–35
De la Fuente D, Castano JG, Morcillo M (2007) Long-term atmospheric corrosion of zinc. Corros
Sci 49:1420–1436
De la Fuente D, Diaz I, Simancas J, Chico B, Morcillo M (2011) Long term atmospheric corrosion
of mild steel. Corros Sci 53:604–617
Dillmann P (2007) Corrosion of metallic heritage artefacts. Investigation, conservation and
prediction for long-term behaviour. In: European federation of corrosion (EFC) series, vol 48.
Woodhead Publishing, London, UK
Dillmann P (2013) Corrosion and conservation of cultural heritage metallic artefacts. In: European
federation of corrosion (EFC) series, vol 65. Woodhead Publishing, London, UK
Knotkova D, Kreislova K, Dean SW (2010) ISO CORRAG international atmospheric exposure
program: summary of results. In: ASTM data series, vol 71. ASTM International, West
Conshohocken PA, USA
LeyGraf C, Wallinder IO, Tidblad J, Graedel T (2016) Atmospheric corrosion. Wiley, New York,
NY
Munger CG (1984) Corrosion prevention by protecting coating. NACE International, Houston, TX
Panchenko YM, Marshakov AI (2016) Long-term prediction of metal corrosion losses in
atmosphere using a power-linear function. Corros Sci 109:217–229
Chapter 23
Corrosion in Concrete
You could not say that a piecework is perfect if it were useful for
a short time.
Andrea Palladio, Italian architect (1508–1580)
Abstract This chapter deals with corrosion of rebars in concrete, specifying the
types of corrosion forms with particular attention to the two most common ones,
carbonation induced corrosion and chloride induced corrosion, due to the penetra-
tion in concrete of CO2 and chloride ions, respectively. Hydrogen embrittlement of
high strength steels and stray current corrosion are also introduced. The preventative
and protection methods that can be adopted are discussed, starting with concrete
quality and dealing with additional protection methods, namely cathodic prevention,
stainless steel and galvanised steel reinforcements, concrete coatings and corrosion
inhibitors. Finally, an outline on inspection and diagnosis is presented.

https://doi.org/10.1007/978-3-319-97625-9_23
510 23 Corrosion in Concrete
Fig. 23.2 Example of carbonation process (Policlinico Hospital, Naples, Italy, 1972)
23.1 Initiation, Propagation and Morphology of Corrosion
Romans built the Pantheon in Rome, Italy, about 2000 years ago and it is still
perfectly conserved, just like structures which remained immersed in seawater for
almost the same period of time. This demonstrates that concrete shows the dura-
bility of natural stones, provided that some specific causes of degradation, as acid
rains, sulphate-enriched waters, freeze-thaw cycling and reactive aggregates are
absent. The case of reinforced concrete structures is much different, as experience
shows daily, and far from being “eternal”, their durability is limited sometimes to
tens of years, because of corrosion of steel reinforcements. In aerated, chloride-free
alkaline solutions, pH > 11.5, iron passivates because a protective oxide film, a few
nanometres thick, forms. In these conditions, corrosion rate is practically nil. This
also happens to steel reinforcements embedded in sound, pristine concrete, which
hosts in its pores a solution of sodium, potassium and calcium hydroxides with a pH
between 13 and 13.5. Unfortunately, over time, concrete can lose its passivating
properties for two main reasons1:
1
Passive reinforcement can also become active if interfered by stray current, as discussed forward.
23.1 Initiation, Propagation and Morphology of Corrosion 511
Corrosion
penetration
Maximum allowable thickness loss
Time
Initiation Propagation
Lifetime
Fig. 23.3 Initiation and propagation stages for steel reinforcement corrosion in concrete (Tuutti’s
model 1982)
• Chloride contamination when concrete is in contact with chloride-containing

environments. When chlorides penetrating the concrete cover exceed a critical
concentration on the reinforcement surface, there is a local passive film
breakdown (Fig. 23.1)
• Carbonation process of concrete due to a reaction with the carbon dioxide
contained in the atmosphere, which brings the pH of pore solution from pH > 13
to pH < 9. This process starts from the concrete surface, then proceeds through
the concrete cover until it reaches steel reinforcements, then causing passivity
breakdown (Fig. 23.2).
Once the passive film breaks, corrosion occurs if water and oxygen are present on
the reinforcement surface.
The service life of a reinforced concrete structure can be divided in two phases
(Fig. 23.3): corrosion initiation, which is the time required for carbonation or
chlorides penetration to reach the reinforcements, then producing passivity break-
down, and corrosion propagation, once corrosion attack has started.
Corrosion by carbonation appears uniformly distributed on the reinforcement
surface; conversely, chloride-induced corrosion is mostly localized, with crater-like
penetrating attacks, surrounded by passive, non-corroded areas, as in pitting cor-
rosion mechanism; the attack spreads in case of large chloride contamination,
especially when pH decreases. High-strength steel reinforcements in pre-stressed
concrete structures can suffer from hydrogen embrittlement when peculiar envi-
ronmental, electrochemical, mechanical and metallurgical conditions concur.
Reinforcement corrosion leads to a progressive reduction in safety margins
established in design (Fig. 23.4), for instance:
• Reduces the cross section of reinforcements, then jeopardizing static and
dynamic structural stability; in particular, corrosion of external supports, which
first begins suffering depassivation by carbonation or chloride contamination,
Reduction in cross
section of rebars decrease of Tensile strength
Elongation
Fatigue strength
Cracking
Loss of bond
of concrete
Effects strength
of Increase in
corrosion corrosion rate
Concrete disbonding
Rust
Hydrogen
embrittlement Brittle failure
of reinforcement
Fig. 23.4 Consequences of structural reinforcement corrosion in reinforced concrete structures
Crate
(m/y)
1000 Heavily chloride-contaminated
RH 95-98%
100 Chloride-contaminated RH 90-95%

Carbonated RH 95-98%
Chloride-contaminated RH 80-90%
10
Chloride-contaminated RH 50-80%
1 Chloride-contaminated RH < 50%

Carbonated RH < 70%
Chloride free not carbonated

0.1
Fig. 23.5 Corrosion rate of steel reinforcements in various conditions adapted from Andrade
(1988)
23.1 Initiation, Propagation and Morphology of Corrosion 513
may compromise the confinement action, therefore weakening the main rein-
forcements stability
• Reduces adhesion between reinforcement and concrete, or even halts it if
thickness loss is of the order of 50 lm
• Produces oxides (rust) with a volume 4–5 times higher than that of corroded
iron, which cause cracks in concrete cover (above 50–200 lm corrosion
thickness) and even its spalling or delamination
• Finally, on some types of high-strength steel, it can give brittle failure.
Corrosion rate is generally measured in lm/year, and varies with environmental
and concrete conditions (Fig. 23.5). As long as corrosion rate is below 1.5–2 lm/
year, there is no consequence on reinforcement integrity.
23.2 Corrosion by Carbonation
Atmospheric carbon dioxide reacts with alkaline components of the pore solution
contained in concrete, as shown schematically by the following reaction:
H2 O;NaOH
CO2 þ Ca(OH)2 ! CaCO3 þ H2 O ð23:1Þ
In reality, also intermediate reactions take place, involving sodium and potassium
hydroxides.
Carbonation does not cause reduction of mechanical strength of concrete;
however, there are important consequences on reinforcements, because the pH of
pore solution decreases from initial values, typically between 13 and 14, to values
close to neutrality, then causing passivity breakdown.
23.2.1 Carbonation Depth
Carbonation reaction starts on the concrete surface and proceeds through the cover,
following a penetration rate derived from the equation below:
s ¼ K t1=2 ð23:2Þ
where s is thickness of carbonated layer (in mm), and t is time (in years). The coef-
ficient K equals mathematically the thickness of carbonated cover in the first year, and
depends on environmental factors (temperature, humidity, carbon dioxide content) as
well as on concrete-related factors, alkalinity and porosity: the most influencing
parameters are humidity and porosity, as described in the following paragraphs.
35 Curing:
28 days
Carbonation depth (mm)

30
1 day
25
20
15
10
0
0.3 0.5 0.7 0.9 1.1
W/C ratio
Fig. 23.6 Influence of W/C ratio and curing time on carbonated thickness (from Page 1992)
Relative humidity. Carbon dioxide diffusion within the concrete cover occurs
through the pores, easily if filled with air, i.e., in gaseous phase, while very slowly if
filled with water, about 104 times slower. Accordingly, diffusion rate decreases as
relative humidity increases (more markedly above 80%) then it zeros in
water-saturated concrete. On the other hand, carbonation takes place if water is
present, and it zeros for relative humidity lower than 40%. For these two opposite
limits, carbonation rate maximises in the relative humidity range 50–80%. It follows
that microclimate, i.e., local temperature and humidity in differently exposed parts of
a structure, outdoor or indoor, exposed or screened from rain, is of utmost importance.
Porosity. All porosity affecting factors (water/cement ratio, installation, com-
paction, curing) are crucial for determining carbonation rate. For example, Fig. 23.6
reports the effect of the water/cement ratio and curing on carbonated thickness,
which decreases as water/cement ratio decreases and curing time increases.
23.2.2 Corrosion Rate
Once carbonation reaches reinforcements, the passive film breaks (i.e., initiation
time ends) and corrosion starts if water and oxygen are present. Except in condi-
tions of permanently water saturated concrete, a sufficient oxygen is always
available for the corrosion process, therefore corrosion rate is governed by water
content in concrete; the highest corrosion rate is of the order of several tens of lm/
year at nearly water saturation conditions. The most common values for atmo-
spherically exposed structures are between 5 and 10 lm/year, and drop to 1–2 lm/
year for indoor concrete. Corrosion by carbonation becomes a concern only in
conditions of high relative humidity or in the presence of alternating wetting, which
affects moisture content on reinforcements.
23.2 Corrosion by Carbonation 515
10
Corrosion rate (mA/m2)

1
0% Cl-
0.4% Cl-
1% Cl-
0.1
40 50 60 70 80 90
Relative humidity (%)
Fig. 23.7 Effect of low chloride content on corrosion rate by carbonation (from Glass 1991)
Fig. 23.8 Corrosion of reinforcements by carbonation in Milan, Italy, on a 1969 building (picture
is dated 2006)
Fig. 23.9 Corrosion of

reinforcement by carbonation
in Milan, Italy (Marchiondi
Institute, 1957)
Corrosion harshens when chlorides are present in concrete even at content below
the threshold of depassivation, as shown in Fig. 23.7. Also the safe range of relative
humidity, at which corrosion rate is negligible, reduces. Figures 23.8 and 23.9 show
two examples of corrosion by carbonation.
23.3 Chloride-Induced Corrosion
Chlorides can penetrate concrete when chloride-containing solutions are in contact

with the concrete cover as for example in marine structures and in bridge slabs
when de-icing salts are spread. Corrosion starts when chloride concentration on
reinforcement exceeds a critical value, which ranges, for atmospherically-exposed
structures with carbon steel reinforcements, from 0.4 to 1% by cement weight. The
time required to reach such critical value is called corrosion initiation time and
23.3 Chloride-Induced Corrosion 517
depends on concentration of chlorides on external surface, concrete cover thickness

and characteristics of cement paste that determines the chloride diffusion coefficient.
Experience shows that, in spite of the presence of several mechanisms, chloride
concentration profile follows with good approximation an equation formally
identical to the second Fick law by introducing the apparent (or effective) diffusion
coefficient, Dce, obtained experimentally:
@C @2C
¼ Dce 2 ð23:3Þ
@t @x
where C is chloride content (% by cement or concrete mass), time, t, is expressed in

s, distance, x, from concrete surface is in cm, and apparent chloride diffusion
coefficient, Dce, is in cm2/s.
Assuming constant in time and space both chloride content on external surface,
Cs, and diffusion coefficient (i.e., concrete is considered homogeneous), the solution
of Fick law is:

x
Cx ¼ Cs 1 erf pffiffiffiffiffiffiffiffiffi ð23:4Þ
2 Dce t
which gives the chloride content Cx at depth x, at time t. Therefore, known Dce and
Cs, it is possible to figure out the time-based evolution of chloride concentration
profiles in concrete cover and predict the time for corrosion initiation.
6
Cs = 5%
t = 10 years
5
3
D = 10-7 cm2/s
2
1 D = 10-8 cm2/s
D= 10-9 cm2/s
0
0 1 2 3 4 5 6 7 8 9 10
Deph (cm)
Fig. 23.10 Diffusion profiles, chloride concentration versus thickness, after 10 years of exposure,
with different apparent chloride diffusion coefficients (chloride concentration: 5% on surface)
100
Cs = 5%
Cx = 1%
80 D = 10-9 cm2/s
60
Time (y)
D = 10-8 cm2/s
40
20
D = 10-7 cm2/s
0
0 1 2 3 4 5 6 7 8 9 10
Deph (cm)
Fig. 23.11 Diffusion profiles, time versus penetration depth, with different apparent chloride
diffusion coefficients (chloride concentration: 5% on surface, 1% in concrete) at the rebar surface
Figure 23.10 reports chloride concentration profiles after 10 years of exposure

for different diffusion coefficients, while Fig. 23.11 shows time dependence of
chloride penetration depth considering a chloride content of 1% by cement mass,
both obtained by applying the second Fick law. Indeed, a pure diffusion mechanism
applies on completely saturated concrete, only; in most practical situations, in
addition to diffusion other transport mechanisms operate, for example, capillary
absorption on dry concrete when in contact with chlorides containing solutions,
often followed by evaporation which increases chloride concentration.
Because the penetration rate of chlorides depends on their concentration on the
surface, Cs, it is important to input reliable values. For marine structures, after an
initial transitory of a few months, chloride concentration on the surface is constant
and reaches values higher than 3–4% in the splash zone. Often, prudentially, 5% is
the value considered for assessment of expected life.
The diffusion coefficient, Dce, typically varies from 10−9 to 10−7 cm2/s
depending on concrete properties, specifically on permeability and related factors
as: water/cement ratio, vibration after casting, curing, presence of cracks and type of
cement. The latter has a decisive role: passing from Portland cement to fly-ash
mixed cements, the diffusion coefficient drops consistently, especially when ground
granulated blast slag (GGBS) is used, and the effect lasts even tens of years.
23.3.1 Corrosion Rate
In atmospherically exposed structures, once the attack has started, corrosion rate
can range from a few tens of lm/year to 1 mm/year, and increases as humidity
23.3 Chloride-Induced Corrosion 519
increases from 70 to 95% and chloride content from 1 to 3% (by cement mass).
Corrosion rate also increases with temperature, as proved by making a comparison
between temperate and tropical weather. In practice, corrosion attacks in
chloride-contaminated structures, once started, can result in unacceptable reductions
of cross section of reinforcements in a very short time.
The lower limit of humidity, below which corrosion rate becomes negligible,
depends on concrete characteristics, chloride content on surface and type of salt. In
conclusion, it is much lower than that for corrosion by carbonation.
23.3.2 Structures at a Risk
Reinforced concrete structures at greater risk of chloride-induced corrosion are

marine structures and highway bridges when exposed to deicing salts.
In marine structures, risky zones are: submerged, tidal and splash, and atmo-
spheric zones. The most critical is doubtlessly the second one because both oxygen
and chlorides are easily available, unlike the other two, where either oxygen or
chlorides are not, as shown in Fig. 23.12. Corrosion attack is often localized, with a
maximum penetration rate of some tenths of mm/year: accordingly, corrosion
propagation time is discarded in corrosion assessment for the evaluation of service
life. For structures near the sea, corrosiveness decreases as the distance from
shoreline increases.
The use of de-icing salts on bridge decks leads to localized corrosion particularly
on floor slabs, pier caps, columns and non-sealed joints; the lack or improper
drainage systems, which cause ponding, increases the risk of reinforcement cor-
rosion (Figs. 23.13 and 23.14). In critical areas, as viaducts joints, corrosion rate is
as high as in the splash zone of marine structures, the producing a severe concrete
spalling (Fig. 23.15).
Fig. 23.12 Chloride content Height (m)

profile in the most critical area 2.5
of a marine structure, adapted
from Bertolini (2013) 2.0
5%
1.5
2% 1.0
1%
0.5%
0.1% 0.5
-0.5
-1.0
5 4 3 2 1 0
Depth (cm)
Fig. 23.13 Detail of localized corrosion caused by chlorides contamination (1980s Bologna—
Florence highway, Italy)
Fig. 23.14 Localized corrosion caused by chlorides contamination (1980s, viaduct of Brennero
highway, Italy)
23.4 Hydrogen Embrittlement 521
Fig. 23.15 Spalling of concrete cover on bridge deck (1980s Milan-Genoa highway, Italy)
23.4 Hydrogen Embrittlement
Hydrogen embrittlement (HE, Figs. 23.16, 23.17 and 23.18) may occur on high
strength steels with yield strength exceeding 700–900 MPa in the presence of
atomic hydrogen. This one does not form on passive reinforcement in sound
chloride-free concrete, instead it forms on de-passivated sites due to carbonation or
chloride contamination or where passivation is absent because of local lack of
concrete. Reinforced concrete structures susceptible of HE are pre-stressed and
post-tensioned structures, where high strength steels are used (Figs. 23.19, 23.20
and 23.21). HE susceptibility is highly dependent on steel microstructure obtained
by thermo-mechanical treatments to achieve the required mechanical strength. In
practice, two processes are used: cold drawing followed by stress relieving or
quenched and tempered steels. The latter, producing a more susceptible
microstructure, is virtually out of production. Also perlitic steel is used for large
diameter bars, obtained by hot working followed by cold deformation and stress
relieving. In any case, HE susceptibility increases as mechanical strength increases.
HE-related failures of pre-stressed structures represent a small percentage with
a decreasing trend because the most susceptible high-strength steels are no longer
in production. Nevertheless, even in the 1990s, several structural collapses
occurred, especially in Germany where the use of quenched and tempered steels
was formerly widespread. A famous example is the failure of the Congress Hall in
Berlin in 1980.
Fig. 23.16 Hydrogen embrittlement of high strength steel pre-stressing strands
Fig. 23.17 Micrograph of cracks caused by hydrogen embrittlement of high strength steel
pre-stressing strands
23.4 Hydrogen Embrittlement 523
Fig. 23.18 Hydrogen embrittlement of a pre-stressed concrete cylinder pipe
Fig. 23.19 Hydrogen embrittlement of pre-stressed bars (Manfredonia Harbour, Italy, built on
1979)
Fig. 23.20 Post tensioned concrete structure collapsed in 1999 due to HE on carbon steel strands
(S. Stefano Bridge, Messina, Italy—courtesy of Prof. E. Proverbio)
Fig. 23.21 Zone of fracture initiation caused by hydrogen embrittlement on a high strenght steel
23.5 Corrosion by Stray Currents
Very rarely, reinforcement of foundations or underground structures, such as rail-

way tunnels, may suffer stray current corrosion, where the interference current
leaves the reinforcement. Initially, on passive reinforcements, the anodic reaction
where current leaves steel is oxygen evolution, but after some time as the result of
the local acidification, which destroys the passive film, corrosion takes place.
Accordingly, two conditions are necessary for stray current corrosion in sound
alkaline and chloride-free concrete:
• First condition. Interfering electric field must be sufficiently strong to cause
current circulation in concrete, overcoming ohmic and overvoltage barriers
• Second condition. Interference current must be stationary, i.e., flow “continu-
ously” for a sufficient time to lead to passivity breakdown. Intermittent flows are
less harmful because the acidity produced is neutralized by the surrounding
alkalinity during any inactive period.
In practice, only the electric field generated in long railway tunnels, with rein-
forcements in electrical continuity, fits the first requirement; about the second one,
as considered above, any interruption of the stray current flow delays or even halts
the passive film breakdown. It can be concluded, in general, that non-stationary
interference, as it occurs in electric transit railway systems, does not represent a real
threat.
23.6 Prevention of Reinforcement Corrosion
Corrosion prevention must begin in design phase, involving conception, structural

details, and materials; it then follows during construction through preparation,
implementation, compaction and concrete curing. Finally, it continues throughout
the operating life by planned maintenance and inspections.
This approach to durability of concrete structures has been called holistic in
order to emphasize that prevention should not be considered as a mere set of
possible prevention measures, but rather as articulated interventions from design to
dismissing.
Preventative measures taken in design, construction and maintenance phase deal
with the following rules of thumb:
• Easy access must be granted for inspection and maintenance activities
• Structure geometry has to minimize cracking
• Design of construction details, also with reference to the build-up phase, must
avoid complex geometries, sharp edges, rebar congestion, water ponding as
promoted by expansion joints and supports
• During transport and execution, necessary precautions must be taken to avoid
segregation of mix. Vibration helps obtain maximum compaction possible
• Concrete cover thickness must comply with design data

• Temperature and humidity must be optimal for a sufficiently long period to
allow and facilitate cement hydration.
In each of these phases all necessary controls need to be implemented to achieve a
product that meets quality requirements. Since different subjects operate (designer,
concrete producer, construction and maintenance companies) it is important to
define battery limits for any controls and responsibility. Some of above issues are
23.6.1 Quality of Concrete
The concrete cover provides protection of reinforcement against aggressive agents

coming from outside, therefore it is sufficient that the surrounding concrete remains
alkaline and chloride-free to ensure passive conditions. Accordingly, to prevent the
corrosion of reinforcements, a low permeability concrete is required and achieved
by following the updated knowledge of concrete technology.
The following parameters are of particular importance: water-to-cement ratio,
content and type of cement, compaction, curing and presence of cracks. The
European Standard EN 206 provides a guide for composition and properties of
concrete to ensure 50-year lifetime. This standard deals with concrete prepared with
Portland cements in accordance with EN 13670-1 standard, with concrete cover
thicknesses complying with EN 1992-1-1 standard.
Water/cement ratio. Water-to-cement ratio is a key factor to determine the cap-
illary porosity of the cement paste and thus its resistance to aggressive species
penetration. Therefore, a low ratio is the primary choice to obtain an impervious
concrete to either carbonation or chloride penetration.
Cement content. The increase in cement content, for a given water-to-cement ratio,
on one hand leads to a higher amount of water, which increases workability of the
mixture, but on the other hand also increases risk of cracking due to hydration heat
or drying shrinkage or alkali-aggregate reaction.
Type of cement. The type of cement is particularly important for structures, which
are exposed to chlorides. At same conditions, blended (except for limestone-based)
and blast furnace cements are the most resistant to chloride penetration.
Unfortunately, some blast furnace cements already contain 0.1–0.2% of chlorides,
then weakening this advantage. Blended cements show also beneficial effects on the
resistance to sulphate attack and alkali-aggregate reaction; a low hydration heat also
characterizes them.
Installation and compaction. Installation and compaction of concrete strongly
influence durability. The pouring of fresh concrete should ensure optimal formwork
filling, avoiding air trapping: this is achieved by vibration. Voids due to segregation
or insufficient vibration increase concrete permeability, jeopardize passivation of
23.6 Prevention of Reinforcement Corrosion 527
steel reinforcement and bring critical chloride content toward values lower than the
typical range, 0.4–1% by cement mass. Excessive vibration can lead to segregation
for high slump concrete. The addition of plasticizers becomes mandatory to achieve
high workability with low w/c ratio. For structures with a complex geometry, it is
possible to use self-compacting concrete, which enables to fill the formwork
without requiring vibration thanks to a special composition.
Curing. Curing of concrete helps promoting cement hydration by a control of either
moisture content or temperature a few days after installation. Adequate curing is
often obtained by simply wetting the surface or reducing water removal and water
evaporation or delaying the removal of formworks. Curing affects primarily dura-
bility and mechanical strength. The recommended minimum time of curing is
available in ENV 13670 standard.
Cracking. When tensile stresses onset inside concrete, due to either mechanical
loads or constraints, cracks may form. For example, internal or external constraints
can prevent shrinkage due to a humidity change (plastic or hygrometric shrinkage).
In the case of thick concrete casting, cracking can take place for excessive tem-
perature changes between surface and core. Cracking can also occur when
expansive compounds form inside a concrete slab, as in the case of steel rein-
forcement corrosion, alkali-aggregate reaction, sulphate attack or freeze-thaw
cycling. Cracks can reduce corrosion initiation time, as they are preferential path-
ways for carbonation and chloride contamination. Within certain limits, cracks are
not dangerous, provided that crack opening does not exceed 0.1 mm, because
corrosion products tend to seal the cracks and favour local conditions for repassi-
vation in the area close to reinforcements.
23.6.2 Cover Thickness
As cover thickness increases, corrosion initiation delays because time for carbon-
ation or chloride contamination increases. Accordingly, based on concrete prop-
erties, carbonation and chloride contamination rates can be evaluated and, once the
minimum time to trigger corrosion attack is fixed, the minimum cover thickness can
be determined. Then, theoretically, it would be possible to ensure the durability of a
structure by fixing a proper concrete cover thickness; in practice, however, cover
thickness cannot exceed some limits for economic and technical reasons, for
example, as concrete cover thickness increases, the risk of cracking strongly
increases due to drying shrinkage.
As far as carbonation is concerned, the specified cover thickness should be
ensured on the whole surface of the structure: in fact, since penetration of car-
bonation follows a parabolic law (Eq. 23.2) the relationship between thickness
reduction and corrosion initiation time reduction is not linear; similar considerations
apply to chloride induced corrosion.
23.6.3 Common Mistakes
Premature degradation of reinforced concrete structures deals with design and

construction mistakes or lack of maintenance. Typical design casualties include:
• Construction procedure favouring local aggressive conditions (for example, an
excessive number of joints or an unnecessarily complex geometry)
• Complex structural frame producing uneven stress distribution, then leading to
cracking
• Not adequate details for construction, such as concrete cover thickness not
suitable for aggressive environmental conditions, or geometric conditions
favouring water ponding; rebar congestion impeding concrete compaction;
sharp edges, which halve design life (Figs. 23.22 and 23.23).
Fig. 23.22 Example of insufficient concrete cover (Belvedere ceiling, 31st floor of Pirelli
skyscraper, Milan, Italy, 1959—picture is dated 2005)
23.6 Prevention of Reinforcement Corrosion 529
Fig. 23.23 Insufficient concrete cover due to segregation and rebar congestion (building La Nave,
Politecnico di Milano, Milan, Italy, 1967—picture is dated 2008)
The most frequent mistakes in mixture proportion are: too high water/cement ratio,
the use of Portland or sulphate resistant cements in chloride-containing environ-
ments. Typical mistakes in construction phase are addition of water, incorrect
compaction, wrong or absent spacers for concrete cover thickness, bad or inaccurate
curing.
23.7 Additional Protections
When design procedure, concrete cover thickness, choice of materials, mix com-
position, pouring, compaction and curing comply with regulations and avoiding
abovementioned errors, durability has proved, in the majority of environmental
conditions, to meet 50 years, as typically required for the design life of concrete
structure.
However, for important structures exposed to chlorides, the compliance to
regulations is not sufficient to avoid corrosion in shorter time, as it may happen for
example on bridge decks where de-icing salts are spread, on splash zone of marine
structure or on surfaces exposed to seawater.
On the other hand, a service life of 50 years may be too short for many important
buildings, such as churches, monuments and public buildings that are expected to
last, with minimum maintenance, 100 years or even more. In these cases, including
conditions associated to severe environments, practical difficulty to build specified
cover thickness or poor accessibility for maintenance or when there is no alternative
for the use of low quality concrete, it becomes necessary to adopt specific additional
preventative measures to increase durability as summarized in Fig. 23.24.
Figure 23.25 illustrates how additional preventative measures work by reducing
aggressive species diffusion or by controlling the anodic corrosion process, since
the cathodic process, i.e., oxygen reduction reaction, cannot be limited (in other
words, today there are no available techniques to do it, unless for permanently water
saturated structures).
physical
intrinsic (increase of 1/D, K, S, ρ)
chemical (inhibitors)
concrete
resistant to CO2
surface resistant to chloride
treatment water repellent
type of material
(stainless steel)
intrinsic
metallurgical/mechanical
(to decrease the
reinforcement susceptibility to HE
Additional protection for high-strenght steel)
methods based
on the control galvanizing
of characteristics surface epoxy coatings
cathodic prevention
(change potential)
control of environment humidity,

external environment chloride content, CO2
control of quantity and
type of de-icing salts
higher thickness
during design of concrete cover
structure monitoring
during maintenance
Fig. 23.24 Classification of additional preventative methods
control of characteristics of
concrete (porosity, composition,
control the thickness of concrete cover)
penetration control of the environment
of CO2 and use of surface treatments
chlorides resistant to CO2
chlorides
inhibitors
stop the galvanized steel
Prevention and
anodic process epoxy - coated bars
protection methods
must stainless steel bars
cathodic protection
control the rate of
the cathodic process
(oxygen reduction) use of cathodic inhibitors
(or mixed)
hinder circulation use of water-repellent coatings

of current in
concrete control of environment
Fig. 23.25 Mechanisms of additional preventative methods

23.7 Additional Protections 531
23.7.1 Concrete Surface Treatments
The main action of surface treatments is to slow down the penetration of aggressive
species to increase initiation time, especially for chloride-induced corrosion. Once
corrosion has started, effective treatments to reduce corrosion rate are those that
enable to stop water penetration; this works also in the case of carbonation. It is
possible to identify four main classes of surface treatments of concrete structures:
• Organic coatings
• Hydrophobic treatments
• Pores obstruction treatments
• High thickness cementitious coatings.
Organic coatings. These coatings must be compatible with concrete alkalinity;
they are based on acrylic, polyurethane and epoxy binder types, containing suitable
pigments, additives, solvents and diluents to ease their application. By forming a
continuous film, typically 100–300 lm thick, on the surface, their action depends
on porosity, i.e., on permeability to CO2 and water vapour.2
Hydrophobic treatments. To reduce capillary absorption of water and dissolved
aggressive substances, in particular chlorides, water repellent agents are used. They
have no effect on gases such as carbon dioxide and oxygen, then useless to reduce
carbonation. Hydrophobic surfaces can be obtained by impregnating concrete with
compounds belonging to the family of silicones, silanes and siloxanes. These
products are also absorbed by capillary action into pores for a few millimetres of
thickness, therefore water remains on the surface of concrete as droplets. The
deeper the capillary absorption of these hydrophobic substances, the longer their
effective life. Ultraviolet radiation promotes degradation of these products.
Application should be carried out when the concrete surface is not too damp.
Pore sealing treatments. To seal pores, silicates or silico-fluorides are used, which
react inside pores with concrete to give clogging reaction products. Also some organic
coatings based on epoxy or acrylic binders can be used, which penetrate into pores
(sometimes impregnation is favoured by applying vacuum) and harden and seal pores.
Cementitious coatings. Cementitious coatings are typically made with a mortar or
concrete containing polymeric materials to give high thickness and low perme-
ability. These coatings exhibit: good adhesion to concrete, high flexibility, high
permeability to water vapour, low permeability to water, high resistance to chlo-
rides, sulphates and carbon dioxide diffusion and good resistance to aging due to
2
There is a parameter, the equivalent air layer thickness, which measures permeability by indicating
the equivalent meters of air that oppose the same resistance to gas diffusion as the coating. The
minimum coating thickness should give a value of this parameter of at least 50 m versus CO2 and
lower than 4 m versus water vapour, to allow concrete to exchange vapour with the atmosphere.
sunlight. Because of their high deformability, these cementitious coatings are rec-
ommended for cracked concrete, since they seal cracks and withstand deformation,
as well as, when compared to other coatings, high mechanical stresses, especially if
variable in time.
23.7.2 Corrosion Inhibitors
Corrosion inhibitors are used primarily to prevent chloride-induced corrosion.

A state of art report has been published by Elsener in 2001. Their efficiency
depends on dosage, concrete permeability, pH of pore solution, temperature,
chlorides and oxygen concentration. Two categories are used: inorganic (i.e., cal-
cium nitrite) and organic.
Calcium nitrite. It is the oldest corrosion inhibitor used in concrete. It is added to
the mixture as a solution that also contains suitable products for limiting side effects
on curing and workability. Dosage depends on maximum expected chloride con-
−
tent, and is given by molar ratio [NO 2 ]/[Cl ] of about 1–1.25. For instance, to
withstand a maximum chloride content of about 3% by cement weight, much above
the critical interval 0.4–1%, a typically recommended dosage is 30 L/m3. Calcium
nitrite works in highest quality concrete only, as porous or cracked ones cannot
prevent inhibitor leaching.
Organic inhibitors. Organic inhibitors include a broad class of products, which
have been studied since 1980s. Mixtures of amines, alkanol-amines and their salts
with organic acids, for instance benzoic acid, have proved to be effective. These
inhibitors can be added to the mix or to mortars used for restoration, or sprayed on
the surface to migrate to the reinforcement. Since they have been introduced
recently, few reliable data on their long-term effectiveness are available; it is
opinion that critical chloride content is increased to about 1.2%, therefore the life
extension is limited (see Ormellese 2006; Bolzoni 2006). With reference to the
effectiveness of migrating inhibitors applied on the concrete surface, opinions are
still differing (Ormellese 2008).
23.7.3 Stainless Steel Reinforcements
To increase the corrosion resistance of reinforcements, stainless steels such as AISI

304L (EN 1.4307), AISI 316L (EN 1.4404) austenitic grades and AISI 318 (EN
1.4462) duplex grade have been used since a few decades. Table 23.1 reports their
chemical composition. Nitrogen containing stainless steels are also used. As far as
yield strength, elastic modulus and ductility properties of stainless steels are con-
cerned, same values as carbon steel reinforcements must be ensured as well as
weldability.
Table 23.1 Composition of stainless steels most commonly used in concrete, following EN, UNS
and AISI designations (% by mass)
Types of steel C max S max Cr Ni Mo
EN UNS AISI
1.4301 S30403 304L 0.3 0.003 17.0–19.5 8.0–10.5 –
1.4436 S31603 316L 0.3 0.015 16.5–18.5 10.5–13 2.5–3.5
1.4462 S31803 318LN 0.3 0.0015 21–23 4.5–6.5 2.5–3.5
(a) (b)
7 7
Critical content of chlorides
Critical content of chlorides

20°C 40°C
6 6
duplex (1.4462)
(% by cement mass)
(% by cement mass)
5 5
duplex (1.4462)
4 4
316L (1.4404)
316L (1.4404)
3 3
2 304L (1.4307) 2 304L (1.4307)
1 Carbon steel 1 Carbon steel

0 0
9 10 11 12 13 9 10 11 12 13
pH pH
Fig. 23.26 Critical chloride content as function of pH and temperature for pickled stainless steels:
a 20 °C; b 40 °C (Bertolini 2002)
Figure 23.26 shows the critical chloride content for mentioned stainless steels as
function of pH: in concrete (pH 13) critical level is 5% by cement weight for
molybdenum-free stainless steels and increases to 7–8% when molybdenum is
present. These values drop down to about 3.5% when passive film is tinted (i.e.,
coloured) because of welding.
In carbonated concrete, with pH 9, the critical content significantly lowers
especially if temperature reaches or exceeds 40 °C. Experience showed that in
heavily cracked structures stainless steel reinforcements behave as in carbonated
ones although concrete is still alkaline. Molybdenum containing stainless steels are
recommended for hot climates, as well as for very cracked or carbonated
chloride-contaminated concrete.
Sometimes stainless steel is used for external reinforcements (skin reinforce-
ments) or critical zones only, while internal and remaining zones can host ordinary
carbon steel. Stainless steel can be conveniently placed in high chloride content
areas and carbon steel only where chloride content is expected not to exceed the
critical threshold of 0.4%. As an important result, all reinforcements operate in
passive conditions, so that no galvanic coupling onsets (in sound concrete the
potential of passive carbon steel and passive stainless steel is the same).
23.7.4 Galvanized Steel Reinforcements
Galvanized reinforcements are obtained by hot dipping in molten zinc at approx-

imately 450 °C. The higher the zinc layer thickness the longer the durability, but
also the higher the coating tendency to crack during bending at yard; best com-
promise is a total zinc layer thickness of 80–120 lm with 10 lm minimum as pure
zinc outer layer.
In alkaline concrete, zinc shows a non-acceptable corrosion rate if chloride
content exceeds 1.2% by cement mass. In carbonated chloride-free concrete, cor-
rosion rate of zinc layer is very low since zinc passivates.
Because of the excellent behaviour in carbonated concrete, galvanized rein-
forcements are recommended for precast elements, in lightweight or thin concrete
cover structures not expected to be contaminated by chlorides.
Provided the zinc layer thickness is of 80–100 lm, carbonated structures with
chloride contamination level below 1% by cement weight are expected to have
service life of 100 years or more. Figure 23.27 shows a church in Rome, Italy,
where galvanised steel was used to increase durability and also to avoid staining of
exposed surfaces.
Fig. 23.27 Dives in Misericordia church, built with galvanized steel reinforcements (Rome, Italy,
2003)
23.7.5 Cathodic Prevention (CPrev)
The cathodic prevention, CPrev, introduced by Pietro Pedeferri in early 1990s, is

the cathodic protection applied since the beginning throughout the entire service life
of the structure. It is based on the dependence of pitting and repassivation potential
of steel reinforcements on chloride content in concrete, as shown in the potential
versus chloride content plot of Fig. 23.28, also called Pedeferri’s diagram, which
defines corrosion conditions of steel reinforcements. CPrev current density is in the
order of 1–3 mA/m2, which produces a potential decrease of 100–200 mV, then
enabling an increase in critical chloride content of one order of magnitude, i.e.,
more than 4% by cement weight.
23.7.6 Comparison of Additional Protections
To choose an additional corrosion prevention method it is important to know

thoroughly the exposure environment, design life, possible constrains for applica-
bility (for instance power source for CP or CPrev) and associated costs (investment
and operating costs).
0.4
0.2
0 Pitting can initiate and propagate
1 2 Epit
-0.2
E (V SHE)
-0.4 Erp Pitting can propagate if started

3
0.6
4
-0.8 Perfect passivity
-1.0 Hydrogen evolution
Loss of adherence
-1.2
0 0.5 1 1.5 2
Fig. 23.28 Pedeferri’s diagram for corrosion initiation and propagation conditions in concrete
contaminated by chlorides, highlighting evolution paths of cathodic protection (see Sect. 23.9.2)
An example of limits of applicability in environments containing chlorides is the

critical chlorides content, which is 0.4 to 1% by cement weight for carbon steel
reinforcements and becomes:
• 1–1.2% for galvanized steel reinforcements and in case of use of organic
inhibitors
• 1–3% range for calcium nitrite based inhibitors
• 3.5–8% range for stainless steels
• Even higher than 5–8% range for CPrev.
A guideline for expected operating life is as follows:
• 10–15 years for water-repellent treatments or coating barriers against carbona-
tion or chlorides
• 100 years for galvanized steel reinforcements with zinc coatings (thickness 80–
100 lm) and chloride content which does not exceed 1%
• No limits for stainless steel in alkaline concrete and less than 5% chlorides after
removal of welding oxides
• CPrev with activated titanium anodes are designed to last up to 30 years and
there are no limits for the concentration of chlorides.
Investment cost varies with the method selected; some general indications are
available for comparison, for example, taking carbon steel reinforcement as refer-
ence, galvanized steel cost approximately doubles, while stainless steel cost is about
8–10 times greater for total replacement or 4–5 times more for partial replacement.
To determine a correct and definitive comparison, LCC (Life Cycle Cost) of each
technical solution has to be considered, because either investment or operating costs
vary for each solution. For example, with stainless steel reinforcements concrete
cover thickness can be much lower, then reducing the initial cost of the concrete
cast, and there is no need for maintenance, then almost zeroing operating costs.
23.7.7 Evaluation of service life by performance

based methods
As discussed before, at the beginning of this paragraph the recommendations given

by EN 206 and Eurocode 2 (EN 1992-1-1) standards about concrete composition,
placing, compaction, curing and cover have proven, in the majority of environ-
mental conditions, to meet 50 years service life. In very aggressive environment,
especially in presence of chlorides and longer service lives performance based
approach should be used to estimate the service life by modeling deterioration
mechanisms; moreover, these methods can provide much more information about
the effect of different options, like the use of preventative techniques. Among
performance based approaches, probabilistic ones are preferred because they are
able to take into account the intrinsic variability of the influencing factors. This
approach has been implemented in different models, among these the most relevant
one is the Model code for service life design, issued by the International Federation
for Concrete (fib) in 2006. The code models the effect of environment on the
structure by using an approach derived from the equations used to describe trans-
port of carbonation and chlorides into concrete, namely (23.2) and (23.3) and
evaluate the probability that a defined limit state (initiation of corrosion, concrete
cracking or spalling) is reached. Nowadays, the use of this model is limited and
there are open questions to solve before more extended applications. First of all,
comparison between the predictions and the real performance of structures is not
easy because few number of structures were designed in agreement with the model.
Moreover, the model does not provide sufficient indications for the determination of
some input parameters, in particular the surface chloride concentration and the
critical chloride content for rebars different from carbon steel.
23.8 Diagnosis
The management of a reinforced concrete structure needs a periodical checking of

structure integrity, through diagnostic testing on both concrete and reinforcement
degradation. Figure 23.29 reports a general procedure for inspection and control,
which involves: gathering of information about location, exposure, design data (mix
design, cover thickness, structural solutions), construction (origin of materials,
construction techniques, qualification of contract company), history (accidental
events, any evidence of oncoming degradation/decay). This information can help
formulate and identify hypotheses on possible causes of degradation.
Preliminary analysis Planning inspection

of the structure and interpretation
(type, hystory, enviromental data) of measurements
Identification of areas of possible
corrosion (honeycomb, voids) and
Visual inspection where corrosion is already
evident (cracks,detachments,
delaminations) Identification
of corroding areas
Identification of areas where
Potential mapping corrosion cannot be observed
from the surface of concrete
Polarization resistance or Evaluation of corrosion rate

concrete resisivity measurements in the areas where corrosion
(low potential areas) is present
Chemical analysis of concrete Evaluation of corrosion causes Evaluation of

and penetration of the the residual life
(carbonatation, depassivating front
chlorides penetration) of the structure
Inspection of rebars Evaluation of the damage already

occurred to the reinforcements
in areas of corrosion
Fig. 23.29 Flow chart for concrete structure inspections

An inspection begins by a visual observation, aiming to estimate type and extent

of damages such as: cracking along the reinforcements, concrete cover spalling,
presence of corrosion products. Construction errors favouring the onset of corrosion
are identified, as: cracking, non-uniform concrete cover thickness, lack of rein-
forcement coverage due to insufficient workability of fresh concrete, joints,
macro-cavities produced by the concrete segregation.
Visual observation is often followed by simple checks to assess concrete con-
ditions: hammer test to identify the presence of hidden delaminated zones based on
the sound emitted, concrete hardness measurements and ultrasonic techniques.
23.8.1 Concrete Cover Thickness Measurements and Rebar

Identification
There are instruments, called pachometers, based on magnetic principles, which

help identify reinforcements position and cover thickness. By matching this
information with the measurement of carbonation depth and chloride concentration
profile, corrosion initiation time can be evaluated.
23.8.2 Analysis of Concrete
Analysis of concrete provides fundamental information on: cement content,

water-to-cement ratio, additives, incorporated air.
Fig. 23.30 Phenolphthalein tests (sound concrete is the pink zone)

23.8 Diagnosis 539
Phenolphthalein test. It is used to determine carbonation depth: the pH of a spec-

imen is checked by spraying its surface with an alcoholic solution of phenolph-
thalein; carbonated concrete does not change colour, while sound alkaline concrete,
not yet carbonated, shows a typical pink colour, as shown in Fig. 23.30. This test
shall be performed on fresh surfaces on a perpendicular core specimen immediately
after its extraction. By comparing carbonated thickness and concrete cover thickness,
it is therefore possible to identify areas where carbonation induced corrosion is a risk.
Chloride content measurement. For structures exposed to chloride containing
environments, chloride profile helps determine the risk of corrosion onset. Core
specimens, cut into slices, or debris gathered at different depths are used for
analysis. Samples are dissolved in nitric acid and chloride concentration is mea-
sured by chemical analyses. Chloride profile and chloride content on the surface,
CS, allow the calculation of the apparent diffusion coefficient, Dce, by applying Fick
law, which in turn allows to predict the evolution of chloride penetration into
concrete (see Sect. 23.3).
23.8.3 Electrochemical Techniques
Some electrochemical techniques are used to determine the corrosion condition of

steel reinforcements, whether passive, i.e., initiation period is still ongoing, or
corroding as well as the corrosion rate.
E
(mV Cu/CuSO4)
Corrosion in carbonated dry concrete

0
Passivity in aerated concrete
Generalized corrosion in carbonated wet concrete
Localized corrosion in concrete with chlorides

-500
Passivity in wet concrete

(reduced oxygen supply)
Activity in water saturated concrete

(immunity for oxygen absence)
-1000
Fig. 23.31 Typical potential ranges of carbon steel reinforcements in concrete at different
conditions
10
Potential
8 (mV CSE)
-150
6
Width (m)
-250
-350
4
-450
2 -550
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Lenght (m)
Fig. 23.32 Potential mapping of a bridge deck. Corrosion risk is in dark grey
Potential mapping. It consists of the measurement of the potential by locating the

reference electrode on a prefixed grid on the external surface in order to determine
anodic and cathodic zones. Figure 23.31 shows typical potentials measured in
presence of carbonation, chlorides, and in water saturation, that is, for passive or
active steel. To assure the electrical contact between reinforcements and the ref-
erence electrode, two checks are performed: the electrical continuity of reinforce-
ments and the electrolytic contact by means of a wet sponge. Figure 23.32 shows a
typical potential mapping of a bridge slab where de-icing salts are spread in winter.
The interpretation of a potential mapping is based on ASTM Standard C876:
potential values more noble than −0.2 V CSE have 90% probability of no corro-
sion, conversely, a value below −0.35 V CSE has 90% probability of corrosion;
probability becomes 50% when potential falls within the interval. As a comple-
mentary evaluation criterion, since corrosion propagation occurs through a
macrocell mechanism, the potential map has to show a clear potential difference of
at least 150 mV to indicate that corrosion is occurring.
Linear polarization measurement. Where potential mapping shows an anodic site
(i.e., a potential lower than −0.35 V CSE) corrosion rate can be estimated by the
measurement of polarization resistance by the technique called Linear Polarization
Resistance (LPR) described in Chap. 29.
Concrete resistivity. Once steel reinforcement has become active, corrosion rate,
either uniform as in the case of carbonation or localized due to chloride contami-
nation, depends on concrete resistivity. This is quite evident when a macrocell
mechanism sets up as in case of chloride contamination, instead is more contro-
versial for carbonation. Accordingly, empirical criteria are used, although they do
not have general validity; for instance, they are not applicable when reinforcements
are still passive and in water-saturated conditions. The most used guideline for
corrosion rate prediction is reported in Table 23.2. Resistivity measurements are
also used to identify changes in concrete, for example, carbonated or chloride
contaminated zones.
23.9 Repair 541
Table 23.2 Empirical Resistivity (Xm) Corrosion rate

relationship between
resistivity and corrosion rate <100 High
100–500 Moderate
500–1000 Low
>1000 Negligible
23.9 Repair
To stop corrosion attacks, three approaches are used: restore passivity; apply
cathodic protection; reduce moisture of concrete through a surface treatment.
Different techniques are applicable for each approach.
23.9.1 Traditional Repair
Carbonated structures. Passivity destroyed by carbonation is generally restored

by replacing the carbonated concrete in contact with reinforcements with fresh
alkaline mortar. This intervention is cost-effective for limited zones, only. Suitable
polymer modified mortars are nowadays available to ensure a good grip with
concrete as well as a good compromise for drying shrinkage and risk of delami-
nation or cracking. Typical properties are: low elastic modulus, low permeability
and expansive action. Coatings slowing down carbonation rate are also often
applied. This intervention becomes problematic when small levels of chlorides are
present because, in spite of the mortar replacement, corrosion can start nearby the
restored zones. When spalling and delamination have not yet occurred, it can be
convenient to apply a water repellent treatment to reduce moisture content in
concrete cover, which reduces considerably the corrosion rate. This treatment is
practically useless if chlorides are present. These treatments have to be repeated
periodically, for example every 10–15 years.
Chloride-contaminated structures. Interventions to stop corrosion induced by
chlorides are more complex than those for carbonation, because repair has to be
extended beyond areas where corrosion took place. Indeed, without doing this,
corrosion starts at nearby repaired areas, where chloride content exceeds the critical
value: it has to be noted that before repair corrosion did not occur there because of a
beneficial galvanic effect exerted by corroding pit areas, as depicted in Fig. 23.33.
After repair, a reverse macrocell starts operating, then simply moving the corrosion
affected zones. A common mistake is the application of a concrete coating on old
sound chloride-contaminated concrete. Another typical mistake is the use of
so-called passivating primer without removing the adjacent chloride-contaminated
concrete.
(a) (b) (c) (d)
Not contaminated concrete Not corroded rebar
Concrete with chloride above Corroded rebar

threshold level
Primer for coating application
Restored concrete Coating
Fig. 23.33 Evolution of corrosion zones after patch repair
For a long lasting repair, it is necessary to identify all areas where concrete, in
contact with reinforcements, is already or will be in a near future chloride con-
taminated above the critical content; then, that concrete, even if mechanically
sound, must be removed completely also in these areas.
Figure 23.34 shows the repair performed on a joint of a viaduct with an organic
coating without removing all the concrete polluted by chlorides. Under the coating,
corrosion continued to advance as before and, after a few years, the situation
confirmed what explained in Fig. 23.33.
Repairing materials. Portland cement-based mortars can be used for conventional
repair with and without addition of pozzolana, fly ash or silica fume to improve
resistance to carbonation and chloride penetration. Also superplasticizers, fibres,
polymers, corrosion inhibitors are added to increase, respectively, workability,
resistance to cracking, adhesion and steel passivation. In any case, for best results a
very low water/cement ratio (less than or equal to 0.4) and an appropriate curing are
mandatory. To control plastic shrinkage, cracking and loss of adhesion, which are
favoured by a high cement dosage, two approaches are used: shrinkage-
compensating mortars, obtained by the addition of expansive chemical agents, or
mortars with a low modulus of elasticity. The use in recent years of self-compacting
concrete seems more advantageous from an economic viewpoint. To strengthen
reinforced concrete structures, regardless the corrosion conditions of reinforce-
ments, polymer matrix composites with carbon, glass or aramid fibres have become
very popular. This intervention does not remove the cause of corrosion, which
requires appropriate techniques as described above.
23.9 Repair 543
Fig. 23.34 Corrosion occurred after a few years from patch repair without removing
chloride-contaminated concrete (E52 highway, Milan, Italy, now repaired)
23.9.2 Electrochemical Repair Techniques
Besides traditional methods, electrochemical techniques are applied to restore

passivity of reinforcements in chloride contaminated or carbonated concrete,
without removal of concrete. These techniques, which include cathodic protection,
electrochemical re-alkalisation and electrochemical chloride removal, utilize the
same electrochemical scheme, shown in Fig. 23.35, composed of a feeder and an
anode, the latter consisting of an activated titanium mesh fixed on concrete surface,
and reinforcements as cathode.
DC feeder
Anode
Current
Reinforcement (cathode)
Concrete
Fig. 23.35 Schematic of system employed to apply electrochemical repair techniques
Current circulation produces on steel reinforcement three effects:

• A decrease in potential
• A reduction or a halt of corrosion rate
• An increase in pH and a removal of chlorides, both facilitating repassivation of
steel.
Potential lowering stops as circulation of current is interrupted, while chemical
modifications are long lasting.
Cathodic protection of chloride-contaminated structures. As previously repor-
ted, Fig. 23.28 shows within Pedeferri’s diagram the path of potential during
chloride contamination and after the application of cathodic protection. Point ①
represents initial passive condition when chloride content is zero; as chloride
content increases corrosion sets up to point ② (region of corrosion). By applying
CP, operating conditions can lead to point ④, where passivity is achieved, or point
③, where passivity is not fully restored but corrosion rate is strongly reduced, since
the flowing cathodic current inhibits macrocell formation. Protection current density
for atmospherically exposed structures is of the order of 2–20 mA/m2, as indicated
in EN 12696 standard.
Electrochemical re-alkalisation. Electrochemical re-alkalisation is a temporary
treatment for the restoration of concrete pH after carbonation, performed by
applying a current density of 0.7–1 A/m2 for a period ranging from 3 to 30 days by
means of a temporary anode placed on the surface of the structure. As anode, a
mesh made of activated titanium or steel, embedded in paper pulp soaked with
sodium carbonate is used. On the surface of reinforcements, cathodic reactions
produce hydroxyl ions, which restore alkalinity by bringing pH close to 14;
meanwhile, due to electro-osmosis, diffusion and capillary absorption, alkalinity
spreads also to concrete surface, then affecting the entire cover thickness.
Electrochemical removal of chlorides. By the same apparatus used for
re-alkalisation, but with slightly higher current densities (1–2 A/m2) and longer
times (from one to several months), electrochemical chloride removal can be carried
23.9 Repair 545
out. In this case, besides the effect of concrete re-alkalisation, there is an ionic
migration of chloride ions, from reinforcements towards the temporary anode,
produced by the applied current.
• ASTM C876, Standard Test Method for Corrosion Potentials of Uncoated

Reinforcing Steel in Concrete, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G109, Standard Test Method for Determining Effects of Chemical
Admixtures on Corrosion of Embedded Steel Reinforcement in Concrete
Exposed to Chloride Environments, American Society for Testing of Materials,
• ASTM C1582/C1582 M, Standard Specification for Admixtures to Inhibit
Chloride-Induced Corrosion of Reinforcing Steel in Concrete, American Society
• CEN/TS 14038-1, Electrochemical realkalization and chloride extraction treat-
ments for reinforced concrete—Part 1: Realkalization, European Committee for
Standardization, Brussels, Belgium.
• CEN/TS 14038-2, Electrochemical realkalization and chloride extraction treat-
ments for reinforced concrete—Part 2: Chloride extraction, European
Committee for Standardization, Brussels, Belgium.
• EN 206, Concrete—Specification, Performance, Production and Conformity,
European Committee for Standardization, Brussels, Belgium.
• EN 1504, Products and systems for the protection and repair of concrete
structures. Definitions, requirements, quality control and evaluation of confor-
mity, European Committee for Standardization, Brussels, Belgium.
• EN 1992-1-1, Eurocode 2: Design of Concrete Structures. General Rules and
Rules for Buildings, European Committee for Standardization, Brussels, Belgium.
• EN 12350, Testing fresh concrete, European Committee for Standardization,
Brussel, Belgium.
• EN 12696, Cathodic Protection of Steel in Concrete, European Committee for
• EN 13670, Execution of Concrete Structures, European Committee for
• ISO 1920-11, Testing of concrete—Part 11: Determination of the chloride
resistance of concrete, unidirectional diffusion, International Standard
• ISO 1920-12, Testing of concrete—Part 12: Determination of the carbonation
resistance of concrete—Accelerated carbonation method, International Standard
23:1 A reinforced concrete structure has to be built in Milan. The requested

service life is 50 years. Determine the minimum concrete cover in order to
assure the requested service life, being carbonation coefficient 4 mm/√year,
corrosion rate equal to 5 lm/year and maximum corrosion penetration
equal to 100 lm.
23:2 Due to error during casting of a reinforced concrete structure, in some
areas the real cover is 10 mm, in some others is 40 mm. After how many
years a repair is mandatory? Where? Consider the same data of exercise
23.1.
23:3 A reinforced concrete pillar is cast with a W/C ratio 0.5 and a concrete
cover equal to 30 mm. The estimated carbonation coefficient is 4.5 mm/
√year. Estimate corrosion initiation time. How does it change if, during
casting, the concrete at the bottom of the pillar is not well compacted?
Consider a W/C ratio equal to 0.7 and use Fig. 23.6, 28 days ageing, to
estimate the new carbonation depth (data reported in the figure have been
collected after 4 years of environmental exposure).
23:4 A jetty is cast with the following concrete mixture proportion: W/C ratio
0.45, cement 360 kg/m3 and cover 35 mm (as suggested by standards).
Galvanized steel rebars are used. With reference to Fig. 23.11 estimate the
service life, being the chloride surface content equal to 5% versus cement
weight, diffusion coefficient 10−8 cm2/s, critical chloride content 1% ver-
sus cement weight.
23:5 With reference to Exercise 23.4, considering the same concrete cover,
which is the maximum value of diffusion coefficient which allows to match
the 50 year service life requirement? In which way the mixture proportions
can be modified to reach this value?
23:6 A pillar of a reinforced concrete structure exposed to the atmosphere was
subjected to measurements of carbonation penetration after 5 and 20 years
from its construction. Measurements are reported in Table 23.3. The pillar
is exposed to rain. Cover thickness is 30 mm. Determine corrosion initi-
ation time in the weakest point of the structure. How does it change if the
mean value of carbonation depth is considered?
23:7 The carbonation depth of a reinforced structure built in an urban envi-
ronment equals its concrete cover after 30 years from its construction.
Table 23.3 Carbonation depth measured after 5 and 20 years of service life
Measurement Depth after 5 years (mm) Depth after 20 years (mm)
1 10 20
2 11 23
3 9 18
4 10 19
What should be the residual service life of the structure, considering a

design service life of 80 y? Evaluate propagation time by choosing a
suitable value for rebars corrosion rate, considering a relative humidity of
90%. Which is the propagation time of corrosion? Is a repair needed and, if
so, when?
23:8 The concrete coating on an offshore platform riser was damaged so that a
part of the steel surface in the splash zone was exposed. Explain which
factors may cause extraordinarily high corrosion rates in this case.
23:9 Compare and discuss how the additional protection methods affect the
critical chloride threshold. Consider also the duration of each method.
23:10 With reference the corroded viaduct reported in Fig. 23.15, describe in
detail how a tradition repair system has to be applied.
23:11 The Tunnel under the English Channel is basically a reinforced concrete
structure. Let’s consider the reinforced concrete wall, 70 cm thick, sepa-
rating seawater and the internal side of the tunnel. Cover is 40 mm on both
the sides.
• Assuming rebars are in carbon steel, discuss the possible form of
corrosion.
• Which additional protection method you suggest to guarantee 100 years
service life? Describe how it should be installed.
• Considering the use of stainless steel rebars, where they have to be
properly placed?
23:12. Is there any risk of galvanic corrosion in coupling carbon steel rebars with
stainless steel rebar in concrete? Why? Describe the electrochemical
behaviour using Evans diagram.
23:13. To face possible rebar corrosion due to DC interference, reinforced con-
crete tunnel of underground are typically electrically sectioned every
500 m. Why? (Refer also to Chap. 21).
Bibliography
Andrade C, Alonso MC, Gonzales JA (1988) An initial effort to use the corrosion rate
measurements for estimating rebar durability, vol 29. ASTM, Baltimore, US
Bertolini L, Pedeferri P (2002) Laboratory and field experience on the use of stainless steel to
improve durability of reinforced concrete. Corros Rev 20(1–2):129–152
Bertolini L, Bolzoni F, Pastore T, Pedeferri P (1996) Behaviour of stainless steel in simulated
concrete pore solution. Br Corros J 31(3):218–222
Bertolini L, Gastaldi M, Pedeferri M, Pedeferri P (2000) Stainless steel in concrete. Annual
progress report, European Community, COST 521 Workshop, References 269 Queens
University, Belfast, pp 27–32
Bertolini L, Elsener B, Pedeferri P, Redaelli E, Polder RB (2013) Corrosion of steel in concrete:
prevention, diagnosis, repair, 2nd edn, Wiley-VCH, Verlag GmbH & Co. KGaA, Weinheim
Bolzoni F, Goidanich S, Lazzari L, Ormellese M (2006) Corrosion inhibitors in reinforced

concrete structures. Part 2: repair system. Corros Eng Sci Technol 41(3):212–220
Brenna A, Bolzoni F, Beretta S, Ormellese M (2013) Long-term chloride-induced corrosion
monitoring of reinforced concrete coated with commercial polymer-modified mortar and
polymeric coatings. Constr Build Mater 48:734–744
CEB (1992) Durable concrete structures. Bull Inf 183
Collepardi M (2006) The new concrete, Grafiche Tintoretto, Castrette di Villorba, Treviso, Italy
Elsener B (2001) Corrosion inhibitors for steel in concrete. State of art, EFC Publication no. 35.
The institute of Materials, Maney Publishing, London, UK
Gastaldi M, Bertolini L (2014) Effect of temperature on the corrosion behaviour of low-nickel
duplex stainless steel bars in concrete. Cem Concr Res 56:52–60
Glass GK, Page CL, Short NR (1991) Factors affecting the corrosion of steel in carbonated
mortars. Corros Sci 32:1283
Ormellese M, Berra M, Bolzoni F, Pastore T (2006) Corrosion inhibitors for chlorides induced
corrosion in reinforced concrete structures. Cem Concr Res 36:536–547
Ormellese M, Bolzoni F, Lazzari L, Pedeferri P (2008) Effect of corrosion inhibitors on the
initiation of chloride-induced corrosion on reinforced concrete structures. Mater Corros 59
(2):98–106
Page CL (1992) Nature and properties of concrete in relation to reinforcement corrosion. In:
International conference on corrosion of steel in concrete, Aachen, Germany
Pedeferri P (1996) Cathodic protection and cathodic prevention. Constr Build Mater 10:391–402
Pedeferri P (2004) Progresses in prevention of corrosion in concrete, Istituto Lombardo (Rend.
Sc.) B 138, 129–143 (in Italian)
Tuutti K (1982) Corrosion of steel in concrete. Swedish Foundation For Concrete Research,
Stockholm, Sweden
Chapter 24
Corrosion in Petrochemical Plant
My god, it takes an ocean of trust

In the kingdom of rust.
Doves
Abstract Production fluids extracted and transported in the oil and gas industry are
multi-phase systems (oil, water and gas) with a variety of compositions. A necessary
condition for corrosion is the metal wetting by an aqueous phase, which in turn
depends on the fluid composition (water content) and on flow regime. If water wetting
is effective on the metal surface, corrosiveness of the environment depends on its
specific composition, for instance, on the presence or absence of CO2 and H2S in the
gas phase, or oxygen in the liquid water phase that can accompany oil. The chapter
deals with on corrosion problems concerning CO2 and H2S for both upstream, mid-
stream and downstream, with a brief mention to some peculiar forms of corrosion

https://doi.org/10.1007/978-3-319-97625-9_24
550 24 Corrosion in Petrochemical Plant
occurring in the refinery plant. The behaviour of most relevant metals in the different
environments is also summarized.
24.1 Petrochemical Plants
In petrochemical plants, three sections can be distinguished: upstream production,

where fluids are extracted from the reservoirs and transported to the wellhead;
midstream, where fluids are transported from the wellhead to the plant for trans-
formation; and downstream, where fluids are treated in the refinery plant.
Accordingly, the main components of a production plant can be divided in:
• Well area (production & injection wells) which comprises tubing, production
casing, liner, downhole equipment, well-head
• Gathering system, including production flow-lines and production manifolds
• Downstream process area: production line, separators, crude oil treatment, gas
treatment, production water treatment, water injection system, gas injection
system, gas/oil storage or export systems.
Metallic structures suffer all the forms of corrosion already seen in the general
chapters and some specific corrosion agents, which are the subject of this chapter
(Fig. 24.1). Therefore, galvanic corrosion, pitting, crevice, corrosion-erosion and
hot corrosion occurring in natural environments (seawater, industrial water and soil)
will not be here resumed.
Production fluids have a variety of compositions. In general, they are a
multi-phase system containing an oil phase, hydrocarbons, a gas phase and a water
phase. Hydrocarbons range from the lighter (methane, CH4) to the heavier (decanes,
C10H20, tridecanes), to heavy compounds as asphaltenes and paraffins. Water can be
present as formation water (brine) or condensed water. In vapour phase, corrosive
agents can be present, such as carbon dioxide (CO2) and hydrogen sulphide (H2S).
Production reservoir fluids are typically oxygen-free; however, oxygen can be
present in some specific items, such as in water injection systems.
24.2 The Corroding Waters
Corrosion can occur if water is present, because an aqueous electrolyte is necessary

for the corrosion process. Therefore, water cut, WCUT, i.e. the percentage of water
phase in production fluids, is the first factor to take into account for a corrosion
assessment.
The water phase associated to hydrocarbons may have two origins:
• Formation water, associated with oil or multiphase hydrocarbons dragged from
the reservoir
• Condensation water, originating from wet gas due to pressure/temperature
variations.
24.2 The Corroding Waters 551
Table 24.1 Comparison of composition of formation water of different reservoirs and seawater
(according to ASTM D1141)
Density pH TDS Na+ K+ Ca2+ Mg2+ Cl− SO42−
(kg/L) (g/L) (g/L) (g/L) (g/L) (g/L) (g/L) (g/L)
Seawater 1.02 8.3 35 10.77 0.40 0.41 1.30 19.35 2.70
Brine 1 1.04 6.9 71 24.90 0.80 2.00 0.40 43.20 0.30
Brine 2 1.08 6.5 130 43.24 1.24 3.36 1.58 75.63 2.84
Brine 3 1.13 6.2 213 56.70 0.19 18.00 2.50 122.00 3.70
Formation waters from different reservoirs have similar composition, all charac-
terized by high salinity, or total dissolved solids, TDS, and slightly acidic (pH 3–6).
Regardless the specific salinity, typically the ratio among the content of the main
ions, such as chloride, sodium, potassium and bicarbonate in formation water with
respect to seawater is almost constant, about 4. Only Ca, Mg and sulphate ions do
not follow this rule, since the relative sulphates precipitate. In other words, for-
mation waters are a concentrated seawater.
Table 24.1 compares the standard composition of seawater, according to ASTM
D1141, and the composition of formation water of some of thousands of reservoirs
known in the world.
Wet hydrocarbon gas contains water in vapour phase: thermodynamic condi-
tions, i.e., temperature and pressure, define its content. These two parameters are
also linked by gas law and may vary during transport and treatment. Water content
increases as temperature increases and pressure decreases. As a rule of thumb, at a
fixed temperature, water content is inversely proportional to pressure. Corrosion
occurs if water condensates, i.e. if working conditions, temperature and pressure,
are below the dew point. Condensed water has a very low ionic content and a lower
pH with respect to formation water, typically 3–4.
24.3 Water Wetting
Metal surfaces in contact with hydrocarbons may undergo corrosion only if they are
wetted by the water phase in a permanent or intermittent way. The conditions
giving rise to water wetting vary depending on the composition of the multi-phase
fluid (hydrocarbon, water and gas) and the operating conditions, mainly tempera-
ture, pressure and flow regime.
A water wetting factor, FWW, is considered to define wettability:
• Fww = 0 when no water is wetting the metal surface (consequently, no corrosion
is expected)
• 0 < Fww < 1 when water wetting is uncertain
• Fww = 1 when there is a permanent condition of water wetting (maximum
corrosiveness).
According to an empirical rule, water wetting (0 < Fww < 1) occurs:

• In vertical flows, for example inside the tubing of wells, when the percentage of
the aqueous phase exceeds 20% in volume
• In horizontal flows, for example inside transportation pipelines, when the per-
centage of water is higher than 1%
• In oil systems, if water percentage is higher than 40%. Water wetting is
uncertain between 5 and 40% of water and is also a function of crude oil type
and flow regime
• In wet gas, water wetting occurs only during water condensation.
For multiphase systems the water wetting factor, Fww, is a function of water cut,
flow velocity, flow pattern and oil/water emulsions. Figure 24.2 reports the water
wetting factor as a function of water cut for a vertical flow, although often adopted
also for horizontal one.
Water wetting is strongly influenced by flow pattern. Gas-liquid mixtures
flowing in a pipe produce a variety of flow patterns. The particular “pattern”
depends mainly on phase flow rates, fluid properties and tube sizes and orientation
(vertical or horizontal).
The apparent velocities (in m/s), defined as the velocities a phase would exhibit
if it was the only phase flowing alone through the whole pipe cross section, are used
to estimate the flow pattern:
QG =86;400
VSG ¼ ð24:1Þ
p D2 =4
ðQW þ QO Þ=86;400
VSL ¼ ð24:2Þ
p D2 =4
1
0.9 EXPECTED
Water wetting factor
0.8
0.7
0.6
0.5
0.4
0.3
UNCERTAIN
0.2
0.1 TRACE
0
0 5 10 15 20 25 30 35 40 45 50 55 60
Water cut (%)
Fig. 24.2 Water wetting factor as a function of water cut

24.3 Water Wetting 553
Dispersed bubble
10
Annular
VSL (m/s) Slug
1
Elongated bubbles
Mist
0.1
Stratified
wavy D = 25 mm
Stratified Brine 3% NaCl
0.01
pCO = 10 bar
2
T = 70°C
0.1 1 10 100
VSG (m/s)
Fig. 24.3 Flow regime determination for an horizontal pipe
where VSG is the gas apparent velocity, VSL is the liquid (oil + water) apparent
velocity, Q is the flow rate (in m3/d) and D is the internal diameter of the pipe (in m).
Figure 24.3 reports a graph—only valid for horizontal pipes—where the flow
regime is determined as a function of the apparent fluid velocities.
24.4 Corrosion Assessment
Several factors strongly influence corrosion occurrence and corrosion rate inside oil
& gas facilities. In addition to water wetting factor and flow pattern, the following
parameters must be considered: pressure, temperature, gas-oil ratio, CO2 and H2S
content. The latter plays an important role; in fact, since production fluids are
typically oxygen-free, CO2 and H2S are the two gases, which dissolve into water
forming weak acids, which in turn are responsible for metal corrosion.
A production fluid is classified sourif H2S is present, and sweet if it is not.
Furthermore, it is called CO2—dominated if the CO2/H2S ratio is greater than 200,
otherwise it is considered H2S dominated.
Corrosion rate is given by a simple relationship:
C rate ¼ F ww C th ð24:3Þ
where Cth is the theoretical corrosion rate when water wetting is 1, depending on
the specific cathodic reactant (CO2 or H2S). Both water wetting factor and
theoretical corrosion rate change during time, since water cut, pressure, tempera-
ture, fluid composition are changing during production.
24.5 CO2-Related Corrosion
CO2 is the most important cause of corrosion for carbon steel structures in oil and
gas production. Carbon dioxide dissolves in water forming carbonic acid
H2 O þ CO2 ! H2 CO3 ð24:4Þ
which is a weak acid, and dissociates to bicarbonates:
H2 CO3 ! H þ þ HCO
3 ð24:5Þ
At pH > 6, bicarbonates dissociate to form H+ and carbonate ions, CO32−. In pro-

duction fluid, pH is lower than 6, so the latter dissociation occurs to a very small extent.
Frequently, fluid pH is unknown because it is difficult to measure. In presence of
only CO2, pH can be estimated based on CO2 partial pressure, pCO2 :
pH ¼ 4 0:5 log pCO2 ð24:6Þ
A more correct pH estimation takes into account composition of the aqueous phase,
partial pressure of CO2 and H2S and concentration of bicarbonates. At a fixed CO2
partial pressure, Henry’s law determines the amount of CO2 dissolved into water
(see box).
pH Estimation
Frequently, pH is unknown because it is difficult to measure: recourse is made
to calculations based on composition of the aqueous phase, partial pressure of
CO2 and H2S and concentration of bicarbonates (Figs. 24.4 and 24.5).
The following empirical formulae are often used:
• In the presence of bicarbonates

pH ¼ 4:4 0:475 ln pCO2 þ pH2 S þ 0:5 lnðHCO3 Þ þ 0:00375 T
• In the absence of bicarbonates

pH ¼ 3:8 0:195 ln pCO2 þ pH2 S þ 0:00375 T
where pCO2 and pH2 S are the partial pressures of CO2 and H2S in the gas, T is
the temperature (°C) and HCO3− is the concentration of bicarbonates in
solution in meq/L.
24.5 CO2-Related Corrosion 555
pH 20°C
100°C
1 10 102 103 104

pCO + pH S (kPa)
2 2
Fig. 24.4 pH of distillate (condensate) water as function of CO2 and H2S in the absence of
bicarbonates
If the concentration of bicarbonates is unknown, it is assumed zero in the

case of condensates alone (ionic strength l < 0.5) and equal to 10 meq/L in
the presence of formation water (ionic strength l > 0.5). The ionic strength of
a solution is a measure of the total concentration of ions present. It is a
chemical-physical quantity that expresses the intensity of the electric field
generated by the charges.
pH 4 5 20°C
3
100°C
7 2
1
6
5
HCO3-
1 0 meq/L 2 0.1 meq/L
4
3 1 meq/L 4 10 meq/L 5 100 meq/L
1 10 102 103 104

pCO + pH S (kPa)
2 2
Fig. 24.5 pH of formation waters (brines) as function of bicarbonate, CO2 and H2S
To calculate the pH, reference can also be made to NORSOK M-506

Model (1998).
A later model has been proposed (De Waard et al. 7) which also takes into
consideration the diffusion of CO2. However, in order to apply this model, it
is necessary to know the fluid dynamic conditions of the aqueous phase.
24.5.1 Corrosion Mechanism
Carbonic acid, though it is a weak acid, is extremely corrosive towards carbon steel.
For example, comparing the corrosion rate of iron in carbonic acid and that in a
strong acid such as hydrochloric acid, both with a pH of 4, the corrosion rate in
carbonic acid is about ten times higher. The reason is the different kinetics involved
in the hydrogen ion reduction reaction.
From an electrochemical point of view, at pH 6, the cathodic reaction is assumed
to follow primarily the equation:
H2 CO3 þ e ! Hads þ HCO3 ð24:7Þ
The hydrogen atoms adsorbed on the surface are there combined to form hydrogen
gas:
2Hads ! H2 ð24:8Þ
When carbon steel corrodes, the anodic reaction is:
Fe ! Fe2 þ þ 2e ð24:9Þ
Then, the total corrosion reaction is:
Fe þ H2 CO3 ! FeCO3 þ H2 ð24:10Þ
Since the solubility of FeCO3 is low and decreases with increasing temperature,
FeCO3 is deposited when temperature exceeds a limit that depends on CO2 partial
pressure. Accordingly, corrosion of carbon steel is:
• Generalized at temperatures below 80 °C, with a characteristic morphology
known as mesa corrosion (Fig. 24.6).
• Generalized with significant localization in the temperature range 80–120 °C
due to the formation of partially protective iron and calcium carbonates
• Negligible at T > 120 °C, since a compact protecting, passivating film forms.
Fig. 24.6 Example of carbon steel pipe suffering mesa corrosion
24.5.2 Corrosion Rate Evaluation
In Sect. 8.2.2, a critical discussion of corrosion in carbonic acid is reported, which

helps understand the corrosion mechanism. For applications, the most used industry
approach is based on laboratory experiments and field data, the corrosion rate of
carbon steel mainly depends on three parameters:
• Partial pressure of CO2, pCO2 , or fugacity at high pressure
• Temperature
• pH of the aqueous phase, also influenced by bicarbonates.
The usual approach in industry to estimate CO2 corrosion rate is mostly derived
from field data and experimental testing. In the 1975, C. De Waard and D.E.
Milliams proposed an equation to calculate corrosion rate in the presence of CO2,
subsequently corrected with U. Lotz (1991, 1995):
1710
log Crate;CO2 ;dWM ¼ 5:8 þ 0:67 log ðpCO2 Þ ð24:11Þ
T þ 273
where C rate;CO2 ;dWM is the corrosion rate (mm/y), T is the temperature (°C), and pCO2
is the CO2 partial pressure (bar) in the gas phase.
Starting from this basic equation, correction factors have been introduced. The
most important take into account gas fugacity at high pressures (system factor),
formation of deposits (scale factor), pH (pH factor) and chromium content in the
steel (Cr factor). Two minor factors are the glycol factor and the condensation
factor.
The final corrosion rate is obtained multiplying the corrosion rate obtained by
the basic De Waard and Milliams equation (Crate;CO2 ;dWM ) by the corrective factors:

Crate;dWM;C ¼ Crate;dWM Fsystem Fscale FpH Fgly Fcond FCr ð24:12Þ
Corrosion rate can be also estimated by applying a pure electrochemical approach

based on the theory of corrosion in acid electrolyte (the so called Tafel-Piontelli
model—see Sect. 8.1 and Lazzari 2017).
24.5.3 Metals for Sweet Condition
Carbon steel and low carbon steel alloys are the first material selection for pipeline
transport of sweet production fluid. Typically, an extra thickness, the so-called , CA,
beyond the value requested by mechanical requirement of the item, is used to take
into account expected thickness loss due to CO2 corrosion.
As a rule of thumb:
• CA = 1.5 mm is usually taken with non-corrosive fluids
• CA = 3 mm is used for weakly corrosive fluids or inhibited fluids
• CA = 6 mm is used for corrosive fluids (or non-inhibited fluids).
Corrosion allowance higher than 6 mm is seldom used.
If corrosion allowance higher than 6 mm is required, even in presence of inhi-
bitors, corrosion resistant alloys (CRA) are used, with an increased cost, but a
practical immunity to CO2 corrosion; even Cr 13% is able to withstand sweet
condition. Selection of proper CRA shall consider occurrence of other corrosion
forms (i.e., SSC, SCC, pitting).
Correcting factors
At high operating pressures, higher than 100 bar, CO2 partial pressure is
substituted by its fugacity, f CO2 , as follow
fCO2 ¼ a pCO2
where a is the fugacity coefficient, obtained as follows (T is temperature in

°C, P is pressure in bar)

1:4
logðaÞ ¼ 0:0031 P
T þ 273
The system factor is introduced to correct the non-ideality of the natural

gas at operating pressures higher than 100 bar. It is estimated as follow:

1:4
log Fsystem ¼ 0:67 0:0031 P
T þ 273
The scale factor takes into account the scale formation (iron carbonate and
magnetite) if operating temperature exceeds a scaling temperature, Tscal,
calculated as a function of pCO2. The presence of a scale reduces the rate of
corrosion, since it reduces the capability of CO2 to diffuse on the metal
surface. Mitigating effects by this factor are not applicable when H2S is
present at high content.
The scaling temperature, Tscale, is determined as follow
2400
Tscale ¼ 273
6:7 þ 0:6 logðfCO2 Þ
If actual T of the fluid is greater than Tscale, a scale factor has to be taken
into account (in this case, pH factor, hereafter described, is taken equal to 1):
2400
logðFscale Þ ¼ 0:6 logðfCO2 Þ 6:7
T þ 273
Otherwise, if real temperature is lower than the scaling temperature, scale

factor is 1.
The pH factor compares the actual pH of the fluid with the saturation pH
of iron carbonate or magnetite: if actual pH is more acidic a factor greater
than 1 is applied, on the contrary if it is more alkaline the factor mitigates
corrosion rate. pH factor applies only if fluid real temperature is lower than
scaling temperature, i.e. scale factor is 1.
Saturation pH, pHsat, is calculated for the precipitation of scales (FeCO3
and Fe3O4), taking into account also scaling temperature.
1307
pHsat; Fe3 O4 ¼ 1:36 þ 0:17 logðfCO2 Þ
T þ 273
pHsat; FeCO3 ¼ 5:4 0:66 logðfCO2 Þ
The minimum value is considered

to estimate FpH.
If pHsat > pHact log FpH ¼ 0:32 ðpHsat pHactÞ

If pHsat < pHact log FpH ¼ 0:13 ðpHact pHsat Þ1:6
The Cr factor takes into account the fact that a small amount of Cr in
carbon steel improves CO2 corrosion resistance, since Cr makes iron car-
bonate film more stable. The addition of 0.5% Cr especially increases
resistance to mesa corrosion, at temperatures below 90 °C, and it is very
beneficial in combination with film forming corrosion inhibitors.
The Cr factor is estimated as follow
1
FCr ¼
1 þ 1:4 %Cr
Considering the typical Cr content in low alloyed carbon steel (0.5%), the
factor is close to 0.6.
The glycol factor takes into account effects of glycol on CO2 corrosion
rate. Glycol is introduced to prevent hydrates formation. The factor is esti-
mated as follows:
F GLY ¼ A logðW CUT %Þ2A
where A is a constant (1.6), weakly dependent on the alcohol type.

The condensation factor applies only to wet gas systems when cooling is
expected. Water condensing under a high partial pressure of CO2 is acid and
quite corrosive, but iron bicarbonate FeCO3 produced as corrosion product is
highly soluble in the thin water film and behaves as an excellent pH con-
troller. For the calculation of the condensation factor, two cases may be in
general expected: slow cooling systems (Fcond = 0.1) and rapid cooling
systems (Fcond = 1), as heat exchangers or coolers. Corrosion rate of steel
exposed to water phase condensing from wet gas quickly decreases with time
only in slowly cooling systems.
Henry’s Law
Henry’s law, formulated by the English chemist William Henry in 1803,
regulates the solubility of gases in a liquid. It states that, at a constant tem-
perature, the amount of dissolved gas is directly proportional to its partial
pressure in the gas phase. The proportionality factor is called Henry’s law
constant.
Once the equilibrium is reached, the liquid is defined as saturated at that
temperature. This state of equilibrium persists until the external pressure of
the gas remains unaltered, otherwise, if it increases, other gas will enter into
solution, if it decreases, the liquid will be in a state of over-saturation and gas
will be released until pressures are balanced again.
There are several ways of describing the solubility of a gas in water.
Usually Henry’s law is written as follow
½GASwater ¼ H pgas
where [GAS]water is the concentration of a species in the aqueous phase (in

mol/L), H is Henry’s constant (in mol/atm L) and pgas is the partial pressure
of that species in the gas phase (in atm).
When the temperature of a system changes, the Henry’s constant also

changes:

DHsol 1 1
HT ¼ HT0 exp
R T T0
where HT is the Henry’s constant at a temperature T, H0T is the Henry’s

constant at room temperature, DHsol is the solution enthalpy, R is the gas
constant, T is temperature (in K) and T0 is room temperature (298 K).
Next table reports some values of Henry’s constant and temperature
dependencies.
Based on Henry’s law, at room temperature, 1500 ppmwt of CO2 are
dissolved in a solution in equilibrium with a CO2 partial pressure of 1 bar.
According to NACE MR0175-ISO 15156 standard, sour condition occurs
when H2S partial pressure is higher than 0.0035 bar, which corresponds to
about 12 ppmwt of H2S in solution at room temperature and 4 ppmwt at 75–
80 °C.
If H2S partial pressure is 1 bar, at room temperature, 3400 ppm of H2S are
dissolved into the solution.
Unit H2S CO2 O2 H2

H at 25 °C (mol/atm L) 10−1 3.4 10−2 1.5 10−3 7.8 10−4
−ΔH/R (K) 2100 2400 1800 500
H at 75 °C (mol/atm L) 3.6 10−2 10−2 5.7 10−4 6 10−4
24.6 H2S-Related Corrosion
According to NACE MR0175-ISO 15156 standard, sour condition occurs if the

H2S partial pressure is higher than 0.0035 bar. Three levels of corrosion severity are
identified as a function of the in situ pH and H2S partial pressure (Fig. 24.7). The
most influencing parameter is the concentration of H2S. The minimum effective
H2S concentration in the electrolyte is as little as 10 ppm, which corresponds,
according to Henry’s law, to a critical H2S partial pressure of 0.0035 bar or 0.05 psi
(see Henry’s law box).
7.5
0.0035 bar
(0.05 psi) SSC Region 1
6.5 (slightly sour service)
SSC Region 2
(moderately sour service)
5.5 SSC Region 0
In situ pH
(sweet service)
4.5
SSC Region 3
(severely sour service)
3.5
2.5
0.0001 0.001 0.01 0.1 1 10 100
Hydrogen sulfide partial pressure, pH S (bar)
2
Fig. 24.7 Sour service condition according to NACE MR0175—ISO 15156
24.6.1 Corrosion Mechanism
Like CO2, H2S dissolves in water, forming a weak acid solution, with pH around 6:
H2 S ! H þ þ HS ð24:14Þ
The hydrogen ions are responsible for the corrosive nature of H2S.
The most important cathodic reaction in a sulphide-containing environment can
be expressed by:
2H2 S þ 2e ! 2Hads þ 2HS ð24:15Þ
Considering carbon steel dissolution, the overall corrosion reaction is:
Fe þ H2 S ! FeS þ 2Hads ð24:16Þ
The adsorption of HS– ions on the steel surface forms iron sulphide films, FeS,
which may inhibit the hydrogen atoms recombination (the so-called “poisoning
effect”), allowing the diffusion of atomic hydrogen into the steel, and then pro-
moting hydrogen damages. The latter is the only form of corrosion occurring in the
bulk of the metal. All of the other corrosion processes happen at the metal surface.
Different forms of corrosion are possible in a sour fluid:
• Generalized corrosion of carbon steel
• Hydrogen Induced Cracking (HIC) with blister formation due to hydrogen
atoms permeating into the steel in the absence of any internal or external stress
• Sulphide Stress Cracking (SSC) occurring on metals susceptible of hydrogen
embrittlement in the presence of internal or external stresses.
24.6 H2S-Related Corrosion 563
24.6.2 Generalized Corrosion
H2S is a weak acid. At pH 6, the corrosion rate of carbon steel should be low or
even negligible; conversely, experience showed that carbon steel corrosion rate in a
H2S containing environment is remarkable (close to 0.5–1 mm/year, see also
Sect. 8.2.3), because insoluble FeS forms, with an extremely low solubility product,
in the order of 10−24. This leads to a decrease in the anodic potential of iron
dissolution and the consequent availability of a greater electrochemical driving
force even in neutral solutions.1
The iron sulphide layer is not always compact and protective, and may lead to
localized corrosion with a galvanic coupling mechanism due to the fact that FeS has
an electronic conductivity and a practical nobility higher than iron.
The prediction of the corrosion rate is based on empirical rules, which can be
summarized as follows:
• At T < 60 °C
• Corrosion rate is negligible for H2S concentrations in solution below 40 ppm
• Significant corrosion (0.5 mm/year) occurs at H2S concentrations above
3500 ppm (corresponding to a H2S partial pressure of 1 bar)
• At T > 60°C
• Corrosion rate is 1 mm/year at H2S concentrations above 40 ppm. Higher
corrosion rates are not possible because of the formation of a protective iron
sulphide.
24.6.3 Hydrogen Induced Cracking (HIC)
The effect of H2S as a cathodic poison for hydrogen recombination (see

Sect. 14.1.2) allows the ingress of atomic hydrogen into the metal. Hydrogen atoms
diffuse into the metal since they reach specific traps, such as inclusions, in particular
elongated MnS2, or micro-voids in the metal matrix. Once accumulated inside the
traps, as no H2S is present, hydrogen atoms recombine to form hydrogen gas, H2.
The hydrogen gas, too large to diffuse through the metal lattice, accumulates and
generates extremely high internal pressures, sufficient to cause local plastic defor-
mation of the metal and blister formation, as shown in Fig. 24.8.
1
The driving force, DE, is given by the difference between equilibrium potential of the cathodic
reaction, EC, and equilibrium potential of the anodic reaction, EA. In neutral conditions,
EC = −0.059 pH = −0.42 V SHE. The equilibrium potential of iron dissolution is
EA = −0.44 + 0.059/2 (log [Fe2+]). In sour conditions, the formation of insoluble FeS reduces
iron ion concentration at 10−12 mol/L. Then the driving force is about 0.4 V. At the same pH, in
de-aerated water, the driving force is 0.2 V.
Fig. 24.8 Examples of HIC and blistering on a carbon steel pipe
The inclusions with the greatest impact on this phenomenon are those of man-
ganese sulphide (MnS2 type II), which during the hot rolling of the carbon steels
used for pipelines and the sheets for pressurized containers are squeezed and
arranged parallel to the direction of rolling, thus forming an easy trap for hydrogen
atoms.
HIC is linked to the quantity of hydrogen atoms diffusing into the metal matrix
and to time:
• For H2S partial pressure above 0.1 bar (corresponding to 400 ppm in the
aqueous phase), HIC occurs in a period of time comparable to the mean service
life of an oil facility, 15–20 years
• For H2S partial pressure below 0.1 bar, HIC occurs in a longer period of time.
From a practical point of view, when H2S partial pressure is higher than 0.03 bar,
two strategies can be adopted to limit HIC: (1) the use of corrosion inhibitors,
which reduces the quantity of hydrogen produced; (2) the use of non-susceptible
steels, for example steels treated with rare earth metals and steels with very low
sulphur content (<30 ppm).
24.6.4 Sulphide Stress Cracking (SSC)
SSC occurs when atomic hydrogen diffuses into the metal remaining in solid
solution in the crystal lattice. This reduces the ductility and deformability of the
metal, promoting the hydrogen embrittlement of the metal (Fig. 24.9).
Several factors influence SSC: steel composition, thermal treatments,
microstructure, mechanical resistance, pH, H2S partial pressure, load applied,
temperature and time. The onset of SSC is firstly evaluated based on the partial
pressure of H2S in the gas phase, which is proportional to its concentration in the
aqueous phase. High yield strength steels (ultimate tensile strength above 700 MPa)
are the more susceptible to SSC, since their microstructure is particularly sensitive
to the effects of hydrogen. Ruptures are characterized by transgranular cracking.
The cracking process is very rapid and has been known to take as little as few hours
for a crack to form and cause catastrophic failure.
24.6 H2S-Related Corrosion 565
Fig. 24.9 Examples of SCC on a carbon steel tubing
The tendency for SSC to occur is increased by the presence of hard microstruc-
tures such as un-tempered or partly tempered low temperature transformation
products (martensite, bainite). These structures may be inherently present in high
strength low alloy steels, may result from inadequate or incorrect heat treatment, may
arise in welds and particularly in low heat input welds in the heat affected zones.
Finally, SSC is a highly temperature dependent phenomenon: the maximum
susceptibility occurs at room temperature.
24.6.5 Metals for Sour Service Condition
Carbon steel for sour service must have some very general mechanical and met-
allurgical characteristics to reduce susceptibility to hydrogen attack: cleanliness to
avoid inclusions and segregation, homogeneity of composition, fine grain size to
improve toughness and stability, i.e. complete release of internal stresses. Mn and S
content should be very low to reduce the formation of a central segregation band.
Steel can be treated with calcium or with rare-earth metals (an alloy is often used of
Ce, La, Nd, Pr, so called Mischmetal alloy) to allow the formation of finely dispersed
and spheroidal inclusions, much less harmful to steel with respect to the elongated
ones. As regard mechanical properties, the maximum acceptable hardness for carbon
steel working in severe sour service condition is 22 HRC (Rockwell C). Finally, to
guarantee weldability in field, carbon equivalent should be less than 0.38, and post
weld heat treatments are recommended both to reduce the hardness of weld deposit
and heat affected zone and to release the residual stresses in the weldment.
Corrosion resistant alloys. Stainless steels are used in the presence of corrosive
fluids, when carbon and low alloy steels are not recommended. As mentioned, all
stainless steels resist to CO2 related corrosion. Furthermore, sour service grades are
available for any content of H2S. Martensitic (13–15% Cr) stainless steels are the
lowest grade. The interest in this stainless steel is twofold: high mechanical resis-
tance, being martensitic, and low cost, because of low alloy content. However, they
have high SSC susceptibility even with modest amounts of H2S, and pitting and
crevice corrosion may occur in chloride-containing environment at high tempera-
ture even with a very low amount of oxygen (Oldfield and Sutton 1978). Austenitic
stainless steels are used because of many good properties: good weldability,
resistance to SSC at low temperature; however, the presence of chlorides limits their
resistance. Super austenitic stainless steels (6Mo and 904L grades) display higher
resistance to pitting and stress corrosion cracking and higher mechanical properties.
Duplex and superduplex stainless steels resist to Cl-induced SCC thanks to the
ferritic microstructure and resist to hydrogen embrittlement thanks to the austenitic
part. They show a good resistance to pitting at high T and Cl-concentrations.
Ni-based alloys have an austenitic microstructure, are resistant to general corrosion
and highly resistant to SSC. Highest grades, with high nickel and molybdenum
content, are resistant to the most severe conditions.
Clad components are products comprising a carbon or low alloy steel base pipe with
an internal layer (approximately 3 mm) of corrosion resistant alloy. The cheap carbon
steel base gives the mechanical strength, while the internal CRA layer guarantees high
corrosion resistance (Fig. 24.10). The internal layer may be metallurgically bonded
(clad pipe) or mechanically bonded (lined pipe). Amongst the available options listed
by API 5LD for the CRA layer, the solutions that found practical application and are
available on the market are AISI 316, nickel alloy 825 and alloy 625.
24.7 Downstream Corrosion
24.7.1 Corrosion by S/H2S Atmosphere
Steels used in oil refining processes undergo corrosion attacks at temperatures

above 260 °C when the sulphur content (such as elemental sulphur, H2S and
Fig. 24.10 Examples of carbon steel pipes with an internal clad in 625 Nickel alloy 3 mm thick
24.7 Downstream Corrosion 567
combined in mercaptans) is high. The extent of the attack depends on sulphur

content, temperature and presence of gaseous hydrogen. At temperatures above
150 °C, mixtures of hydrogen and sulphur compounds lead to the formation of
H2S. The H2S amount becomes significant at T higher than 260 °C, with a maxi-
mum at 370 °C. Carbon steel has a very low corrosion resistance. Small addition of
chromium improves the resistance to attacks: at 370 °C, the addition of 5% Cr
reduces corrosion rate from 3 to 1 mm/year. At higher chromium content, corrosion
rate is further reduced to 0.5 mm/year if 9Cr–0.5Mo steel is used, to 0.1 mm/year
when 12Cr steel or 18Cr steel are used. The corrosion resistance depends on the
formation of a protective sulphide layer, which is more robust when the chromium
content is increased.
24.7.2 Corrosion by Sulphur
Sulphur (melting point 113 °C and boiling point 445 °C) is present in some pet-
roleum reservoirs in association with H2S. The formation of sulphur may occur due
to the reduction of sulphates to sulphur by methane
4 þ CH4 ! S þ 2H2 O þ CO2

SO2 ð24:17Þ
or by catalytic decomposition of hydrogen sulphide or the oxidation of hydrogen

sulphide by oxygen (due to contaminations).
Sulphur reacts with hydrogen sulphide to form polysulphides which in turn
release sulphur to form deposits (slugs) and entrainment in the tubing of oil wells.
Sulphur is an effective cathodic reactant, acting as an electron acceptor through
the catalytic action of the sulphide film which has electronic conductivity, and gives
rise to high corrosion rates when it comes into direct contact with steels; if it is
present in a hydrocarbon solution, corrosion rate is controlled by diffusion pro-
cesses. At high temperatures (above 120 °C), sulphur dismutes to H2S and sul-
phuric acid, causing the rupture of the passivation films and the onset of localized
corrosion (crevice and SSC) on stainless steel alloys and corrosion resistant alloys.
The sulphur corrosion rate on carbon and low alloy steels depends on temperature:
• At T < 120 °C and in direct contact with sulphur, corrosion rate is in the order
of several mm/year and is only slightly influenced by temperature. The sul-
phides present on the surface catalyse the reaction and lead to macrocell con-
ditions similar to corrosion by differential aeration
• At T > 120 °C corrosion rate increases due to the formation of sulphuric acid,
but only up to about 150 °C
• At T > 150 °C corrosion rate begins to decrease due to the protective action of
corrosion products
• At 180 °C corrosion rate is nonetheless so high (above 10 mm/year) that these
materials cannot be used.
The presence of elemental sulphur generally leads to the localized corrosion of

stainless steels: duplex stainless steels undergo generalized corrosion even at
ambient temperature like carbon steels, whereas austenitic stainless steels present
low resistance only above 120 °C. Martensitic stainless steels generally have low
resistance. The presence of sulphur increases vulnerability to SCC: when T is higher
than 120 °C, resistance to corrosion increases with increasing Ni, Cr and Mo
content. Nickel alloys offering good resistance in severely aggressive conditions (S,
H2S, CO2, Cl−) at high temperatures must generally have a basic composition of the
type Ni > 55%, Mo > 12%, Cr > 15% (typically Alloy G-50 22Cr–52Ni–11Mo–
0.7 W–0.8Cu). Grade 2 titanium gives rise to crevices when T > 130 °C; beta-C
titanium alloys present greater resistance.
24.7.3 Corrosion by H2/H2S
In the presence of H2/H2S atmospheres, Cr–Mo steels do not resist at temperatures

above 315 °C. It is necessary to use proper austenitic stainless steels, with an
aluminium-enriched surface. In this case, corrosion rate is lower than 0.25 mm/year
even at 500 °C.
24.7.4 Corrosion by Naphthenic Acid
In the presence of organic acids in crude oil, particularly those with naphthenic
structure, carbon and low alloy steels undergo corrosion at temperatures between
200 and 400 °C with a maximum corrosion rate at about 270–280 °C.
Aggressiveness is measured based on the neutralization number, or total acid
number (TAN), which measures the acidity of the organic content. Once the acidity
of the crude oil has been established, a crude oil is considered aggressive if the
TAN is greater than 0.5 mg KOH/g. On a rough estimate, corrosion rate increases
by three times every 100 °C increase in temperature above 230 °C, up to about
400 °C.
Corrosion is often associated with corrosion-erosion phenomena due to high
turbulence of the fluids, for example in centrifugal pumps, in heaters (especially in
the bends of coils), in the connecting line between heater and fractionating column
and in the inlet section where the partially vaporized crude oil enters the column.
The corrosion mechanism involves the formation of iron complexes with organic
acids.
Carbon steel has a good behaviour at temperatures below 220 °C. For higher
temperatures cast iron and Cr–Mo steels with increasing chromium content up to
12% must be used. In very severe condition, stainless steels, AISI 316, AISI 309
and AISI 310, should be used. Monel, Inconel and Alloys B are suitable, but
attention must be paid to the presence of sulphur and organic sulphur compounds.
24.7.5 Hydrogen Attack
Hydrogen atmospheres above 200 °C and pressures above 7 bar cause hydrogen
damage with blister formation and decarburization of steel and also a reduction of
mechanical properties. Cr–Mo steels are resistant to hydrogen damage (due to the
stability of carbides). The resistance is verified using the Nelson curves; for more
details please refer to Chap. 14.
The formation of blisters and cracks is due to the formation of methane by the
reaction of hydrogen with free carbon.
In the presence of acid attack and hydrogen sulphide (H2S), the atomic hydrogen
penetrates into the crystal lattice of the iron causing:
• Cracking (Step Wise Cracking) or swelling (blisters). This phenomenon is often
referred to as HIC (Hydrogen Induced Cracking) for C-Mn steels even without
tensile stresses
• At low temperature, hydrogen embrittlement on susceptible materials (high
strength steels) in the presence of tensile stresses above a critical threshold.
24.7.6 Organic Acid Corrosion
Organic compounds present in some crude oils decompose in the crude furnace to
form low molecular weight organic acids which condense in distillation tower
overhead systems. The low molecular weight organic acids that are formed include
formic acid, acetic acid, propionic acid, and butyric acid. They may also result from
additives used in upstream operations or desalting. Corrosion is a function of the
type and quantity of organic acids, metal temperature, fluid velocity, system pH,
and presence of other acids. Formic acid and acetic acid are the most corrosive.
They are soluble in naphtha and are extracted into the water phase, once water
condensates, and contribute to a reduction of pH. The presence of organic acids will
contribute to the overall demand for neutralizing chemicals but their effects may be
completely masked by the presence of other acids such as HCl, H2S, carbonic acid
and others. Corrosion is most likely to be a problem where relatively non-corrosive
conditions exist in an overhead system and if there is a sudden increase in low
molecular weight organic acids. The latter reduces the pH of water in the overhead
system, requiring a potentially unexpected increase in neutralizer demand. The
corrosion mechanism of organic acids is reported in Chap. 8.
All carbon steel piping and process equipment in crude tower, vacuum tower and
coker fractionator overhead systems including heat exchangers, towers and drums
are susceptible to damage where acidic conditions occur. Corrosion tends to occur
where water accumulates or where hydrocarbon flow directs water droplets against
metal surfaces. Corrosion is also sensitive to flow rate and tends to be more severe
in turbulent areas in piping systems.
24.7.7 Polythionic Acid Stress Corrosion Cracking
It is a form of stress corrosion cracking normally occurring during shutdowns,

start-ups or during operation when air and moisture are present. This type of cor-
rosion occurs on austenitic stainless steels, alloy 600/600H and alloy 800/800H.
A combination of environment, material, and stress are required. Cracking is due to
sulphur acids forming from sulphide scale, air and moisture acting on sensitized
austenitic stainless steels. It is usually adjacent to welds or high stress areas.
Cracking may rapidly propagate through the wall thickness of piping and com-
ponents in a matter of minutes or hours.
24.7.8 High Temperature Sulphidation
Elevated temperature sulphidation in crude oil processing units is one of the most
relevant materials problems encountered in the refining industry. It generally occurs
in the temperature range 250–550 °C. This phenomenon is encountered in distil-
lation units processing crude oils, which contain a significant concentration of
sulphur compounds (such as mercaptans, sulphides, disulphides, etc.) with total
sulphur higher than 0.6%, by weight. Most severe sulphidation attack in crude
distillation units occurs in flash zones of towers, furnace tubes, and transfer lines.
The relative corrosiveness of different sulphur compounds for carbon steel
increases with temperature, chemistry of the sulphur functional group and type of
the organic group. Thiophene was found to be the least aggressive compound.
Above 450 °C the aggressiveness of this attack starts to decrease, owing to the
decomposition of reactive sulphur organic compounds and to the formation of a
protective coke layer on steel.
Iron sulphide scales are only partially protective and do not eliminate further
attack. At long exposure times the iron sulphide scales increase in thickness and
eventually spall, resulting in fresh metal surface exposed to the sulphidizing
environment. The cycle of growth and spalling of sulphide scales is periodically
repeated. Velocity also plays a role, particularly in turbulent vapour/liquid mixtures,
which are most prone to continuously erode the sulphide scale and significantly
accelerate the rate of attack.
Steel alloyed with Cr exhibits a two-layer scale: a mixed inner scale composed
by iron sulphide and a sulpho-spinel FeCr2S4, and outer scale by Fe1−xS. When Cr
content increases, the inner layer tends towards single-phase sulpho-spinel FeCr2S4.
It is generally thought that this scale is more protective than iron sulphide.
Poisoning Effect of H2S on Human Beings

H2S is considered a broad-spectrum poison, which means it can damage
various body organs and apparatuses. At high concentrations, it paralyzes the
olfactory system making it impossible to perceive its unpleasant odour and
can cause unconsciousness within a few minutes. Typical thresholds are as
follows:
• 0.0047 ppm is the recognition threshold, the concentration at which 50%
of human beings can perceive the characteristic odour described as “rotten
eggs”
• <10 ppm is the exposure limit 8 h a day, without permanent damages
• 10–20 ppm is the limit beyond which eyes are irritated
• 50–100 ppm cause permanent ocular damages
• 100–150 ppm paralyze the olfactory nerve after few inhalations, pre-
venting the smell from being detected and therefore danger is not
recognized
• 320–530 ppm cause pulmonary edema with high risk of death
• 530–1000 ppm strongly stimulate the central nervous system and accel-
erate breathing, causing even more gas to be inhaled and causing
hyperventilation
• 800 ppm is the deadly concentration for 50% of human beings for 5 min
of exposure (LD50)
• >1000 ppm cause the immediate collapse with suffocation, even after a
single breath (“blow of lead of the barrel workers”, so called because the
victims were the workers using barrels in the tanning of skins).
24.8 International Standards
• API RP 14-E, Design and installation of offshore production platform piping

system, American Petroleum Institute, Dallas, TX.
• API RP 571, Damage Mechanisms Affecting Fixed Equipment in the Refining
Industry, American Petroleum Institute, Washington, DC.
• API RP 941, Steels for Hydrogen Service at Elevated Temperatures and
Pressures, American Petroleum Institute, Dallas, TX.
• EFC 16, European federation of corrosion publications (1996) Number 16,
Guidelines on materials requirements for carbon and low alloy steels for H2S—
Containing environments in oil and gas production. The Institute of Materials.
• EN ISO 3183, Petroleum and natural gas industries—Steel pipe for pipeline
transportation systems
• ISO 15156, Petroleum, petrochemical and natural gas industries—Materials for

use in H2S-containing environments in oil and gas production. Part 1: General
principles for selection of cracking-resistant materials; Part 2: Cracking-resistant
carbon and low alloy steels, and the use of cast irons; Part 3: Cracking-resistant
CRAs (corrosion-resistant alloys) and other alloys.
• ISO 21457—Materials selection and corrosion control for O&G production
systems
• NACE MR0103, Materials Resistant to Sulfide Stress Cracking in Corrosive
Petroleum Refining Environments”, NACE international, Houston, TX.
• NACE MR0175, Sulphide stress cracking metallic material for oil field equip-
ment, NACE international, Houston, TX.
• NACE TM0177, Laboratory Testing of Metals for Resistance to Sulfide Stress
Cracking and Stress Corrosion Cracking in H2S Environments” NACE inter-
national, Houston, TX.
• NACE TM0284, Evaluation of Pipeline and Pressure Vessel Steels for
Resistance to Hydrogen-Induced Cracking” NACE international, Houston, TX.
• NORSOK M-001, Materials Selection, Oslo, Norway.
• NORSOK M-506, CO2 corrosion rate calculation model, Lysaker, Norway.
24:1 The working condition of a carbon steel pipeline (with a tensile strength of
about 500 MPa, i.e. approx. 70 ksi) transporting a multiphase fluid are as
follow: P 100 bar, T 80 °C, in situ pH 4.3 (no bicarbonates), water cut 25%,
horizontal flux, fluid velocity 2 m/s, CO2 molar fraction 1%, H2S molar
fraction 0.01%. Design life is 20 years.
• Which corrosion do you expect?
• Estimate the corrosion rate using De Waard Milliams approach
• Is the corrosion allowance a possible solution?
• Calculate the corrosion rate and the corrosion allowance in the presence
of a corrosion inhibitor with a 95% efficiency.
24:2 Referring to the same working condition reported in Ex 24.1, how corrosion
rate and corrosion allowance change if a carbon steel alloy with 0.6 Cr is
used?
24:3 The working conditions of a carbon steel pipeline transporting a multiphase
fluid are as follow: P 80 bar, T 75 °C, in situ pH 4.0 (no bicarbonates),
fluid velocity 1.5 m/s, CO2 molar fraction 1.3%. H2S is absent. Water cut is
less than 5% for the first 5 years, 20% from year 6 to year 11, 25% from
year 12 to year 17, 35% till 20 years (design life). Estimate the thickness
loss corrosion rate using De Waard Milliams approach.
24:4 What is the difference between sweet service and sour service?
24:5 Describe in a qualitative way the mathematical approach used to estimate
CO2-corrosion rate. Referring to Chap. 8, make some numerical example of
corrosion rate evaluation comparing the De Waard Milliams approach with
the Tafel-Piontelli model.
24:6 A multiphase fluid is transported through a carbon steel pipeline. Working
conditions are as follow: T 70°C—P 80 bar—CO2 3.5%—H2S 0.6%—pH
3.9. According to NACE MR0175—ISO 15156 (Fig. 24.7) which is the
corrosion condition?
24:7 Which are the additional requirements for carbon steel (according to ISO,
NACE and EFC standards) in order to guarantee a safe use of the pipeline in
the declared working conditions. Justify each of them and give values of the
relevant parameters.
24:8 A new pipeline has to transport a gas hydrocarbons stream under the fol-
lowing conditions: required capacity 108 Nm3 per month (density 1.5 kg/
Nm3); condensed water (20% by weight); CO2 content 5% by volume on
the separated gas; chlorides in the formation water 30 g/L; temperature 40 °
C; pressure 7 MPa. Make a corrosion assessment in order to perform a
proper material selection. [Hint: fix a pipe diameter, estimate a wall
thickness; suggest toughness, consider the use of inhibitor, if the case,
compare carbon steel, copper alloys and stainless steels].
24:9 A cladded pipe (base metal carbon steel, clad in Alloy 625) is used to
convey a sour fluid from a platform to the onshore plant. After two years a
severe leakage is detected at a weld. Make a corrosion assessment.
24:10 Describe the main differences among the localized corrosion form in the
presence of H2S.
24:11 A carbon steel pipe (24″ in diameter, nominal OD 609.6 mm, thickness wall
12.70 mm) suffered internal localised corrosion attacks located at 3 and 9
o’clock position. Perforation occurred after 10 years. Working condition
were as follow: P 50 bar, T 30 °C, CO2 1.3%. The pipeline was carrying
formation water and methane. Corrosion was observed at the water line, in a
portion of the line where the pipe was half filled with formation water.
Which is the cause of corrosion?
Bibliography
Corrosion Data Survey (1985) Metal section, 6th edn. NACE International, Houston, TX
Corrosion in the Oil Refining Industry Conference (1998) NACE Group Committee T-8. NACE
International, Houston, TX, 17–18 Sept 1998
De Waard C, Milliams DE (1975) Carbonic acid corrosion of steel. Corrosion 31:5
De Waard C, Lotz U, Milliams DE (1991) Predictive model for CO2 corrosion engineering in wet
natural gas pipelines. Corrosion 47(12):976
De Waard C, Lotz U, Dugstad A (1995) Influence of liquid flow velocity on CO2 corrosion: a
semi-empirical model. Corrosion, 95, paper n. 128, NACE International, Houston, TX
Kane RD (2006) Corrosion in petroleum refining and petrochemical operations. In: ASM
handbook. ASM International, vol 13C, pp 967–1014
Lazzari L (2017) Engineering tools for corrosion. Design and diagnosis. In: European federation of
corrosion (EFC) series, vol 68. Woodhead Publishing, London, UK
Oldfield JW, Sutton MH (1978) Crevice corrosion of stainless steels. Br Corros J 13:104
Chapter 25
Corrosion in the Human Body
Human blood seeks revenge upon iron, In fact once

encountered it, it tends to get rusty, faster and faster.
Plinio, Nat., 34, 146
Abstract Metallic materials can find many kinds of applications in the human body:
for example, in orthopaedics, for hip and knee prostheses, for osteosynthesis devices,
in the cardiovascular sector, for endovascular prostheses, cardiac valves, pace-
makers; in stomatological areas and for osteointegrated dental implants. Herein, some
corrosion problems linked to the metallic materials used in the human body are
examined, focusing in particular on orthopaedic materials. Failure mechanisms of
these materials is briefly revised, dealing with fatigue, general and localised corrosion,
fretting. Finally, a brief outline of the surface finishing treatments is presented.

https://doi.org/10.1007/978-3-319-97625-9_25
576 25 Corrosion in the Human Body
25.1 Characteristics of Metals for Orthopaedic Purpose
All materials applied in the human body need to be resistant to degradation and
biocompatible (Fig. 25.1); metals used for orthopaedic prostheses or for
osteosynthesis, beyond to be corrosion resistant, need to have also high mechanical
resistance and fatigue resistance and an adequate modulus of elasticity.
25.1.1 Mechanical Resistance
The cross section area of an osteosynthesis device that fits the femoral head can also
be 10 times smaller than the one of the osseous structure; since the bone mechanical
resistance is of 90–120 MPa, the metal with which the nail is made needs to have a
resistance higher than 1000 MPa. Likewise, to realize a hip prosthesis stem, since
its resistant section is considerably inferior to the bone’s one, it is necessary to use a
material with tensile resistance of at least 600–800 MPa. The request of such high
mechanical characteristics limits the choice of employable metals and excludes the
use of ceramic or polymeric materials. Only some composite materials may be used,
but their clinical employment is still far.
25.1.2 Fatigue Resistance1
The bone capacity of regenerating itself ensures that it is not subject to fatigue
phenomena, even if it is submitted to frequent cyclical loadings. This does not
happen with synthetic materials (metals, polymers). Also people that conduct a
sedentary lifestyle load their weight on each leg from 105 to more than 106 times
per year. Taking also into account the reduced cross sections of the implants, these
conditions can cause fatigue problems. Besides the application of cyclic loads, the
onset of these phenomena depends on implant design and surface finishing con-
ditions. It is particularly favoured by the fact that implants present discontinuities of
various nature introduced for design requirements (abrupt section variations, holes,
etc.), defects introduced in fabrication (inadequate surface finishing) or during
application (defects due to surgical instruments, or to the need to modify the
implant shape in order to adapt it to the patient) or finally arisen during service
(localized forms of corrosion).
1
The term fatigue is commonly used even though, since the phenomenon occurs in an aggressive
environment, it would be more appropriate to say corrosion-fatigue.
25.1 Characteristics of Metals for Orthopaedic Purpose 577
25.1.3 Resistance to Generalized Corrosion
Human body fluids, characterized by the presence of chlorides and rich in oxygen,
are very aggressive. Only some noble metals like gold and others belonging to the
platinum family are immune from corrosion in human body; yet, in the orthopaedic
field these metals cannot be employed due to their poor mechanical characteristics.
For orthopaedic applications, active-passive metals are used, characterized by a low
—but not nil—corrosion rate. A uniform corrosion rate can be hypothesized as high
as 0.03 lg/cm2 day, so the amount of metal ions released by a synthesis tool or by a
prosthesis is less than 0.5 mg/year (Table 25.1), which does not cause significant
problems to the patient, in absence of other types of corrosion.
25.1.4 Resistance to Crevice Corrosion
Crevice corrosion is the most widespread corrosion form for osteosynthesis tools
devices. Activation sites mostly consist of the matching of the screws (that fix the
implant) and their housings, i.e., they are localized where friction is present between
metallic surfaces, which damages the passive film. The presence of crevice cor-
rosion in these areas can increase by even 100 times the quantity of metal ions
released in the tissues (Table 25.1). The analysis of corrosion cases encountered in
removed implants shows that the susceptibility to crevice corrosion is high for
stainless steel, low for cobalt alloys, nil for titanium and its alloys.
25.1.5 Resistance to Fretting Corrosion
The conditions existing in contact areas between two metal surfaces, in particular in
the conical coupling between femoral head and stem, and under the heads of screws
that fix ostheosythesis tools, are the cause of fretting corrosion. In these areas the
contact surfaces are subjected to continuous relative movements of very small slip
(even 10−2 lm).
Table 25.1 Metal ions release in the human body from orthopaedic implants
AISI 316L screw/plate Ti6Al4V hip prosthesis
Ion release after 1 year in passive 500 lg Ion release after 1 year in 400 lg
conditions passive conditions
Ion release in 1 year in presence of 5 50 mg Ion release in conditions of 40 mg
triggers (2 mm2 each) of crevice fretting corrosion
corrosion (1 cm2 0.1 mm)
In the case of stainless steel, particularly susceptible to crevice corrosion, friction

intensifies this phenomenon, as it causes a continuous mechanical damage to the
protective film. In cobalt alloys friction makes crevice corrosion possible.
Considering titanium and its alloys, fretting corrosion is the main cause of degra-
dation and the main limit of these materials, also because cracking due to fatigue or
simply brittle cracking are often triggered in the corroded areas. Table 25.1 also
shows how fretting corrosion can determine an increase by 100 times in the amount
of metallic ions released from a hip prosthesis in Ti6Al4V.
25.1.6 Corrosion for Galvanic Coupling
Currently, it is rare to use implants of different nobility that may cause galvanic
corrosion. Anyways, not all couplings turn out to be dangerous. For example, it is
dangerous to couple titanium and cobalt alloys with stainless steel, conversely the
combination of titanium and cobalt alloys is safe.
25.1.7 Biocompatibility
All of the metals employed in the field of orthopaedics undergo corrosion to some
extent, therefore releasing ions in the tissues around the implant. Some of these ions
are eliminated by the organism through physiological mechanisms (iron for
example), others (above all chromium, nickel and cobalt) tend to concentrate in
specific organs (liver, kidney, spleen). It is therefore mandatory that ions released
are tolerated by the organism, without giving problems of local irritation, allergic
reaction, carcinogenicity, mutagenicity. If this is verified, materials are called
biocompatible. Biocompatibilty can be defined as the characteristic of a material to
be well accepted in the human body; the degree of biocompatibility is measured by
the entity of the provoked reactions.
For each metallic ion there exists a limit of tolerance. The presence of various
elements can lead to a synergic action. For example, let’s consider nickel, an element
often present in alloys used in human body. The release of its ions in the tissues that
surround the implant can determine local irritations and systemic effects. The most
widespread reaction is allergy, which affects a relevant number of patients, espe-
cially women. In fact, about 30% of women report phenomena of cutaneous allergy
just by having a simple contact with objects containing nickel (costume jewelry,
watch cases, glasses) against the 3% of men. A study on cutaneous sensitivity to
various metals has been carried out on patients that had reported nickel allergy:
results are reported in Table 25.2. Data demonstrate that no patient shows allergy by
25.1 Characteristics of Metals for Orthopaedic Purpose 579
touching stainless steel AISI 316, which shows a low corrosion rate in synthetic
sweat (<1 lA/cm2), while practically all of them do if in contact with materials
coated with nickel, which presents a high corrosion rate (>1 mA/cm2).2
25.2 Classes of Metals Employed in Orthopaedics
As a matter of fact, only few metals have adequate characteristics in order to be

employed in orthopaedics, among them some kinds of austenitic stainless steels,
some cobalt- chromium-molybdenum alloys and some titanium alloys.
25.2.1 Austenitic Stainless Steels
The majority of metallic components for temporary applications (osteosynthesis

devices) are made of these alloys, as well as a little part of permanent implants
(prostheses). The main advantages are: low cost, good mechanical properties if
hardened, ease of production by plastic deformation, ease of shaping by machining.
The main defects are the presence of nickel and the susceptibility to crevice cor-
rosion, in particular at low percentages of molybdenum and nitrogen. In the past,
various types of austenitic stainless steels were employed; currently, the ISO
standard 5832-1 allows the use of three classes of steel (Table 25.2).
The most traditional steel is the ISO 5832-1D, which corresponds to AISI 316L
steel with higher molybdenum, which contains chromium (17–19%), nickel (13–
15%), molybdenum (2.25–3.5%) and nitrogen (<0.10%) and it is characterized by
low levels of sulphur, phosphorus, and inclusions. It is the most economic material
indicated by the standard and can be easily processed by plastic deformation and
chip removal. Mechanical characteristics, not particularly high at the solubilized
state, (tensile strength equal to 690 MPa, yield strength equal to 190 MPa) can be
increased by means of cold working (reaching 1100 and 690 MPa, respectively).
Unfortunately, this steel is sensitive to crevice corrosion. It is the most employed
material for ostheosythesis devices, as they are generally removed once they have
fulfilled the task.
ISO 5832-1E steel contains chromium (17–19%), nickel (14–16%), molybde-
num (2.35–4.2%) and nitrogen (0.1–0.2%); compared to the traditional steel ISO
2
The EU directive 94727, 1994 imposes that metal parts aimed to skin contact must not release
more than 2 mg/cm2 week of nickel. The fulfillment of this directive has brought to a sensitive
reduction of dermatitis due to nickel contact. Unfortunately, European Bank technicians did not
take this into account if what Nature (2002) writes is true, namely, that 1 and 2 euro coins have a
nickel release rate 230–320 times higher than the limit level, for this reason they induce allergic
reactions in individuals sensitive to this metal.
Table 25.2 Allergic reactions due to prolonged skin contact on patients that had previously
witnessed nickel allergy
Steel Passivation Ni released in artificial sweat (lg/ Patients with allergic
current cm2 week) reaction (%)
AISI 316L <1 lA/cm2 <0.05 0
AISI 303 >1 lA/cm2 0.5 14
Ni coating >1 mA/cm2 >70 96
5832-1D it is much more resistant to crevice corrosion—even though it is not

immune—and has higher mechanical characteristics.
ISO 5832-9 steel contains chromium (19.5–22%), nickel (9–11%), molybdenum
(2–3%), manganese (2–4.25%) and nitrogen (0.25–0.5%). The high level of nitrogen
ensures a better resistance to crevice corrosion, especially if molybdenum content is
near 3%, and better mechanical characteristics both in the solubilized state (tensile
strength 740 MPa, yield strength 430 MPa) and after cold working (for cold worked
bars tensile strength can be as high as 1800 MPa). Such better characteristics come
with the drawbacks of a higher cost and a more difficult processing.
During the past years, stainless steels with high nitrogen and manganese and
practically lacking nickel (even lower than 0.1%) have been introduced, with
mechanical resistance and resistance to localized corrosion comparable to the steel
ISO 5832-9 ones.
25.2.2 Cobalt Alloys
Cobalt alloys used in orthopaedics may be of two types: cast alloys and wrought
alloys. Cast alloys (ISO 5832-4) contain, apart from cobalt, chromium (26.5–30%)
and molybdenum (4.5–7%). They exhibit a tensile strength of 655 MPa and yield
strength equal to 450 MPa. The main advantages of cobalt cast alloys are: high
mechanical properties, excellent resistance to corrosion, in particular to fretting
corrosion. The main disadvantages are: high cost, low fatigue resistance, impos-
sibility of both plastic deformation and machining.
Wrought alloys (ISO 5832-5, 6, 7, 8) are expensive, more than titanium and
characterized by the presence of nickel. The advantages of these alloys are:
excellent mechanical characteristics, good resistance to corrosion. The disadvan-
tages are: high cost, complex production technology and presence of nickel.
Wrought cobalt alloy ISO 5832-12, which has been developed more recently,
contains chromium (28%) and molybdenum (6%), and other elements (Ni, Mn, Si
lower than 1%). After cold working it reaches high values of mechanical resistance
(yield strength 830 MPa) with a good toughness (12% elongation). This alloy is
currently the most employed for the production of orthopaedic tools by plastic
deformation, in particular for stems and articular heads.
25.2 Classes of Metals Employed in Orthopaedics 581
25.2.3 Titanium and Titanium Alloys
Titanium is considered the most biocompatible metal. Pure titanium has poor
mechanical properties, therefore, for some applications it is replaced by titanium
alloys. The most commonly used titanium alloy is Ti6Al4V (ISO 5832-3), with a
tensile strength of 860 MPa in the annealed state, which can be increased with
quenching and aging treatments. In order to replace vanadium, which has arisen
many doubts on its biocompatibility, Ti7Al8Nb (ISO 5832-11) and beta alloy
Ti15Mo5Zr3Al have been introduced. These alloys have mechanical characteristics
and corrosion resistance similar to Ti6Al4V, but at present they are less widespread
and more expensive.
The sensitivity to fretting corrosion is the main limit of titanium and its alloys,
especially because corrosion sites often trigger fatigue failures or simply brittle
fractures.
The main advantages of titanium are: good biocompatibility, especially since it
does not obstacle osseointegration, good workability by machining, possibility of
hot plastic deformation. Disadvantages are: low mechanical properties, sensitivity
to fretting corrosion, difficulty of cold plastic deformation. Titanium alloys are more
expensive, less biocompatible, but with better mechanical properties compared to
pure titanium.
The near-equiatomic Ni–Ti alloy (55% by weight of nickel and 45% by weight
of titanium) is particularly interesting for bioengineering applications: it is not
commonly employed in orthopaedics yet, but it is currently being studied for its
super-elasticity and shape memory properties. This alloy has been used in the
orthodontic industry for a few decades, being responsible for the main improve-
ments in the field, and is becoming an important material for endovascular stents
(see Box). However, there is still concern (although not shared by everyone) about
its biocompatibility, due to its high nickel content.
25.3 Surface Finishing Treatments
Before being implanted, certain materials may require surface finishing treatments
such as barrel finishing, electro-polishing, passivation and anodising or other
specific processes.
25.3.1 Barrel Finishing
Tumbling, or barrelling, is a mechanical finishing operation consisting in inserting

the metal components in vibrant or rotating machines, known as barrels, along with
inert materials of specific shape. It eliminates surface defects caused on metal
components by previous operations (turning burrs, small pressing defects, sharp

edges) and is used to obtain very fine surface finishing (for example, such as that
necessary in polishing hip prostheses metal heads). This process can occur in
different stages by using inert elements of progressively decreasing size and it can
allow to obtain surface finishing comparable to those obtained by hand polishing
with diamond polishing pads.
25.3.2 Electropolishing
It is an electrochemical process that allows to obtain a fine surface finishing of

metal components (polishing). The component is immersed in an appropriate bath
and acts as the anode. Process effectiveness and speed depend on type of bath,
temperature, time, current density and metal alloy that has to be treated. Unlike the
other mechanical finishing processes, this technique does not cause deformations,
inclusions or contaminations on the treated surface. It is commonly used for
stainless steel finishing, but it can be used for any metallic biomaterial. After the
electropolishing process, the metallic components are generally passivated.
25.3.3 Passivation
It is possible to apply to metal components some treatments that increase the

thickness of the protective passive film. These treatments can be carried out by
immersion and permanence of the metal components in specific baths, for instance
containing concentrated nitric acid.
25.3.4 Titanium Anodising
In order to improve corrosion resistance, titanium and titanium alloys can be oxi-
dised through electrochemical methods. As the applied potential increases, thicker
titanium dioxide films can be obtained.
Endovascular Prostheses
All metals which are to be implanted into the human body must be corrosion
resistant and biocompatible. Depending on the type of application, other
characteristics are required. For example, endovascular prostheses—stent—
must be easy to extend, radiopaque, rigid, fatigue and compression resistant
and possibly not too expensive, therefore sometimes corrosion resistance is
25.3 Surface Finishing Treatments 583
not considered as first requirement. To learn more, let’s interview a technician

working in this field: “Dear Paolo, can you give me a few brief information
about stents used today, the materials employed and the specific problems
that this application causes to them?”
Answer: “Dear dad, this is not a simple matter. In coronary arteries
(where 75% of stents are used) stents are implanted through angioplasty
balloon inflation. This type of stent (Fig. 25.2) has a greater radial force,
lower risks of misplacement and can be seen with fluoroscopy. Unfortunately,
it is neither very elastic nor flexible (this also depends on stent design). It is
good for vessels such as coronary or renal arteries, which are positioned in
depth and do not risk external compression or deformation. The most used
material for this type of stent is stainless steel, typically AISI 316L, even if
recently, more corrosion-resistant—but especially more radiopaque and
more rigid—cobalt alloys have been introduced. Cr–Co stents allow to
maintain the same level of radial resistance, flexibility and radiopacity, with
smaller mesh thickness, with subsequent smaller risks of restenosis (a partial
or total narrowing of a blood vessel).
Stents of larger diameter (5–10 mm vs. 2–4 mm of the coronary arteries),
both self-expanding and balloon-expandable stents, are used in non-coronary
arteries (e.g., iliac, femoral, renal, carotid arteries). Balloon-expandable
stents are used to treat deep arteries (ex. renal, iliac arteries) and are similar
to coronary stents, while self-expanding stents, which do not need the balloon
technique to expand—even if in more calcified artheriosclerotic plaques they
may require a successive post-dilation of this type—are very flexible and
elastically deformable. The frequent artery movements, especially in legs, can
cause fatigue cracks with hemodynamic and clinical consequences in some
stent models available commercially.
Fig. 25.2 Self-expanding stent (diameter 3 mm)

Self-expanding stents are made of a nickel-titanium alloy. Corrosion and

fatigue resistance improves if the electro-polishing surface finishing is
properly performed. Other alloys have been discarded because they make the
stent difficult to expand, non-radiopaque, non-biocompatible, rigid or too
expensive to produce.
Drug-eluting stents able to inhibit cell proliferation, which leads to
restenosis, are now implanted. In the future, we aim to develop bio-ab-
sorbable stents: magnesium prototypes are currently undergoing a clinical
evaluation (God bless corrosion in this case!), even though drug delivery
systems based on polylactic acid are the most promising. The first experi-
ments on men are now being carried out after a number of preclinical
studies”.
Two Memories
I have two precise memories from my job within the field of orthopaedics.
The first one is of the early 70s, when I observed stress corrosion cracking
in prostheses and osteosynthesis plaques coming from a clinic and two
hospitals in Lombardy, Italy. They were nominally AISI 316 stainless steel
implants, about thirty of which were removed from patients for various
reasons in the previous ten years after different in vivo periods, spanning from
six months to three years. Some of them suffered very harsh corrosion (one
example is reported in Fig. 25.3). Chemical analyses showed that different
components, in particular some screws, contained insufficient molybdenum
levels to be classified as AISI 316. Yet, at that time the essential role of this
element in increasing corrosion resistance in chloride-containing environ-
ments, such as human body, was already known. Today, international stan-
dards provide the chemical composition, structure, surface and mechanical
characteristics of implanted alloys, and most importantly require strict con-
trols. Consequently, a patient who undergoes total hip replacement or has a
plaque implanted can be sure (at least, almost sure) not to run the same risk as
his forty-years-ago fellows, namely, the risk of corrosion.
The second memory dates back to the 1978 spring-summer season that I
spent in Connecticut State University as a guest of Professor N.D. Green.
During those years, among other things, the professor was responsible for
corrosion problems within human body and he collaborated with his col-
leagues in biology who were investigating the potential side effects of cor-
rosion of stainless steel implants. In fact, there was concern, which ultimately
turned out to be unfounded, about a potential carcinogenicity of nickel
released during corrosion along with iron, chromium and molybdenum.
I spent some hours at the Department of Biology where some researchers
25.3 Surface Finishing Treatments 585
Fig. 25.3 Crevice cracking in osteosynthesis device for femoral fractures, occurring at the
screw head-plaque coupling
were working on this topic. In the previous months, two plates of AISI 316
were implanted into the superior neck region of dozens of test animals; the
plates were welded to create a crevice, together with an AISI 304 plate to
accelerate the corrosion attack (no corrosion was starting on a single plate
and, therefore, in the absence of crevice). By placing a small electrode near
the plates, they measured its potential for weeks and, once the corrosion was
triggered, they began to perform periodic in vivo measurements of corrosion
rate using the linear polarisation technique. That was what they were doing in
that moment. After a few months, they would have sacrificed the test animals
to determine the concentration of chromium, nickel and molybdenum in their
lung, pancreas and spleen and to provide cancer evidence, which actually was
never found. I participated in some measurements of corrosion rate. They
required time, because the animal was subjected to local anaesthesia, and they
were boring and repetitive, so they used to work with the radio on. I still
remember the newscast announcing the assassination of Aldo Moro, an
eminent Italian politician, during one of those measurements.
Pietro Pedeferri’s memories
• ASTM A967, Standard specification for chemical passivation treatments for

stainless steel parts, ASTM International, West Conshohocken, PA.
• ASTM F-86, Standard practice for surface preparation and marking of metallic
surgical implants, ASTM International, West Conshohocken, PA.
• ASTM F-2129, Standard test method for conducting cyclic potentiodynamic
polarization measurements to determine the corrosion susceptibility of small
implant devices, ASTM International, West Conshohocken, PA.
• ISO 5832, Implants for Surgery—Metallic Materials, International Standard
25:1 Discuss the galvanic coupling between stainless steels and cobalt-based
alloys used for prostheses. Consider the influence on crevice corrosion.
25:2 In vivo studies on the use of NiTi orthodontic devices have reported several
cases of severe inflammatory reactions resulting in contact dermatitis. Which
degradation mechanism would you envision? How can you increase the
service life of these materials?
25:3 Due to issues related to possible flammatory responses, the maximum ion
release allowed from the acetabular cup of a hip prosthesis with surface area
80 cm2 is 0.6 mg/year. Calculate the maximum corrosion rate allowed for a
stainless steel AISI 316L, in the simplified hypothesis that all elements are
released with the same rate (use an average molecular mass of 56 g/mol).
25:4 The same alloy of the previous exercise is used to manufacture bone plate
and screws of an osteosynthesis device. Crevice corrosion onsets. To which
extent does corrosion rate change? Which influence does it have on the
implant service life? First try to hypothesize reasonable values based on the
new corrosion mechanism. You can then refer to Table 25.1 to have reliable
values of crevice corrosion rate.
25:5 The EU directive 94727, 1994 imposes that metal parts aimed to skin contact
must not release more than 2 lg/cm2 week of nickel. Calculate the related
maximum corrosion rate of an AISI 303 stainless steel, with Ni content 9%,
in the simplified hypothesis that all alloy elements are released with the same
rate (i.e., Ni release accounts for 9% of the overall corrosion current).
25:6 A 65-year old man undergoes dental surgery. Which implant material would
you select to meet an expected service life of 20 years?
25:7 Which is the role of surface treatments in extending a metal implant service
life?
25:8 Which are the advantages of using cobalt-based alloys or titanium alloys
with respect to austenitic stainless steels?
Bibliography
Cigada A, Chiesa R, Pinasco RM, Hisatsune K (2002) Metallic materials. In: Barbucci R
(ed) Integrated biomaterials science. Kluwer Academic Press, Plenum Publisher, New York,
USA
Hansen DC (2008) Metal corrosion in the human body: the ultimate bio-corrosion scenario. The
Electrochem Soc Interface 17(2):31–34
Chapter 26
High Temperature Corrosion
Iron, made glowing by the action of fire, gets corrupted.

Pliny, Hist. Nat., 34
Abstract A metal in contact with a hot gas, typically at temperatures above 400 °C,
in absence of liquid water phase, can suffer corrosion, also called hot corrosion.
While aqueous (wet) corrosion processes are of electrochemical nature, hot corro-
sion is a chemical process, i.e., governed by chemical process kinetics in gas phase.
Nevertheless, the oxide layer that forms at the metal surface is influenced by ionic
diffusion and electronic conductivity within the oxide, as typical of an electro-
chemical mechanism. Corrosion attacks include: thinning due to the formation of
non-protective scale, corrosion products and metal evaporation, metal degradation
by molten salts, erosion-corrosion assisted by entrained solid particles, localized
attack at grain boundaries, embrittlement. In this Chapter, the properties of oxides, as
morphology, conductivity, protectiveness are described, together with the oxidation
behaviour of metals and alloys; other processes (sulphidation, carburisation) and
different environments, like steam and combustion gases, are briefly outlined.
Fig. 26.1 Case study at the PoliLaPP corrosion Museum of Politecnico di Milano

https://doi.org/10.1007/978-3-319-97625-9_26
590 26 High Temperature Corrosion
26.1 Corrosive Gases
Hot gas, typically from combustion and chemical processes, contains oxygen,
nitrogen and water vapour, plus other gases, for example: H2, CO, CO2, H2S, SO2,
SO3, NH3, S, HCl, in variable concentrations, giving rise to specific alteration
processes called carburization, sulphidation, chlorination and nitriding (Fig. 26.1).
Moreover, in particular when sulphur, sodium and vanadium are present, salts may
form, which at the operating temperatures can melt. These conditions are
encountered in many industrial applications, petrochemical, nuclear and metallur-
gical, as in examples shown in Table 26.1.
26.2 Thermodynamics and Kinetics
Metals, except gold, oxidize spontaneously when exposed to oxygen because the
standard energy variation, ΔG0, is negative. ΔG0 varies with temperature as follows
(activities of metal and relevant oxide are by definition unitary):
Table 26.1 Examples of hot corrosion in industrial plants

Temperatures Application Types of hot corrosion
1100 °C Ethylene-pyrolysis furnaces Carburization, oxidation
Gas turbines Oxidation, sulphidation, sulphate/
chloride assisted corrosion,
ash-related corrosion
1000 °C Reformer catalyst tubes for Oxidation, carburization
production of ammonia, methanol,
oxo-alcohol, etc.
Reformer catalyst tubes for Oxidation, combustion induced
hydrogen production corrosion
950 °C Reactor and catalyst support grid for Nitriding/oxidation
nitric acid production
Superheater supports in oil fired Fuel ash corrosion and oxidation
refinery boilers
700–850 °C Furnace tubes in carbon disulphide H2S sulphidation, carburization
production
Heater tubes in hydrodealkylation H2S/H2 corrosion
550–650 °C EDC cracker tubes in vinyl chloride Halide gas corrosion
monomer production
Convertors, ammonia plant, reactors Nitriding, hydrogen attack
for hydrocracking H2S/H2 corrosion
450–550 Gas combustion, boilers Oxidation
26.2 Thermodynamics and Kinetics 591

1
DG ¼ RT ln
0
ð26:1Þ
pO2
The plot of ΔG0 as a function of T, which is a set of straight lines, is called

Ellingham1 diagram.
From a thermodynamic point of view, hot corrosion cannot be avoided, but
rather slowed down by ensuring the formation of a protective scale, which should
satisfy these following general requirements:
• High thermodynamic stability
• High melting temperature
• Low growth rate
• Good adhesion to the metal surface
• Good healing properties when damaged or cracked
• Thermal expansion coefficient close to the one of metal
• Good erosion resistance.
Among corrosion products that may form, only oxides satisfy these requirements,
specifically: Al2O3, SiO2 and Cr2O3. This suggests that the metal, at least at the
substrate surface, must contain high enough quantities of one of these elements.
26.3 Scales
The oxidation resistance is therefore necessarily linked to the formation of an oxide

scale, its covering power and its adherence to the substrate, therefore preventing or
slowing down further oxidation. To predict the protection properties of the oxide,
the Pilling–Bedworth Ratio (PBR) is used. This index is the ratio between volumes
of oxide and oxidized metal, respectively. An index lower than one indicates that
the oxide is not protective (i.e., oxide volume is not sufficient to cover the metal
surface); conversely, if the index is much greater than one (i.e., higher than 1.8) and
the oxide reaches high thickness, its volume is too big, then giving rise to
mechanical stresses within its layer, which lead to the oxide rupture. In practice,
compact and adherent oxides can form only if their PBR is about 1.5. Table 26.2
shows the PBR for most common metals.
1
Harold Johann Thomas Ellingham (1897–1975) was a British physical chemist and is best known
for the diagrams named after him that plot the change in standard free energy with respect to
temperature for reactions like the formation of oxides, sulphides and chlorides of various elements.
Table 26.2 Pilling– Oxide PBR Oxide PBR

Bedworth ratio for some
metal oxides CaO 0.6 MnO 1.8
BaO 0.7 TiO2 1.9
MgO 0.8 CoO; Cr2O3 2.0a
CdO; CeO2 1.2 Fe3O4; Fe2O3; SiO2 2.1a
Al2O3 1.3 Ta2O5 2.3
Pb3O4 1.4 Nb2O5 2.7
NiO 1.5 V2O5 3.2
ZnO; BeO; PdO; ZrO2 1.6 MoO3 3.4
FeO; CuO 1.7 WO3 3.4
a
The PBRs of Cr2O3 and SiO2 are higher than 2, which would
indicate a non-protective scale; yet, these oxides are so protective
that the actual quantity of oxide forming is very limited, which
hinders oxide cracking and spalling due to the accumulation of
large volume oxide
26.3.1 Non Protective Oxides
When a metal oxidizes and forms an oxide with Pilling–Bedworth Ratio lower than
one, the metal is continuously exposed to hot gas, then oxidation proceeds at
constant rate; the metal thickness loss, x, is given by:
x ¼ C1 t ð26:2Þ
where t is time, and C1 is a constant of the metal. Oxide thickness to time rela-
tionship is linear (Fig. 26.2).
An example of this behaviour is Mg. Also Mo follows the same kinetics
although for a different cause, which is because its oxide, MoO3, is volatile (melting
temperature 795 °C and boiling temperature 1100 °C).
Fig. 26.2 Kinetic trend of

mass change of samples
r
ea
Lin
subject to hot corrosion

Mass increase
Parabolic
Logarithmic
Time
26.3 Scales 593
26.3.2 Protective Oxides
When the oxide is protective, i.e., Pilling–Bedworth Ratio exceeds one, the cor-
rosion rate decreases with time by following two trends: parabolic and logarithmic
(Fig. 26.2):
pffi
x ¼ C2 t ð26:3Þ
x ¼ C3 ln ðC4 t þ 1Þ ð26:4Þ
where t is time, and C2, C3, and C4 are constants related to the metal.
Some common metals, such as aluminium, beryllium, zinc and chromium, show
a logarithmic kinetics of growth. The reason for this deviation from the parabolic
behaviour is complex: in the aluminium and beryllium is the low mobility of
electrons participating in the oxidation process, while for zinc and chromium it is
the slower diffusion rate of ions. Aluminium and chromium oxides have a crys-
talline structure compliant with that of the underlying metal and therefore are
adherent and protective.
A parabolic dependence is achieved when diffusion of oxygen ions, O2−, is slow
and determines process rate. In these cases, the growth rate is proportional to the ion
flux, Jion, given by Fick’s law, hence giving a parabolic dependence. Since the
diffusion coefficient has an Arrhenius type dependence with temperature, oxide
growth rate increases with temperature accordingly.
The parabolic oxidation rate constants, C2, for some metals at a temperature of
1000 °C are reported in Table 26.3. As an example, the thickness loss after 10 year
exposure time for Fe, Cr and Al is 18 mm, 180 lm and 72 lm, respectively. As
temperature changes, oxidation rate changes through the variation of the constant,
C2, with temperature. As mentioned, the relationship is of Arrhenius type, that is:
C2 ¼ C02 eRT
Q
ð26:5Þ
where C02 is constant at a reference temperature. By plotting constant C2 versus

temperature, Fig. 26.3 is obtained.
Table 26.3 Parabolic oxidation rate constants, C2, for some metals (1000 °C, pO2 = 1 bar)
Metal C2 (g2/m4s) C2 (m/s½) Metal C2 (g2/m4s) C2 (m/s½)
−3
Fe 50 1 Cr 5 10 0.01
Co 2 0.15 Si 10−3 0.01
Ti 1 0.2 Al 10−4 0.004
Ni 2 10−2 0.02 Ta, Nb 2 10−4 (g/m2s) (linear)
Temperature (K)
1400 1350 1300 1250
log k (g2 cm-4 s-1) -6 FeO
-8 CoO
-10 NiO
Cr2O3
-12
SiO2
α-Al2O3
-14
7.0 7.2 7.4 7.6 7.8 8.0 8.2
1/T 104 (K-1)
Fig. 26.3 Variation of parabolic oxide growth rate constant, C2, with temperature for some oxides
26.4 Wagner Theory
In 1933 C. Wagner2 proposed an electrochemical mechanism for oxide growth

based on:
• An anodic reaction that takes place at the metal-oxide interface that produces
metal ions and electrons
• A cathodic reaction of oxygen reduction into O2−, by consuming electrons. This
reaction can take place at the oxide-atmosphere interface or within the growing
oxide
• A transport of ions inside the oxide film (positive ions or anionic vacancies from
metal toward gas atmosphere and in opposite direction negative ions or cationic
vacancies)
• A transport of electrons inside the oxide film.
Figure 26.4 compares the electrochemical mechanism for aqueous and hot
corrosion assuming the transport of ions and electrons, only. Then, the metal works
as anode, the oxide provides both electronic and ionic conductivity, the cathode is
the oxide surface in contact with the atmosphere.
2
Carl Wagner (1901–1977) is also remembered as the “father of solid-state chemistry” for his
pioneering work in a variety of fields including tarnishing reactions, catalysis, photochemistry, fuel
cells, semiconductors, and defect chemistry.
26.4 Wagner Theory 595
(a) (b)
Metal Oxide
e-
e-
O2 O2
Mz+ O2-
Mz+ O2- Mz+ OH-
Mz+ OH-
e-
Metal
Fig. 26.4 Corrosion mechanism comparison: a hot corrosion; b aqueous corrosion (from
Fontana)
As in aqueous corrosion, the slowest of the four processes determines the cor-
rosion rate. Since in hot corrosion overvoltage of anodic and cathodic processes are
negligible, because of the high temperature, the kinetically controlling process is
electronic or ionic transport within the oxide.
A laboratory test that proves the electrochemical mechanism of hot corrosion is
the growth of silver bromide on a silver strip exposed to a bromine atmosphere at
high temperature: this case study involves a salt instead of an oxide, but the
mechanism is the same. Silver bromide is a solid electrolyte with ionic conduction
by Ag+ ions but not an electronic conductor, therefore the bromide film does not
grow. However, by placing a platinum grid on the film surface, electrically con-
nected with the silver strip, electrons can circulate from silver to platinum and
corrosion can proceed with formation of AgBr (Fig. 26.5).
This case study shows that both ionic and electronic conductivity is necessary
for oxide film growth: one of the two is not sufficient condition for metal oxidation.
Silver bromide is a good ionic but not electronic conductor; conversely, magnetite
is a good electronic but not ionic conductor, therefore both form protective films.
An oxide film can be considered protective if, provided it is uniform and compact
(PBR higher than one), it is either ionically or electronically non-conductive: this is a
sufficient condition to ensure low oxidation rate. Therefore, oxide film resistivity is a
further index for protection degree evaluation. The most protective oxides are those
of aluminium, beryllium, zirconium and silicon, which are precisely the most
resistive oxides. Also calcium and magnesium oxides have high resistivity.
26.4.1 Oxide Conductivity and Lattice Defects
To better understand how oxides grow, it is necessary to analyse the mechanism of

ionic and electronic conduction.
Electrons Electrons
Silver AgBr
Ag Br2 atmosphere
Ag+
Pt grid
Fig. 26.5 Corrosive system consisting of silver foil-silver bromide-platinum in an atmosphere of

high temperature bromine (from Bianchi-Mazza)
Table 26.4 Oxide types of several metals

Oxide type Oxides
Metal excess BeO, MgO, CaO, SrO, BaO, CeO2, ThO2, UO3, TiO2, ZrO2, V2O5,
(n-type) Ta2O5, MoO3, WO3, Fe2O3, ZnO, CdO, Al2O3, SiO2, SnO2, PbO2
Metal deficient Cr2O3, UO2, FeO, NiO, CoO, Co3O4, PdO, Cu2O, Ag2O
(p-type)
Perfect ionic crystals are not conductive. In the presence of lattice defects as
interstitial ions and ionic vacancies, always present, ionic crystals become con-
ductive through either movement of electrons and electron vacancies (electronic
conductivity) or movement of ions and ionic vacancies (ionic conductivity).
Oxides are not fully stoichiometric, i.e. oxygen and metal in the lattice do not
have exact ratio as in their chemical composition. For example, in copper oxide
(Cu2O) the number of Cu+ ions is not exactly twice the number of O2− ions, instead
it is slightly lower. The opposite occurs for zinc oxide (ZnO) where the number of
Zn2+ cations slightly exceeds that of O2− ions.
For electroneutrality requisites, an excess of electrons (e−○)3or electron
vacancies (e−□) is present to counterbalance stoichiometry defects. When con-
ductivity is due to electron vacancies (i.e., formally as positive charge movement)
oxides are semiconductors of p-type (Cu2O, NiO, FeO, CoO, Ag2O, MnO and SnO
are of this type); when electrons are involved, oxides are semiconductors of n-type
(Table 26.4). The latter can be created also by oxygen ion vacancies as in zirconia,
ZrO2. Other n-type oxides are: CdO, Al2O3, V2O5, TiO2.
Figure 26.6 shows the oxide growth mechanism for copper, zinc and zirconium,
respectively of p-type (Cu2O) and n-type (ZnO and ZrO2). For copper oxide
3
Symbols (□) and (○) indicate vacancy and interstitial, respectively.
26.4 Wagner Theory 597
(a) (b) (c)

Cu Cu2O O2 Zn ZnO O2 Zr ZrO2 O2
Ii Ii Ii
O2 O2
(Cu+ ) (Zn2+ {) (O2- )
(e- ) (e- {) (e- )
Ie Ie Ie
Metal Oxide Gas Metal Oxide Gas Metal Oxide Gas
2Cu → 2Cu+ + 2e- ½O2 + 2e- → O2- Zn → Zn2+ + 2e- ½O2 + 2e- → O2- Zr → Zr4+ + 4e- O2 + 4e- → 2O2-
Fig. 26.6 Growth mechanism of oxide on copper (p-type oxide), zinc (n-type oxide) and
zirconium (n-type oxide)
growth, charge carriers are electron vacancies, (e−□), moving in the same direction
of current and ionic vacancies, (Cu+□), which move in the opposite direction
(Fig. 26.6a). In case of zinc oxidation, which gives an n-type oxide, carriers are
electrons, (e−○), which move in the opposite direction to current, and interstitial
ions, (Zn2+○), which move in the same direction of the current (Fig. 26.6b).
Finally, for zirconium oxidation, which gives an n-type oxide for oxygen defi-
ciency, carriers are electrons moving in the opposite direction of current and oxygen
vacancies, (O2−□), which move in the same direction (Fig. 26.6c). In summary, the
oxide grows by ion migration from the metal-oxide interface to the oxide surface
and electron movement in opposite direction, or by ionic vacancies migration from
outer to inner oxide surface and electronic vacancies in opposite direction.
26.5 Morphology of Oxide Films
Oxide and metal maintain a good adhesion if the respective crystal lattices fit one
another. When the oxide film is very thin, adherence is good in spite of a high
mismatch between the two lattices because the oxide assumes an amorphous
structure. However, as soon as the oxide grows, the amorphous structure, which has
a high internal energy, tends to crystallize and spalls off if no crystalline rear-
rangement between oxide and metal takes place. Oxidation process proceeds at high
rate following an almost linear trend through parabolic sections, as Fig. 26.7 shows.
Hauffe’s Rules
The oxidation rate is determined by the conduction mechanism which has the
lowest rate within the oxide. The latter can be modified by adding some
impurities in the oxide.
Fig. 26.7 Pseudo-linear

dependence of mass change
against oxidation time
Mass increase
Oxide fracture
Time
With n-type oxides, the presence of an impurity cation with a higher

valence than the oxide reduces either the concentration of oxygen vacancies
(for oxygen deficient, MO1−x), or the concentration of interstitial metal
cations (cation excess, M1+xO), hence reducing the conductivity of the oxide
and then oxidation rates. The opposite happens by adding lower valence
impurity cations.
With p-type oxides, the presence of an impurity cation with a lower
valence than the oxide reduces either the concentration of metal cation
vacancies (for metal cation deficient, M1−xO), or the concentration of inter-
stitial oxide anions (oxygen excess, MO1+x), hence reducing the conductivity
of the oxide and then oxidation rates. Again, the opposite occurs by adding
higher valence impurity cations.
Another cause of oxide spalling is internal stress in the film. Figure 26.8a shows
the case of an oxide that grows by metal ions diffusion: the metal-oxide interface
grows inward while the external oxide surface grows outward. If the involved
surface is flat, no stresses arise, while the opposite occurs with a curved surface
(Fig. 26.8b): as corrosion proceeds, a convex metal surface causes compression
stresses inside the film, hence the film remains adherent, conversely, concave
surface causes tensile stresses which spall off the film.
Figure 26.9a shows the opposite case, when the oxide grows by anions diffu-
sion: the oxide grows at metal-oxide interface: if the PBR is higher than unity (i.e.,
oxide volume is greater than that of metal) and the surface is not flat, convex
surfaces lead to a tensile stress inside the film (new oxide formed pushes the present
layer) and concave surfaces exert a compressive one.
In general, metal oxides are brittle, then resisting compression better than tensile
stress. Furthermore, under compression, internal micro-voids tend to form by
coalescence of vacancies or blisters aroused at metal-oxide interface as shown in
26.5 Morphology of Oxide Films 599
(a) (b) Oxide
Metal Oxide Oxygen Voids
Mz+
Metal
e-
Oxide
Metal Formed
consumed oxide (∆Vox-met)
Oxide
displacement Metal
Fig. 26.8 a Ions moving in the oxide during its growth by cation transport; b stress induced by
the oxide growing on curved surfaces (from Shreir)
Figs. 26.8b and 26.9b, and contribute to reduce stresses. When the metal works at
constant load and at a continuous or cycling high temperature, creep induces a
tensile stress to the oxide if thermal expansion coefficients of metal and oxide are
different. Oxides can withstand these stresses, i.e., ability to deform by allowing
dislocation movement; conversely, there is the need of a high hardness to resist
abrasion due to solid particles in the gas (ash, dust, condensed water drops), low
volatility and high melting temperature.
The corrosion behaviour is influenced by working temperature conditions, i.e.,
constant or cycling. In the former case (i.e., equipment operating at a constant
temperature) an oxide layer easily forms, stable and adherent, assisted by internal
stress rearrangement. In case of equipment subject to frequent thermal cycling,
allotropic transformation of oxides can occur, causing a variation of structure and
volume of oxide, which may be a further cause of the layer spalling, together with
the mismatch between the metal thermal expansion coefficient and that of the
related oxide.
Alloys containing molybdenum, tungsten and vanadium suffer catastrophic
oxidation because oxides that form on them have a low melting temperature,
therefore they can be easily removed due to either gas turbulence or evaporation.
This catastrophic attack tends to localize because where it starts there is a local
increase in temperature, hence enhancing the oxidation process.
(a) (b) Oxide
Metal Oxide Oxygen

Metal
O2-
e-
ΔVox-met
Oxide
Metal
consumed
Oxide
displacement Metal
Voids
Fig. 26.9 a Ions moving in the oxide during its growth by anion transport; b stress induced by the
oxide growing on curved surfaces (from Shreir)
26.6 Oxidation of Metals
The factors influencing the oxidation rate for a metal or alloy are different.
Concerning the metal: chemical composition, impurities, crystal lattice orientation,
surface finishing, geometry and thickness; from the hot gas standpoint: composi-
tion, impurities, pressure, flow rate, temperature and its variations. In the following,
the behaviour of some relevant metals is highlighted.
Nickel. It forms a stable p-type oxide, Ni1−xO, where x is 10−4 at 900 °C at an

oxygen partial pressure of 1 bar. The oxide grows as columnar grains at the
oxide-gas interface by migration of metal ions. The presence of impurities influ-
ences oxide structure, favouring the formation of porous, fine grains at the
metal-oxide interface.
Iron. Iron forms a multi-layered scale consisting of the following three stable
oxides: hematite, Fe2O3, magnetite, Fe3O4 and wüstite, FeO, as shown in
Fig. 26.10. In practice, the following scales form:
• below 570 °C, the sequence of oxides is: Fe/Fe3O4/Fe2O3/O2,
• above 570 °C the sequence becomes: Fe/FeO/Fe3O4/Fe2O3/O2.
Wüstite, FeO, is stable at temperatures above 570 °C only, and because the mo-
bility of Fe2+ within FeO is very high, oxidation rate is very high, too. Moreover,
26.6 Oxidation of Metals 601
Würstite Magnetite Haematite

FeO Fe3O4 Fe2O3
Fe2+
Iron Fe2+ O2- Oxygen
Fe3+
Fig. 26.10 Schematic illustration of iron oxide formation
Fig. 26.11 Phase diagram of

Würstite Magnetite Haematite
the Fe–O system 1200
γ + FeO
Temperature (°C)
FeO
1100 FeO Fe2O3 O2
+ + +
Fe3O4 Fe3O4 Fe2O3
800
α + FeO
600 570°C
α + Fe3O4
22 24 26 28 30
Percentage of oxygen
FeO Fe3O4 Fe2O3
FeO has poor protective properties, so based on that, iron and low alloy steels can
be used at temperatures below 570 °C, only; furthermore, below this temperature
the diffusion of ions, Fe2+, into magnetite is slow, hence resistance to oxidation is
further increased (Fig. 26.11).
Chromium. Chromium forms Cr2O3 oxide (corundum with spinel structure) of p-

type (although at low oxygen pressures it seems that it becomes of n-type). Cr2−xO3
has a value of x = 9 10−5 at 1100 °C and oxygen partial pressure of 1 bar. Since
the oxide is relatively stoichiometric (low concentration of defects) its transport
mechanism is affected by diffusion at grain boundaries. Above 900 °C in an at-
mosphere rich in oxygen, it is oxidized to hexavalent oxide, CrO3, volatile, with
loss of protection properties.
Aluminium. It forms the oxide Al2O3 which is very stable and very protective,
since it is stoichiometric. Some alloys are designed to form a film of Al2O3 that
offers protection up to 1300 °C.
Silicon. As aluminium, it forms an oxide, SiO2, very stable and very protective
because stoichiometric. New alloys are designed to form a layer of SiO2 that offers
protection up to 1200 °C.
Titanium. Titanium oxidation appears complex due to the formation of many stable
oxides (Ti2O, TiO, Ti2O3, Ti3O5, TiO2). At temperatures below 1000 °C and oxygen
partial pressure of 1 bar only TiO2 is formed. At temperatures above 600 °C the
growth kinetics is parabolic and can become pseudo-linear after long exposures. At
high temperature oxygen dissolves in the metal in significant quantities causing the
formation of cracks and exfoliation of the metal.
Molybdenum. The oxidation of molybdenum leads to the formation of volatile

oxides (MoO3 melts at 795 °C). These oxides are not protective and oxidation has a
catastrophic trend.
26.7 Oxidation of Alloys
In case of alloys, the different affinity with oxygen of components determines the
formation of oxides of more reactive metals, as for silicon, aluminium and beryl-
lium, which also produce high resistance oxides; their presence, even in low con-
tent, allows the formation of a protective oxide film.
To highlight the complexity of high temperature corrosion of alloys, let’s con-
sider the simplest case of oxidation of a binary alloy AB, in which A is the solvent
metal and B the solute one.
26.7.1 Oxidation of Only One of Two Metals in Alloy
We take into account two cases: one in which the alloy element (solute) oxidizes
and one in which the solvent oxidizes.
In case the alloy element oxidizes, this can occur internally to the matrix, which
consists of a solid solution of a solute B in a solvent A (it is the case of silicon–silver
alloys, where silica globules, SiO2, are formed, dispersed in non-oxidized silver,
Fig. 26.12a); or it may undergo external oxidation (in case of iron–chromium alloys
in which, when the partial pressure of oxygen is lower than that of iron oxide
dissociation, it forms a film entirely made of Cr2O3, Fig. 26.12b).
In case the solvent metal oxidizes, the film consists of solvent metal oxide, in
which particles of solute element B are dispersed. This is the case of copper–gold,
Au–Cu, or copper–silver, Cu–Ag, alloys (Fig. 26.12c). The metal B may some-
times form a layer at the alloy surface. This is for example the case of the Ni–Pt
alloys, in which oxidation forms nickel oxide supported by a layer of practically
pure platinum (Fig. 26.12d); it is also the case of steels where impurities such as
copper, tin or silver are concentrated on the alloy surface in a layer in direct contact
with the oxide.
26.7 Oxidation of Alloys 603
(a) (b)
Cr2O3
A BO
Ag
B B B
SiO2
BO Ag-Si Alloy Fe-Cr Alloy
(c) (d)
Cu2O AO NiO
AO
Rich area
B in B Pt
Au
Cu-Au Alloy Ni-Pt Alloy
(e) (f)
AO NiO
(Ni,Co)O
(A,B)O
NiCr2O4
(A,B)O
Ni-Co Alloy Ni-Cr Alloy
Fig. 26.12 Schematic illustration of the various possibilities of oxidation of the alloy AB
described in the text: a and b oxidation of the metal solute; c and d oxidation of the metal solvent;
e and f oxidation of the alloy of the two metals
26.7.2 Oxidation of Both Metals in Alloy
It is possible to observe two more cases, depending on whether the oxides that are
formed are insoluble or soluble in one another. The first is that of copper–nickel
(Cu–Ni), copper–zinc (Cu–Zn), copper–aluminium (Cu–Al) and copper–beryllium
(Cu–Be) alloys. The second is the case of nickel–cobalt (Ni–Co) alloys which form
a film consisting of solid solutions between NiO and CoO (Fig. 26.12e).
If the two metals form a double oxide AO-BO, the film is generally biphasic in
that the second oxide is found dispersed in the oxide of the base metal. This is the
case of the oxidation of Ni–Cr alloys (Fig. 26.12f).
26.8 Other Processes
26.8.1 Sulphidation
Similarly to oxygen, sulphur reacts with metals to form a sulphide scale (i.e.,
M + ½ S2 = MS), following the same steps consisting of nucleation and growth of
sulphide through an internal sulphidation reaction. The sulphidation rate is the
result of the following processes:
• Sulphur supply
• Metal cations transport inside the scale
• Electrons transport inside the scale.
Sulphur ions, S2−, do not migrate because of their big size. The controlling
process is the transport of metal cations, since electronic conductance of sulphides
is generally high.
Three important issues differentiate sulphides from oxides: sulphides of the main
elements in alloys for high temperature applications are more stable than corre-
sponding oxides, their volume is greater than the corresponding oxide volume, and
the melting point is lower. Accordingly, sulphidation is more dangerous and more
severe than oxidation.
Table 26.5 reports melting temperatures of eutectics between a metal and its
sulphides for some metals of interest for high temperature applications. If the scale
melts, there is no protection effect.
As shown in Table 26.6, sulphidation rates are five orders of magnitude higher
than oxidation rates. In practice, metals and alloys used for hot corrosion appli-
cations to resist oxidation are not suitable for sulphidation. A possible temperature
range for applications is below 500 °C.
26.8.2 Carburization
Metals exposed to gas mixtures containing CH4 (and other hydrocarbons), CO2,
CO, H2 and H2O at temperatures above 800 °C may suffer carburization and metal
dusting due to the deposition of elemental carbon, which forms by decomposition
reactions, easily catalysed by the metal itself.
Table 26.5 Melting Eutectic Temperature (°C) Eutectic Temperature (°C)

temperature of eutectic
between metals and their Ni–Ni3S2 645 Fe–FeS 985
sulphides Co–Co4S3 880 Cr–CrS 1350
26.8 Other Processes 605
Table 26.6 Constant rate comparison between oxidation and sulphidation (800 °C, pO2 = 1 bar
or pS2 = 1 bar)
Metal Oxidation rate Sulphidation Metal Oxidation rate Sulphidation
(g2/m4 s) rate (g2/m4 s) (g2/m4 s) rate (g2/m4 s)
Ni 6 10−3 200
Co 5 10−2 90 Co–20% 10−5 1
Cr
Cr 10−5 3 Fe–20% Cr 10−5 1
Ni-20% 10−5 1.5 Fe–20% 0.5 10−5 0.5
Cr Cr–5% Al
Carburization is the result of diffusion of carbon into the alloy, taking place
quickly at temperatures exceeding 900 °C. It is common in ethylene furnaces after
ethylene pyrolysis. As carbon diffuses into the alloy, it reacts with alloy elements to
form isolated carbides on the metal surface and internal precipitates. Typically, in
iron–chromium alloys, carbides are (Fe/Cr)7C3 and (Fe/Cr)23C6 and others when Nb
and W are present. Internal carbides decrease the mechanical properties of the alloy.
As often happens, the presence of small quantities of oxygen inhibits carbon
deposition by forming an oxide scale. Because in many process environments,
oxygen quantity is too low to form protective metal oxides (NiO, CoO, Fe2O3 and
also Cr2O3), elements similar to oxygen as Si and Al are added. For instance, the
presence of minimum 2% of silicon helps prevent carburization of AISI 314 (25%
Cr, 20% Ni, 2% Si). Grinding the metal surface, which increases dislocation
density, helps the development of a protective oxide layer of SiO2, and facilitating
the nucleation spreading of the protective SiO2 layer; this treatment has become
common practice for ethylene pyrolysis tubes.
Metal dusting is a severe damage of all iron and nickel-based alloys at tem-
peratures in the range 450–800 °C in atmospheres containing CO2, CO, H2 and
H2O, where carbon disintegrates the metal surface into dust consisting of carbides,
oxides and metal particles. As for carburization, the presence of an oxide scale
helps inhibiting metal dusting; however, oxides form hardly at these relatively low
temperatures. It is suggested that damage starts from local flaws in the oxide scale
and proceeds locally as pit-type appearance, leaving undamaged the surrounding
surface. The mechanism of metal dusting is not fully understood, yet.
26.8.3 Halogenation
In the combustion of waste, hot gases may contain halogens, typically HCl and Cl2.
Reactions between metals and halogens are similar to oxidation and sulphidation,
but products, i.e., metal halides, are volatile, hence cannot develop any type of
protection and kinetics approaches the linear dependence.
26.9 Environments
26.9.1 Oxygen and Air
Oxygen is the most common oxidant, which is present in air and process gas, often
entraining ash. Typical metals operating in air at high temperature are resistors of
electric heaters and machinery for heat treatments. In these conditions, the oxidation
rate is influenced by the presence of pollutants and velocity of gas. About the latter,
high flow rates cause a corrosion rate decrease by locally reducing the temperature
of the metal surface. In oxygen-rich atmospheres a local overheating can lead to
metal self-ignition.
26.9.2 Steam
Corrosion by steam occurs in power plants, either conventional, thermal or nuclear.

The corrosion product is a metal oxide which protects the metal. In the case of low
alloy steels containing small amounts of Cr–Mo–V, the oxide also resists decar-
burization caused by hydrogen produced in the oxidation reaction,
Fe + H2O ! FeO + H2. A negative effect is caused by drops of condensation on
turbine blades due to mechanical shock on the oxide layer.
The most severely stressed point in the steam circuit of a thermal power plant is
in superheater tubes, where, however, most critical problems are on the external
surface exposed to hot combustion gases, which may contain sulphur compounds,
ash and others elements.
26.9.3 Sulphur Compounds
In reducing environments, i.e., without oxygen, sulphur-containing compounds

form sulphides that alter the protection properties of surface layers of exposed
metals. The greatest danger comes from the formation of liquid phases, which—
similarly to the molybdenum oxide—do not allow the formation of a protective
scale. The case of nickel is remarkable, as it forms a eutectic metallic nickel–nickel
sulphide, Ni3S2, with melting temperature 645 °C, which excludes the use of nickel
and nickel-based alloys in sulphur containing environments. In this case, iron–
nickel alloys with high chromium content (about 20%) or cobalt alloys are used
when high mechanical properties are not required.
Elemental sulphur and hydrogen sulphide are the most dangerous substances
with regard to this type of attack. Sulphur oxides are less dangerous since they form
protective oxide layers.
26.9 Environments 607
Sulphur and sodium chloride containing fuels lead to another severe form of
attack due to the formation of sodium sulphate. Sodium chloride may be present in
fuels for several reasons: for example, for the presence of brackish water coming
directly from production wells, or seawater used to wash crude oil tanks, or
introduced with the combustion air in aircraft engines. Sodium sulphate has a
melting temperature in the range between 700 and 850 °C, hence it forms a liquid
phase causing oxide film rupture and rapid metal wastage.
26.9.4 Combustion Gas
Combustion gases of clean fuels are mixtures of CO, CO2, H2O, N2, NOx and O2; in
case of partial combustion, hydrocarbons, carbon and hydrogen may also be present.
The composition, or better the content ratio, determines the aggressiveness of the hot
gas, whether there is an excess of C, CO and hydrocarbons (carburizing condition),
or conversely a high content of H2O, H2 or CO2 (decarburizing condition). In the
first case, carbon can form carbides within the metal matrix with carbon-affinity
elements as chromium, titanium, niobium, causing two detrimental effects: a
mechanical one, i.e., embrittlement due to the formation of precipitates at grain
boundaries, and one on corrosion resistance, because the precipitation of chromium
carbides depletes chromium content, hence reducing oxidation resistance.
There is a particular corrosion form called green rot, which occurs on iron–
chromium–nickel alloys in an environment that is oxidizing for chromium, but not
for iron, when carburizing characteristics change over time; during carburizing
periods, carbon enrichment takes place and successively, during the oxidation phase
(i.e., decarburizing condition), an internal oxidation happens on the chromium
depleted matrix. It follows that internal oxidation spreads through grain boundaries,
then allowing the formation of bulky nickel oxides, which give a typical green
colour to the fracture surface.
Conversely, in decarburizing environments, enriched in CO2, H2O or H2, decar-
burization can occur through the diffusion of carbon to the metal surface followed by
its reaction; carbon depletion in the matrix leads to the loss of mechanical properties.
When the decarburizing species is atomic hydrogen, this diffuses easily within
the metal and reacts with carbon or with carbides according to the reaction:
C + 4H ! CH4. The methane formed is not soluble in the metal, so it accumulates
in micro cavities then increasing internal pressures which deform the metal. On
carbon steel, methane begins to form at temperatures around 300 °C, while for low
alloy steels at 400–500 °C.
The combustion of coal and fuel produces substances that are solid at room
temperature, called ashes; these could be metal oxides formed in the combustion
process or also already present in the fuel. Oxides of aluminium and silicon mixed
with coal and vanadium oxides are examples of ashes. The action of solid ashes is
the abrasion of the oxide layer or, conversely, a screening effect; melted ashes are
more dangerous.
26.9.5 Nitridation
It occurs in ammonia plants when internal nitrides form as a result of nitrogen

diffusion, similarly to carburization. Among those most commonly used in practice,
the most susceptible element to form nitrides is chromium.
26.10 Materials for Use at High Temperatures
To improve resistance to high temperature corrosion, two ways can be envisaged:

alloying and cladding. When using alloying elements, neither mechanical nor
structural characteristics should be jeopardized. Effective alloying elements are
chromium, aluminium and silicon, which form stable and adherent oxides on the
metal surface. When increasing chromium content in iron and iron–nickel alloys to
improve the resistance to oxidation and sulphidation, there is the risk of formation
of a brittle phase. Accordingly, the composition of alloys for high temperature is
always a compromise between mechanical and corrosion resistance requirements,
where one of the two will prevail according to the need of application.
In the following, iron alloys are considered, only. Carbon steel resists oxidation
up to 570 °C regardless the addition of small amounts of alloy elements (Cr, Mo, V)
for improving mechanical properties through heat treatments. To increase the tem-
perature limit, higher contents of chromium and silicon must be added, as sum-
marized in Table 26.7, with focus on alloys used in refineries.
Among stainless steels, the best behaviour is given by cast austenitic ones.
Corrosion resistance and structural stability increase with both chromium and nickel
content; AISI 309 and 310 steels show the best performance among semi-finished
wrought and can withstand significant stresses at temperatures up to 950 °C, for
example in hydrocarbons pyrolysis plants. The current trend is the use of cast alloys
Table 26.7 Scaling Metals Temperature (°C)

temperature of steels used for
high temperature applications Carbon steel (0.1% C) 570
in refineries 5 Cr–0.5 Mo 620
7 Cr–0.5 Mo 650
9 Cr–1.0 Mo 680
AISI 410 (12 Cr) 760
AISI 304, 321, 347 (18 Cr–8 Ni) 900
AISI 316 (18 Cr–10 Ni–3 Mo) 900
AISI 446 (27 Cr) 1030
AISI 309 (22 Cr–20 Ni) 1100
AISI 310 (25 Cr–20 Ni) 1150
Alloy 218 (17 Cr–8 Mn–8.5 Ni–4 Si) 980
26.10 Materials for Use at High Temperatures 609
with higher carbon content for better mechanical characteristics and high silicon
content (up to 2.5%) to improve carburization resistance.
The application limit of these alloys is the mechanical resistance, which becomes
unacceptable at approximately 950 °C, while hot corrosion resistance is extended to
temperatures as high as 1100–1150 °C due to high content of alloying elements.
Above 900 °C, also nickel–cobalt-iron superalloys are used, often with addition of
aluminium (about 1.5%) or chromium to improve the resistance to cyclic oxidation
or carbides formation.
26:1 Discuss the different oxidation kinetics of metals in hot environment: which
characteristics of the metal oxide determine oxidation kinetics? Make
examples of linear oxidation rate and parabolic oxidation rate.
26:2 Which properties of the metal oxide determine whether the oxide is pro-
tective or not, and why? Based on these considerations, explain why silicon
dioxide is more protective than hematite.
26:3 With the help of Table 26.3, calculate the thickness loss of iron, nickel and
chromium after exposure to an oxidizing environment at 1000 °C for
1 month in the hypothesis of a parabolic oxidation rate. Use these data to
draw considerations on the composition of high temperature alloys.
26:4 If the oxidation of a steel alloy produces mostly wüstite, FeO, with an
oxidation rate constant, C2, equal to 50 g2/m4 s and PBR of 1.7, calculate the
weight gain that the metal experiences in 1 year. Compare it with the
thickness loss provided in the text (Sect. 26.3.2).
26:5 An alloy is exposed to an oxidizing environment at 1000 °C. The weight
gain due to oxidation is 0.0015 mg/cm2 after 1 h, 0.005 mg/cm2 after 12 h,
0.007 mg/cm2 after 24 h, and 0.01 mg/cm2 after 48 h. To which growth
mechanism does this alloy adhere?
26:6 Consider data from the previous exercise. In the hypothesis of a parabolic
oxidation, estimate the oxidation rate constant C2 (in lm/s½), knowing that
oxide density is 6.67 g/cm3 and PBR is 1.5.
26:7 Which metal or metal alloy would you select for a gas turbine? Explain why.
26:8 Why is sulphidation more dangerous than oxidation?
26:9 Steels suffer sulphidation, but the addition of chromium and aluminium
decreases the sulphidation rate, as proved by sulphidation rate constants
reported in Table 26.6. Why?
Bibliography
Bianchi G, Mazza F (1989) Corrosione e protezione dei metalli, 3rd edn. Masson Italia Editori,
Milano (in Italian)
Birks N, Meier GH, Petit FS (2006) Introduction to the high-temperature oxidation of metals, 2nd
edn. Cambridge University Press
Rapp RA (ed) (1983) NACE-6, High temperature corrosion. NACE International, Houston, TX
Pilling NB, Bedworth RE (1923) The oxidation of metals at high temperatures. J Inst Met 29:529–
591
Chapter 27
Prevention of Corrosion in Design
[for a civil structure] one euro spent in design with the aim to
prevent corrosion produces same benefits as in construction
phase by paying five euros, or after construction by spending
twenty-five euros, one hundred twenty-five euros just before
corrosion initiation and eventually six hundred twenty-five
euros after corrosion had occurred.
W. R. De Sitter (Law of five, 1984).
Abstract This chapter deals with the principles that should guide the design of a
structure based on corrosion prevention. This includes a series of preventative
measures that can be chosen once the environment and its criticalities are identified,
as well as a careful metal selection. Information on the main classes of metallic
alloys and their corrosion resistance are provided, as a help to guide the selection.

https://doi.org/10.1007/978-3-319-97625-9_27
612 27 Prevention of Corrosion in Design
The main preventative methods that should be adopted in the construction, storage
and operating phases are also examined.
27.1 Design Life and Reliability
Corrosion prevention aims to preserve stability, functionality, characteristic of a

structure exposed to an aggressive environment (for instance, a bridge, an equip-
ment, a car body, any plant item) with the scope of maintaining reliability and
quality as required.
The design life of a structure is the expected operating time that would require
no extraordinary maintenance. It can be a few years for goods, 10 years for a car, 20
for a chemical plant, 30 or more for thermal power plant, an offshore platform or
industrial building, 50 years for a civil building and more than 100 years for a
public infrastructure such as a bridge, a church or a public building.
As far as corrosion is concerned, the reliability of a structure or a plant is the
probability that corrosion does not happen. The more severe the consequences of
corrosion, the higher must be that probability.
Reliability depends on materials adopted, corrosion monitoring and corrosion
control on the design, construction and operational phase (Fig. 27.1) together with
maintenance strategy: this is an economic matter. Ensuring an absolute reliability is
nonsense; conversely, it is worth fixing a required reliability for the specific
application, which implies to search the so-called optimum as the minimum cost
given by the sum of the cost of material and corrosion prevention measures (design
expenses) and the cost of remedial actions (corrosion related costs), necessary when
corrosion takes place. A high reliability is chosen when consequences are severe,
implying either high prevention costs or design costs (i.e., highly corrosion resistant
metals) and the opposite applies when corrosion-related costs are modest.
27.1.1 How to Choose Reliability and Related Solutions
Let’s consider, as often happens, that many different technical options can ensure a
chosen reliability; a question arises: which solution fits better? For example, one can
argue: is it wiser to select cheap metals and plan a frequent substitution (for instance,
yearly) or to choose an expensive corrosion resistant metal or even a combination of
corroding metal and an additional corrosion prevention method (CP or a corrosion
inhibitor)? Obviously, some options are not applicable either technically (for
instance, a corrosion allowance cannot be used for tubes of heat exchangers) or
operationally (for instance, a shutdown may be required for material substitution).
There are constrains due to the process. For instance, reactors for chlorination of
toluene could be made of carbon steel, from a corrosion viewpoint, but steel
catalyses secondary reactions, therefore it cannot be employed; lead cladding must
be used. Similarly, copper alloys cannot be used in plants for soap production
27.1 Design Life and Reliability 613
because copper ions catalyse the oxidation reaction; furthermore, corrosion products
of nickel interact with polyethylene reaction, impeding the correct polymerization.
Among various technical solutions, characterized by the same and necessarily
agreed reliability, the final choice is based on the economic appraisal, through the
Life Cycle Cost approach, which returns the cheapest, although reliable, option.
A more sophisticated analysis is a probabilistic Life Cycle Cost approach by
introducing the expected probability of failure; in this case, rather than a minimum
cost option, a distribution of LCC is obtained, which shows the expected proba-
bility of expenditure that is, by this approach, equivalent to the reliability.
27.2 Prevention in Design Phase
As reference, let us consider a chemical plant, although these considerations are

general. First of all, corrosion prevention starts from design, for which the fol-
lowing must be done:
• Definition of the environment in all parts of the plant from the corrosion
viewpoint. Evaluation of need and possibility to change operating conditions
• Selection of materials on the basis of agreed reliability through LCC analysis.
Further considerations have to take into account the market purchasing and
mechanical properties
• Evaluation of construction constrains and grounding requirements to assess any
possible galvanic coupling.
As learned from experience, about 90% of juvenile failures related to corrosion
are because of lack of one of above issues.
27.2.1 Evaluation of Aggressiveness
The aggressiveness of an environment depends on many parameters (for instance,

for waters: temperature, oxygen content, flow regime and others) which vary in
time and space. For example, crude oil can be aggressive on the basis of water cut,
carbon dioxide and hydrogen sulphide content, naphthenic acids, flow regime,
gas-oil-ratio, pressure and temperature, vertical or horizontal flux and others; all
these factors may change well by well and as a function of the exploitation grade.
27.2.2 Reduction of Aggressiveness
In industrial plants, operating conditions are often modified to allow the use of less
expensive metals, ensuring the agreed reliability. For example, for water circuits, by
removing oxygen and keeping water near neutral or slightly alkaline, carbon steel
can be successfully used.
In plants for production of diluted nitric acid by using sulphuric acid, acid ratio
is fixed in order to reduce corrosion rather than on the basis of a process opti-
mization. It follows that sulphuric acid concentration is maintained above 70%,
then allowing the use of cast iron for piping and steel for tanks after cooling down.
Similarly, to avoid chloride-induced SCC on austenitic stainless steels, tem-
perature is kept below 50 °C then avoiding the use of nickel alloys. More generally,
compatibly with the process, when an inorganic acid is required, sulphuric or nitric
acids are preferred instead of hydrochloric acid, because less expensive metals can
be adopted.
27.2.3 Local Conditions
In a plant, different corrosion conditions can establish locally for a couple of

reasons: different hydrodynamics and water phase separation, either for unmixing
or for condensation. The former occurs in production and refinery of hydrocarbons
and the latter typically from combustion gas and exhausts. Condensed water is
acidic when CO2, SO2, HCl and others are present in the vapour. These species are
not aggressive in gas phase: for example, carbon steel is used in presence of steam
containing carbon dioxide at 300 °C, provided no condensation takes place.
Accordingly, shutdowns are dangerous because condensation happens forming
carbonic acid; corrosion is controlled by injecting ammonia or amines in steam to
neutralize possible condensates. In critical zones, more resistant metals can be
employed.
27.2.4 Homogeneity Is Preferred
Often, aggressiveness depends on non-uniform conditions of oxygen content, pH,

chemical concentration, temperature, flowing or stagnant conditions; or presence of
not uniform scales. An example is the following. A vertical heat exchanger serves
for cooling a process fluid by means of water flowing at the shell side. On top of the
heat exchanger, gas and steam separate causing an increase in temperature because
cooling water cannot be effective. This leads to concentrate salts giving rise to
chloride-induced SCC of austenitic stainless steel, when industrial water is used
(Fig. 27.2). With a horizontal heat exchanger this occurrence does not happen
because cooling water wets continuously all tubes.
Inside fissures and interstices, aggressiveness often increases; typical conditions
are: threaded joints, flanges, deposits and scales. Heat transfer further increases
aggressiveness, as it occurs between tube sheet and tube where tightness is obtained
by mechanical expansion. On the other side, at tube inlet, local turbulence
27.2 Prevention in Design Phase 615
Steam
inlet
Dead space
Presence of gas
Cooling water
outlet
Fissure
Deposits
Cracks
Steam process
Fig. 27.2 SCC on top of tubes in a vertical heat exchanger (from Fontana)
conditions increase aggressiveness, jeopardizing the resistance of copper alloys.

Pumps, cross section area variations, agitators, weld beads and the presence of a
heater may generate local turbulence conditions.
When aggressiveness changes downstream a chemical process and different
metals are used, galvanic corrosion conditions can arise; on the other hand, one-way
valves can help avoid fluid reversal during shutdowns.
27.2.5 Change of Aggressiveness in Space and with Time
Aggressiveness can change with time. There are typically three moments charac-
terizing a structure lifetime: testing and starting, normal operating and shutdown:
materials and prevention measures have to cope successfully with all these
situations.
Concerning location, inlet and outlet zones can show different turbulence con-
ditions as well as screened zones and interstices may face increased concentration
of some species.
Unfortunately, during operation, exposure conditions can change, then jeopar-
dizing the resistance of materials selected; this is inevitably a risk, hard to foresee.
Sometimes, impurities may rise corrosion concern. For example, an AISI 316 grade
stainless steel reactor, designed for neutralisation of hot solutions (up to 90 °C) of
sulphuric acid (3%) and oxygenated water (1–2%) with cobalt carbonate,
worked properly for almost two years; however, as the carbonate supplier changed
for a cheaper, chloride-polluted product, pitting occurred with perforation of the
reactor bottom, 15 mm thick, in a few months.
27.3 Metal Selection
In design phase, corrosion engineers select resisting metals at specified operating

conditions, complying with design life at fixed reliability. Obviously, for those
many applications for which corrosion is not a concern, materials are selected on
mere mechanical requisites, while corrosion engineering should assist material
selection when corrosion is an important issue, starting from so-called basic criteria
and taking into account so-called technological criteria.
27.3.1 Basic Criteria
They deal with basic knowledge of corrosion principles, starting from thermody-
namics, i.e., Pourbaix diagrams, to establish corrosion or immunity or passive
condition, then following with kinetics to determine corrosion rate. Evaluation of
applicable and helpful corrosion prevention methods, as injection of inhibitors and
cathodic or anodic protection, should be included in the corrosion assessment study.
27.3.2 Technological Criteria
Criteria are based on standards (NACE, ASTM, ISO, CEN, UNI, DIN, BS) or by
companies as proprietary standards, which cover almost all applications. Rather
than a theoretical approach, standards highlight guidelines based on knowhow and
experience. The inherent limit of these documents is that instructions are synthetic
and without justification; for this, it is important that users patronize the basic
criteria to avoid unwise mistakes.
Besides corrosion requirements, material selection takes into account other
requirements, as for example mechanical, thermal and electrical ones, as well as
weldability. An economic appraisal is generally the last step for final choice.
27.4 Some General Features of Used Metals
27.4.1 Carbon and Low Alloy Steels
These metals are the most used because they meet cost and mechanical require-
ments. About cost, they are the cheapest ones; parametrically by mass, if carbon
steel cost is one, for zinc is two; for aluminium and lead is four; for copper and
stainless steel is ten; for chromium and tin is twenty; for nickel alloys and titanium
is thirty to fifty. Mechanical properties are good and can be changed by alloying,
heat and mechanical treatments.
27.4 Some General Features of Used Metals 617
Carbon steel
Organic Organic Inhibitors Cathodic

coating or cementitious (eventually) protection
or galvanizing coatings and coatings
Cooling
Atmosphere Fresh waters waters Seawater
(pipeline)
Organic coatings Filming Cathodic

and inhibitors protection
cathodic protection
Process Seawater
Soil water (offshore platform)
Fig. 27.3 Guideline for the use of carbon steel in neutral and low aggressiveness environments
Figure 27.3 summarises the use of carbon and low alloy steels for industrial
processes or fluids, provided the adoption of a suitable prevention method, as
coatings, cathodic protection and corrosion inhibitors. Typical applications are for
atmospheric exposure structures (by using COR-TEN® or with the addition of
painting), buried structures (with coatings and cathodic protection), water plants
and water carrying piping (coatings, oxygen removal and cathodic protection).
In alkaline solutions, steel is passive, so it can be used bare, as in sound, pristine
concrete, i.e., neither carbonated nor chloride-contaminated; in boilers after
deoxygenation and slight alkalization. In heating circuits, no treatment is required,
provided there is no refilling after start-up (water is spontaneously deoxygenated,
being oxygen depleted by corrosion in early stages). Potable fresh wasters are
generally non-corrosive provided they are scaling (i.e., positive saturation index).
There are specific environments, as sulphuric and nitric acids, generally considered
highly corrosive, to which steel fairly resists because it passivates.
Carbon and low alloy steels suffer SCC in specific environments and operating
conditions: for instance, when temperature exceeds 70 °C in solutions containing
nitrates, hydroxides, carbonates/bicarbonates, or at room temperature in the pres-
ence of sulphides by hydrogen embrittlement mechanism for high strength steels
(tensile strength exceeding 750 MPa).
27.4.2 Stainless Steels
These alloys fit the requirements relating to reliability, safety and durability in

almost all industries: manufacturing, chemical, energy, transportation, construc-
tions. As far as civil industry, furniture goods, health and food industry are
Table 27.1 Chemical composition (% by mass) of most used stainless steels

Type C Cr Ni Mo Others PREN
(max)
Austenitic AISI 304 0.08 18–20 8–11 18
Austenitic AISI 304 L 0.03 18–20 8–12 18
Austenitic AISI 321 0.08 17–19 9–12 Ti = 5 x %C 18
Austenitic AISI 347 0.08 17–19 9–13 Nb + Ta = 10x%C 18
Austenitic AISI 316 0.08 16–18 10–14 2–3 24–28
Austenitic AISI 316Ti 0.08 16–18 10–14 2–3 Ti = 5 x %C 24–28
Austenitic AISI 317L 0.03 18–20 11–15 3–4 28–32
Austenitic AISI 309 0.20 22–24 12–15 – Low C as L and EL 22–24
grades
Austenitic AISI 310 0.25 24–26 19–22 – Low C as L and EL 24–26
grades
Super-austenitic 0.02 19.5–21.5 17.5–18.5 6–6.5 N = 0.5–1 42–43
0.02 19–21 24–26 6–8 N = 0.2–0.3 44–48
Duplex 2304 0.03 22–24 5.5–7.5 0.1–0.6 N = 0.1–0.5 24–26
Duplex 2205 0.03 24–26 6–8 2.7–4.5 N = 0.1 36–38
SuperDuplex 2507 0.003 25 7 4 N = 0.25 36
Ferritic AISI 405 0.15 11.5–13.5 – – – 12
Ferritic AISI 430 0.15 15–17 – – – 16
17-4 PH 0.07 15–17 3–5 Cu = 3.0; Nb = 5 x % 17
C – 0.45
concerned, operating, aesthetic and economic targets are achieved. Table 27.1
reports main commercial stainless steels, while Fig. 27.4 summarizes the devel-
opment philosophy of most common compositions.
Their corrosion resistance relies on the passive film, a few nanometres thick,
made of chromium oxide mainly. Provided the passive film is flawless and
self-healing if locally destroyed for either mechanical or chemical reasons, stainless
steel behaves as a noble, corrosion-resistant metal; conversely, when the passive
film is permanently destroyed locally, localized corrosion happens.
Chromium is fundamental for stainless steels to build a corrosion resistant
passive film. The minimum Cr content is 11%: this stainless steel resists oxidation
in non-polluted atmospheres. To enhance corrosion resistance, a minimum of 18%
is needed, as for ordinary and most common stainless steels. To further increase
resistance, a higher Cr content in combination with Mo (generally 2–4%) and N is
specified. Further resistance is achieved by anodic or cathodic protection.
Superferritic Ni-Cr-Fe alloys 303, 303 Se

stainless steels
+Ni for corrosion resistance in

+Cr and Mo high-temperature environment
309, 310, 314, 330 +S or Se

430
machinability
Duplex SS
+Cr e Ni 2205, 2304, 2507
347 No Ni for strenght and
+Nb, Ta ferritic oxidation resistance +Cr, -Ni
to reduce for higher strenght
sensitization
304 Precipitation
+Ti to reduce +Cu, Ti, Al,
321 Fe + Cr (18-20%) hardening
sensitization -Ni
+ Ni (8-10%) steels
304L +Mn, N e Ni
+Mo for higher strenght
for pitting resistance
316L -C to reduce 201, 202

sensitization 316
No Ni, -Cr
martenitic
+Mo e N
for pitting resistance
321L
Superaustenitic +Ni, Mo, N

317 403, 410, 420
stainless steel for corrosion
resistance
Fig. 27.4 Logical graph for stainless steel composition, AISI designation (from Sedriks)
The addition of nickel (8–10%) stabilizes the austenitic (FCC) structure,

enhancing low temperature toughness, ductility and high temperature corrosion
resistance. By adjusting the Ni concentration to about a half, i.e., 4–5%, both
austenitic and ferritic phases stabilize to about 50% each, obtaining the so-called
duplex stainless steels. These grades show enhanced mechanical resistance and an
improved resistance to SCC, either chloride-induced, through an anodic mecha-
nism, or hydrogen embrittlement, for instance in the presence of hydrogen sulphide;
the addition of Mo and N increases the resistance to pitting.
Ferritic stainless steels, although cheaper, are less used because they are more
brittle on welds. As general feature, they offer the advantage to be chloride-induced
SCC resistant but a weakness associated to the high susceptibility to hydrogen
embrittlement. Other stainless steel types are the martensitic ones and those
obtained by precipitation hardening.
To predict the structure of a stainless steel on the basis of composition, the
Schaffler diagram can be used (Fig. 27.5). It is obtained by plotting two parameters,
32
ite te
i
Fe Ferr
28
Nieq = Ni + 30 C + 0.5 Mn
rr
e
5% No
rrit
24 Fe
Austenite %
10
e
20 r rit
Fe
% te
20 rri
16 A+M Fe
%
40 e
rrit
12 A+F % Fe
8 0
rrite
8 Martensite % Fe
A+M+F 100
4
F M+F Ferrite
+
M
0
0 4 8 12 16 20 24 28 32 36 40
Creq = Cr + Mo + 1.5 Si + 0.5 Nb
Fig. 27.5 Schaffler diagram
Ni-equivalent and Cr-equivalent, where Ni-equivalent reflects the austenizing ele-

ments and similarly Cr-equivalent for ferritic ones. Unlike carbon, other elements
tend to stabilize their own structure (for instance, Cr, as BCC, stabilizes the ferritic
phase and Ni, as FCC, the austenitic one, and so on for other elements).
27.4.3 Nickel Alloys
The FCC structure of nickel alloys, which gives high ductility at low temperature,
in combination with a high resistance to corrosion (chloride-containing, alkaline
and reducing solutions), leads to a huge use in chemical and petrochemical industry.
In addition, pure Ni is also used for sodium and potassium hydroxide solutions,
provided they are ammonia-free.
Table 27.2 reports the most used grades of Ni-based alloys. Alloy-20 derives its
name from the composition—approximately 20% Ni–20% Cr (plus Mo)—which is
one step forward from ordinary stainless steel (for instance, 316 grade); alloy B and
alloy C, known with the commercial name Hastelloy, contain high Mo concen-
tration and resist very aggressive environments, from strong acids to high chloride
content solutions. Alloy 600 resists oxidizing solutions and high temperature gas.
Alloy 400 and k-500 (also known as Monel) are Ni-Cu alloys, which implies both a
noble behaviour (i.e., potential above hydrogen equilibrium potential) and a passive
state; they are used for deaerated hydrofluoric acid.
Table 27.2 Chemical composition (% by mass) of nickel alloys

Type Fe C Cr Ni Mo Others Notes
(max)
Alloy 20 Balance 0.07 19–21 32–38 2–3 Cu, Nb, Ta, Mn,
P, S, Si
Alloy 400 (Monel) 2.5 0.3 Balance Cu = 28–34; Mn;
S; Si
Monel K-500 2 0.25 Balance Cu = 27–33; Precipitation
Al = 2.3–3.15; hardened
Mn; Ti; S; Si
Alloy 600 6–10 0.15 14–17 Balance Cu, Mn, Si, S
Alloy B 2 0.01 1 65–69 26–30 Co, Mn, Si, P, S
Alloy C 1.5–6 0.01 16–23 56–65 13–18.5 Al, Cu, Mn, Si,
Ti, V
27.4.4 Aluminium Alloys
Aluminium and aluminium alloys resist corrosion in solutions with pH in the

interval 4–9 because they passivate, forming a strong, protective passive film,
which—unlike that of stainless steels—is an insulator, then reducing electron
transport. The passive film can be strengthened by anodizing. Strong acids and
strong alkaline solutions destroy the passive film, which causes then a fast uniform
attack. Impurities are always detrimental.
Corrosion resistance depends on composition, as Table 27.3 reports. The Cu
containing 2xxx series, widely used in aerospace industry, suffers corrosion because
heat treatments separate a noble phase, triggering localized attack. Mg-containing
series, as 3xxx and 5xxx, show a better corrosion resistance because the separated
phase is less noble. To improve corrosion resistance, plating (cladding) with pure
Al and anodizing are widely used.
Table 27.3 Corrosion behaviour of aluminium alloys (wrought)

Series Alloy elements Uniform Corrosion Pitting Exfoliation SCC
1xxx O O O I
a
2xxx Cu M P P–M VS–Ra
3xxx Mn, Mn + Mg O O O R
4xxx Si M G G G
5xxx Mn, Mg, Cr O G G I–R
6xxx Mg, Si O G O I
7xxx Zn, Mg, Mn, Cu M M M–P VS–Ra
O optimal; G good; M mediocre; P poor; I immune; R resistant; S susceptible; VS very susceptible
a
Depending on thermal treatment
27.4.5 Copper Alloys
Copper and copper alloys show a good corrosion resistance due to a passivation
process: in urban atmosphere, a basic sulphate (brocantite) forms, in marine atmo-
sphere, basic chloride (atacamite) forms. Also in waters, copper alloys passivate.
Brass is largely used for seawater applications although suffering from
corrosion-erosion, SCC if in presence of ammonia, and selective corrosion (i.e.,
dezincification).
Brass and bronze are employed in all environments (acidic, neutral and alkaline)
provided oxidants, like nitrates and chromates, or complexants, like ammonia, or
chemical species reacting with copper, like sulphur, mercury and hydrogen sul-
phide, are not present.
Table 27.4 reports composition and properties of the main copper alloys.
27.4.6 Titanium and Its Alloys
Titanium passivates by means of its oxide that is highly resistant to oxidizing

electrolytes and high chloride concentration. It suffers from corrosion in the pres-
ence of fluoride ions and some organic acids because of complexing effects, crevice
corrosion in acids at temperature above 70 °C and hydrogen embrittlement for
formation of titanium hydrides.
Commercial purity titanium is used in 4 grades (namely, 1, 2, 3 and 4, with
different oxygen content, in the range 0.18–0.45%) with tensile strength from
240 MPa for grade 1–550 MPa for solubilized grade 4, which is less ductile and
less resistant to corrosion.
Titanium alloys classify in three types: a (compact hexagonal), b (BCC) and
biphasic, a + b. The most used alloy is grade 5, biphasic type, Ti6Al4 V (6% Al,
4% V) which finds applications in aerospace industry thanks to its mechanical
resistance. Pd containing alloys, typically 0.2% Pd, resist both oxidant and reducing
environments due to so-called cathodic alloying (see Sect. 7.1.4).
27.5 General Philosophy for Metal Selection in Industry1
A rational approach to material selection for most of industrial process fluids is

1
This paragraph is based on Giuseppe Faita training Courses.
27.5 General Philosophy for Metal Selection in Industry 623
Table 27.4 Copper alloys for pipes and tube-sheet

Type Cu Zn Ni Sn Al As Fe Mn vmax, Notes
seawater
(m/s)
Alloys for pipes
Brass 70/30 70 30 0.04 1
Admiralty 70 29 1 0.04 1.2 Highly resistant
brass H2S
Al brass 76 22 2 0.04 2.5 Good resistance
to impingement
CuNi 70/30 68.5 30 0.7 0.8 3 Better resistance
to impingement
than Al brass
Resistant to
ammonia and to
SCC
CuNi 70/30 66 30 2.0 2 4 Resistant to
modified ammonia and to
SCC
CuNi 90/10 87 30 2.0 1 3 Resistant to
modified ammonia and to
SCC
Al brass 95 5 3
mono-phase
Alloys for tube-sheet
Munts metal 58–61 Bal. 0.25 0.15 Suffer
dezincification
Do not couple
with pipes in Al
brass
Naval brass 59–62 Bal. 0.5– 6–8 0.10
1
Al brass 88–92 1.5–3.5
(type D)
Type E 78–85 4–7 8–11 0.5–2 Promotes
galvanic
corrosion on
pipes in
admiralty brass
and Al brass
27.5.1 Alkaline Solutions
In alkaline solutions, most metals and alloys are passive or passivated because of
the formation of oxide and hydroxide scales, therefore resisting corrosion.
A guideline for material selection is reported in Fig. 27.6.
Carbon and low alloy steels are used in diluted alkalis, with pH in the range 9.5–
10.5 as typical in boilers, provided a complete oxygen depletion, at almost all
operating temperatures.
In concentrated alkalis, carbon steel is employed at temperatures below 100 °C

to avoid amphoteric dissolution; ordinary stainless steels, as 18Cr-10Ni, only resist
up to slightly higher temperatures. For high temperatures, up to 350 °C as for
melted soda, Ni has to be used.
Attention must be paid to the risk of SCC on carbon and low alloy steels, as well
as on austenitic stainless steels, when temperature exceeds 50 °C and tensile stress,
even locally, is close to the yield strength, as shown in Fig. 27.7. Stress relieving
carried out at about 600 °C, especially after welding, reduces local tensile stress
fields, then reducing the risk of SCC occurrence. For austenitic stainless steels,
since stress relieving can cause carbide precipitation, the treatment is questionable.
Ni and Ni-based alloys are not susceptible of SCC in alkalis at any temperatures.
27.5.2 Chloride-Free Acidic Solutions
Carbon and low alloy steels cannot be used in acidic solutions (pH < 5) unless
corrosion inhibitors are added. To select resisting metals, a first check is required:
presence or not of chlorides, followed by a second check: presence of nitric acid or
other strong acids. Organic acids are considered separately.
Almost all stainless steel grades resist chloride-free acids at pH exceeding 2. At
lower pH, i.e., highly concentrated acids, in the presence of oxidizing species,
primarily oxygen, high PREN stainless steels are required (i.e., high Cr and Mo
content) or low iron content alloys (alloy 20 and nickel-based alloys). As rule of
thumb, PREN > 25 and Fe% < 50% should be selected. When oxidizing species
are absent, although alloy 20 and nickel-based alloys can resist corrosion attacks,
the best choices are alloy 400 and alloy B. However, these two latter alloys fail in
the presence of oxidizing species, even if present accidentally for short exposure
time.
Alkaline solutions
Diluted alkalis Concentrated alkalis

(pH 9-11)
T < 100°C T > 100°C
Carbon steel
Carbon steel Stainless Alloys 20 Nickel alloys,
steel (Ni < 45%) Nickel
(AISI 304L)
Fig. 27.6 Guidelines for selection of metals in alkalis (from Faita)

27.5 General Philosophy for Metal Selection in Industry 625
150
Temperature (°C) Nickel and nickel alloys
100
Carbon steel
+ distention
50 Carbon steel
50 100
NaOH concentration (g/L)
Fig. 27.7 Application map for selection of steels and Ni alloys in alkalis (Graver, 1985)
To resist nitric acid, Mo-free stainless steels have to be used (AISI 304, AISI
347, duplex 2304 and AISI 310 for high temperatures, as low carbon grade (L) and
extra low carbon grade (EL)).
Figure 27.8 summarizes the indications to be followed in chloride-free acidic
environments.
27.5.3 Chloride-Containing Environments
Figure 27.9 shows the guideline for metal selection in chloride-containing envi-
ronments. Two conditions have to be considered: alkaline solutions (pH 7) and
acidic solutions (pH < 7).
pH 7. For chloride content above 100 ppm and in the presence of oxidants,
low PREN stainless steels (below 26) suffer localized corrosion and even SCC (for
austenitic grade) for temperature exceeding 60 °C when under tensile stresses. To
resist pitting, a stainless steel grade with proper PREN must be used, such as alloy
20 and alloy C. To avoid SCC occurrence, duplex stainless steels, 2205 and 2507
grades, can be used. For high chloride contents, copper alloys and titanium are best
choices. Without the presence of oxidants, even with high chloride concentrations,
depending on pH, carbon steel, copper alloy and low PREN stainless steels can be
conveniently considered.
pH < 7. In practice, since acidic conditions increase aggressiveness, even for
relatively low chloride content exceeding 100 ppm the use of highly resisting
metals becomes mandatory, as alloy C, B and titanium.
Acid solutions
Stainless steel
Ferritic Austenitic and

(Cr-Mo-Fe) austenoferritic
(Cr-Mo-Ni-Fe) (Cr-Ni-Fe)
Cast Wrought
Other acids Nitric acid
316L - 316Ti - 316Nb 304 - 347

AISI 317L 2304 (austenoferritic)
2205 (austenoferritic)
T > 100-120°C
High concentration
high temperature 310L - 310EL
With Without
oxidants oxidants
Alloys 20 Alloy 400

2507 (austenoferritic)
Alloys B
Nickel alloys
Fig. 27.8 Guidelines for selection of metals in chloride-free acids (from Faita)
27.6 Prevention by Design
Non-homogeneous conditions, either metallurgical or environmental, are the most

frequent causes for corrosion attacks, accordingly they must be carefully avoided in
design. For example, galvanic couplings, local mechanical stresses, turbulence
conditions, local condensations, should be avoided. Some hints are reported in
Figs. 27.10, 27.11 and 27.12. Figure 27.13 deals with heat exchangers conditions
and provides a practical guide to avoid most common corrosion attacks.
27.7 Prevention in Construction
The construction phase may require mechanical work (for instance plastic defor-
mation), thermal treatments, welding or mechanical assembling, which can cause
damages on coatings (if present) or induce residual stress or phase precipitation.
Non-destructive tests can be used to check the metal status during construction and
before commissioning.
27.7 Prevention in Construction 627
Chloride-containing
environments
pH ≥ 7 pH < 7
With Without
> 100 ppm < 100 ppm
oxidants oxidants
(all concentration)
Acid solution
Carbon steel Fig. 27.7
< 100 ppm > 100 ppm Stainless steel
(AISI 316L)
Copper alloys With
AISI 316L Without
(Brass, Cupronickel) oxidants oxidants
(all concentration)
Alloys C
Copper alloys Alloys B
(Brass, Cupronickel) Titanium
Titanium alloys
< 60 °C > 60 °C (Ti-0,2% Pd)
(pits with (cracks with

AISI 316L) AISI 316L)
Alloys 20 2205, 2507
Alloys C Alloys 20
Titanium Alloys C
Titanium
Fig. 27.9 Guidelines for selection of metals in chloride-containing environments (from Faita)
To facilitate final assembling, each component should be properly identified

especially when various metals are used.
27.8 Prevention in Storage
Before final assembling, components often require to be stored. Accordingly,

attention should be paid to avoid chloride contamination in chloride-containing
atmospheres, such as in marine locations.
Correct To avoid
Possible corrosion
attack areas
Possible corrosion
attack areas
Fig. 27.10 Schematic representation of correct joints and joints to be avoided
27.9 Commissioning and Start-up
Hydrotesting before and during commissioning is twofold important. Firstly, cor-

rosion must be avoided during testing, by employing treated non-corrosive fluids,
as inhibited or deaerated and low chloride-containing water. Secondly, it is
important to avoid conditions that can trigger corrosion once production has started.
This is a typical situation occurring on stainless steel piping in food industry plants
where, after hydrotesting, water is not totally drained, so that in some zones
entrained water concentrates by evaporation and critical chloride concentration for
pitting initiation is reached. At production start-up pitting can eventually proceed,
because already initiated in this former phase.
Also in boilers, localized corrosion can happen for similar reasons once oper-
ating starts. As it appears evident, attention is crucial during hydrotesting and
following drainage operation, which must be thoroughly done by drying with dry
nitrogen flow.
27.9 Commissioning and Start-up 629
No Ok No Ok
Smooth surfaces witout sharp angles Free air flow circulation

around the equipment
No Ok
Guarantee drainage and cleaning
No Ok
Minimize surface/volume ration
No Ok
Guarantee full filling avoiding discontinuous wetting
Fig. 27.11 Schematic representation of correct equipment details and elements to be avoided
Start-up is a critical phase when passive conditions are involved, too. Passive
films must form uniformly with suitable structure, composition and protective
properties. Often, before starting production, a passivating treatment is required; for
stainless steels, nitric acid is used, followed by a neutralizing treatment with sodium
hydroxide. Another example is the pre-passivation of copper alloys before starting
seawater circulation, obtained by a treatment with ferrous sulphate solution, which
helps the passivation of brass and nickel-copper alloys.
No Ok
Steel Hot gas Hot gas

casing Steel
Condensation
casing
Insulation Insulation
Hot gas vessel condensation avoid
No Ok
Concetrated
solution
Concetrated
solution
Possible Diluted
Diluted attack areas solution
solution
Solution inlet pipe positioning
No Ok
Over-heating areas Heaters

and crevice
corrosion risk
Heaters
Heaters positioning in a reactor
Fig. 27.12 Schematic representation of correct equipment details and elements to be avoided
27.10 Prevention During Operation 631
a f
e g
b c h
d
Fig. 27.13 Corrosion forms typical of heat exchangers and their position: a) crevice corrosion
under joints; b) crevice corrosion between tube and tube sheet in the back of the tube sheet; c)
erosion-corrosion grooves on the outside of tubes due to excessive fluid velocity; d) crevice
corrosion or fretting corrosion of tubes in the diaphragms contact area; e) corrosion by differential
aeration due to preferential deposition of sludge; f) erosion-corrosion grooves outside tubes; g)
corrosion caused by turbulence at the tube inlet; h) corrosion by differential aeration under deposit
in the distributor; i) SCC in all positions where tensile stresses originate due to non-allowed
thermal expansions or other reasons
27.10 Prevention During Operation
During operating or production, corrosion control is achieved by monitoring and

planned inspections. As far as monitoring is concerned, corrosion rate is measured
in combination with environment-related parameters, such as temperature, fluid
velocity, pH, cathodic reactant concentration, as oxygen, chlorine and others.
27.11 Planned Maintenance
Almost every year, or in specified periods, a corrosion-oriented inspection is carried

out on plants. This requires a preparation of the plant and facilities, which normally
consists of removal of internal fluids, often followed by a purge with inert atmo-
sphere. When etching is required to prepare internal surfaces for visual inspection,
conditioned solutions should be used to avoid damages; generally, an inhibited,
acidic, chloride-free solution is recommended, also considering any potential side
effect at start-up conditions.
When possible, emptying the plant is discouraged because process fluid is often
less corrosive than the uncontrolled transitory conditions set up during fluid dis-
charge. A typical situation is when fluid in entrapped zones concentrates, then
leading to local aggressive conditions.
Final Remark
Professor Roberto Piontelli in his pioneering book, Elementi di teoria della
corrosione a umido, Ed. Longanesi, 1961, never translated, stated:
L’arte di scegliere correttamente i materiali e i metodi di prevenzione della corro-
sione in relazione alle condizioni in cui andranno a operare; di evitare accuratamente
le cause di eterogeneità o di procedere a neutralizzarne le conseguenze; di evitare le
condizioni di spazio morto, le azioni abrasive, di prestare attenzione alla presenza in
ambiente anche apparentemente poco aggressivi di sollecitazioni di trazione o a
fatica; di controllare le condizioni ambientali chimiche o di moto relativo, e tutte le
altre forme di insidia generali o specifiche che una rassegna incompleta come quella
sviluppata in questo volume può servire ad additare, a spiegare, a riconoscere; ecco
il primo requisito di un corrosionista.
The art of selecting correct materials and corrosion prevention methods on

the basis of operating conditions; of avoiding heterogeneity or select pre-
vention measures; of avoiding recesses, abrasion and turbulence conditions
and paying attention to mechanical stresses and fatigue also for fairly
aggressive fluids; of specifying chemical parameters and flow regime and
foreseeing general and specific insidious events, some of them this book
illustrate; all this is the primary role of a corrosion engineer.
27:1 As reported in Sect. 27.2.5, the bottom of a chemical reactor was perforated
in a few months because of an unexpected chloride contamination. Explain
the pitting mechanism occurred and the prediction of time to perforation.
Highlight a strategy to avoid such inconvenient.
27:2 Draw Evans diagrams for alloy B and C in the presence and absence of
oxidants.
27:3 Try to demonstrate why Cu containing series 2xxx suffers corrosion, and
Mg-containing series, 3xxx and 5xxx, resist corrosion basis on separated
phases, which are more noble in series 2xxx and less noble in the others.
27:4 Which are the candidate materials for a heat exchanger? The cooling fluid is
seawater. Distinguish among water box, tube sheet and tubes. Justify your
selection. Which corrosion phenomena do you want to avoid?
27:5 A water injection plant is used to inject at high-pressure huge quantities of
water into the reservoir in order to increase oil recovery from an oil and gas
formation. The following five (5) components may be identified: water
supply pump (lifting pump); flow-line from supply well area to injection
area (with a length from 100 m up to few km); booster pump to increase
pressure; distribution system (manifold); injection wells. Considering the
use of carbon steel, please for each plant unit indicate and justify the
corrosion-related problems considering the three types of waters:
• Low salinity water from supply wells (for instance, fresh water,
underground water table or river water)
• High salinity water, such as formation water from hydrocarbons (Total
Dissolved Salt higher than 200 g/L, as NaCl)
• Seawater
27:6 For the same plant of Ex. 27.5, make a justified material selection in order to
avoid any corrosion problem, considering also the possibility to add treat-
ments such as oxygen removal (physical and/or chemical treatment),
anti-bacteria treatment, erosion control system.
27:7 A plant is composed of two distinct sections. Section one for the treatment
of an acidic aqueous solution; section two for the treatment of a basic
aqueous solution. Each section is constituted by a tank, a pump, a heat
exchanger and a mixer for the dilution with water. The two streams are
finally mixed in a reactor to obtain a neutral salt soluble in water. For at
least one of the two sections indicate: materials for the main components
(tanks, pumps, transfer pipes, heat exchangers) justifying their choice
(taking into account chlorides, salinity, pH, oxygen, chlorine, etc.); any
corrosion prevention treatments. Operating conditions: atmospheric pres-
sure, tanks at room temperature, acidic solution at 40 °C, basic solvent
heated at 100 °C, demi water used for preparation and dilution; final pro-
duct temperature 80 °C.
27:8 Market lead companies to replace in heat exchangers copper with alu-
minium for both cost and material issues. When it possible to do this?
27:9 What kind of insulated panels (base metal) would you use for zootechnical
applications?
27:10 After production of a carbon steel fire protection system, a hydrotest has
been performed to verify the quality of the welds. Which water you would
suggest to use? After the test, what would you suggest to do for the internal
water: complete or partial emptying, constant pressurized filling? Justify
your answer. If the fire system piping is in stainless steel, do you suggest the
same water and the same after-test treatment?
Bibliography

Graver D (1985) Corrosion Data Survey, NACE, Houston
Milano (in Italian)
Chapter 28
Monitoring and Inspections
In the Venetians’ arsenal as boils

Through wintry months tenacious pitch, to smear
Their unsound vessels; for the inclement time
Seafaring men restrains, and in that while
His bark one builds anew, another stops
The ribs of his that hath made many a voyage,
One hammers at the prow, one at the poop,
This shapeth oars, that other cables twirls,
The mizzen one repairs, and main-sail rent;
Dante, Inferno, XXI, 7–15
Abstract Corrosion of industrial equipment can lead to risk conditions for eco-
nomic losses and safety of personnel. To minimize that risky, besides the correct
selection of material and the use of proper preventative methods, the design of a
corrosion monitoring system plays an important role, followed by programmed
inspections during operation. The analysis of monitoring and inspection results is
also important to plan maintenance activities. This Chapter deals with the selection
of the correct monitoring strategy and its application to operating systems: the most
common monitoring techniques, as the use of corrosion coupon, electrical probes,
linear polarisation resistance, galvanic probes, corrosion potential are presented.
A brief outline of the most important non-destructive techniques is also reported.

https://doi.org/10.1007/978-3-319-97625-9_28
636 28 Monitoring and Inspections
28.1 Corrosion Monitoring
To operate safely in the presence of corrosive fluids, it is necessary to control the

corrosion process by following how it proceeds over time, based on the expected
damage as, for instance, uniform thinning or localized attack (Fig. 28.1). This
activity is known as corrosion monitoring.
Corrosion rate is the main and typical parameter measured, continuously or
periodically; it is also used to optimize the dosage of corrosion inhibitors. Type of
measurement, frequency and devices depend on the expected corrosion attack. The
following classification can be adopted:
• Thinning: measurement of corrosion rate by means of coupons or electro-
chemical techniques
• Localized corrosion, as galvanic corrosion or pitting and crevice of stainless
steels: measurement of electrical parameters, i.e., potential and current
• Cracking due to SCC or corrosion-fatigue: unlike other corrosion forms, no
monitoring techniques are used, although sophisticated methods such as elec-
trochemical noise and acoustic emission have been proposed.
Corrosion monitoring greatly contributes to increase the safety level of a plant by
gathering important information on the corrosion process that takes place in the
period between inspections, which are usually planned during shutdowns; more-
over, corrosion monitoring is a very cheap activity compared to an inspection.
Nowadays, available monitoring systems deal with general corrosion in easily
accessible locations, only; therefore a lot must be done for either localized corrosion
or harsh operating conditions, for example at high temperature or in deep oil and
gas wells. Most recent progress is mainly related to hardware or software for
electronic devices to gather and elaborate data, then improving on-line remote
control.
Corrosion monitoring is essentially based on intrusive systems that require the
insertion of sensors or devices inside equipment, vessels, reactors or piping, to be
exposed to the process fluid. A non-intrusive method is based on the measurement
of residual thickness from the accessible external surface by ultrasound technique.
As a general philosophy, corrosion monitoring should be based on at least two
methods or measuring techniques to increase the reliability of gathered data; at least
the corrosion coupon technique should be used.
Corrosion rate depends on many factors, as environment and metal chemical
composition, operating conditions (temperature, pressure and flow rates), presence
of galvanic couplings. Accordingly, a monitoring system can be based on the
measurement of one of these factors, as temperature to check conditions favourable
to SCC, or concentration of corroding metals as iron in the fluid, or of species that
provide the cathodic process (pH, oxygen content, chlorine).
28.1 Corrosion Monitoring 637
28.1.1 Selection of Monitoring Locations
Only a few points of a plant are monitored for either technical availability or
economics. Selected locations have to be representative of the plant, at least
according to a criterion of conservativeness (most severe corrosion condition). For
instance, the most adopted criteria to select monitoring posts are the following:
• Zones where turbulence is higher (for instance, downstream elbows or sharp
cross section variations) in case of risk of erosion-corrosion or in general where
the corrosion rate is under of oxygen diffusion control
• Stagnant zones, in case of pitting of stainless steel, since initiation is favoured
• Presence of galvanic couplings (hazardous contact with different materials)
• High stress zones or zones with different microstructure (as in case of welds) in
case of risk of SCC
• Areas where corrosion inhibitors, or chemicals in general, are added
• Anodic zones in case of buried structures, which can be affected by stray
currents.
Once a monitoring point has been selected, the exposure to the fluid must also be
considered, such as centre or bottom or upper position inside a line, taking into
account any possible stratification of phases.
28.2 Common Monitoring Methods
To monitor a corrosion process, two distinguished approaches are followed:

• Direct methods that provide direct measurement of corrosion rate. This is
achieved through the use of corrosion coupons and spools
• Indirect methods, which allow the calculation of the corrosion rate through the
measurement of parameters useful to assess the corrosion process, such as
electrochemical techniques (potential and linear polarization resistance mea-
surements) when fluid is an electrolyte, electrical resistance probe and hydrogen
probe.
28.2.1 Corrosion Coupon
A corrosion coupon is a specimen made of the same construction metal with

suitable shape, such as a strip or a disk. The disk shape coupon better reproduces
the real exposure conditions, since it replaces a portion of the equipment wall.
Coupons are inserted inside the process lines for a fixed period, then recovered for
visual examination and weighing, for calculation of average corrosion rate.
Stainless steel
coupon holder
Stainless steel
nuts
Insulating
seals
Stainless steel Corrosion

screws coupons
Fig. 28.2 Assembly of strip specimen type
Insertion and recovery of corrosion coupons are carried out either during shutdowns
or during operation by suitable pressurized retrievable devices. Attention must be
paid to two aspects:
• The risk of galvanic contact with the coupon holder, typically made of stainless
steel, if not electrically insulated (Fig. 28.2)
• The metal composition, which has to be the same of the exposed one; for carbon
steel structures, mild steel or pure iron is usually used for a more conservative
approach.
The main drawback of this method is that the information on corrosion rate is
delayed and available once corrosion has already occurred, because necessarily
exposure time must exceed one month or so to allow mass loss measurement.
Figure 28.3 shows schematically two types of corrosion coupons: two strips
immersed in the process fluid and a disk flash mounted at the bottom of the pipe.
28.2.2 Corrosion Spool
A spool is a span of line usually 0.5–1 m long, inserted by flanges, which can be
retrieved periodically during a shutdown or by means of a dedicated by-pass for
visual examination. Compared to the use of corrosion coupons, it shows the
advantage to reproduce the true exposure condition, while showing the same dis-
advantage of providing only delayed information.
28.2 Common Monitoring Methods 639
(a) (b)
Fig. 28.3 Types of corrosion coupon: a strip; b flash-mounted type (used when water separates at
the bottom of a line)
28.2.3 Electrical Resistance Probe
The electrical resistance probe consists of a metal coupon of the same material of
the pipe, which allows the calculation of corrosion rate through the measurement of
its electrical resistance (Fig. 28.4). As corrosion proceeds, the electrical resistance
of the coupon increases because the corrosion attack reduces its cross section area,
according the second Ohm’s law. By plotting the electrical resistance against time, a
straight line is obtained with a slope proportional to corrosion rate. Advantages of
the method are many: no retrieve operation is required because the measurement is
easily carried out externally; corrosion rate (i.e., the slope) can be calculated after
very short exposure time (a few days is enough) and it works in any H2S-free
environment. In the presence of hydrogen sulphide, the electrical resistance is
influenced by the formation of iron sulphide, which has an electronic conductivity,
therefore readings are erratic. Since resistance is temperature-dependent, the device
is provided with a calibration system to take into account the effect of temperature.
The main drawback of this method is that in case of very low expected corrosion
rate, the thinning of the coupon and consequently the electrical resistance variation
are small, so that a great accuracy of the electrical instrumentation is required.
28.2.4 Linear Polarisation Resistance
LPR gives the instant corrosion rate, as will be discussed in Chap. 29 for laboratory
testing techniques. The method can be applied only in the presence of an elec-
trolyte, for instance water-handling plants. Two devices are available (Fig. 28.5): a
three-electrode device and a two-electrode one. The latter system is often used
because simpler: counter and reference electrodes are made of same material.
(a) (b)
Fig. 28.4 Electrical resistance probe: a flash-mounted type; b coupon type
(a) (b)
Aggressive environment
Couterelectrode
Reference
Working
electrode
Power Supply Power Supply
Fig. 28.5 LPR measurement on field: a three-electrode device; b two-electrode device
Sometimes as counter-electrode the base metal of the structure is used. Working

electrode is made of same metal of the line. Figure 28.6 shows some types of
electrodes: flash-mounted (Fig. 28.6a) and strip type (Fig. 28.6b), where the former
is advantageous because reproducing the real exposure conditions and avoiding risk
of obstruction.
28.2.5 Galvanic Probe
This simple device is used when the cathodic process is oxygen and chlorine
reduction in waters. The cathode is gold plated to limit either overvoltage or
Fig. 28.6 LPR device: a (a) (b)

flash-mounted type; b strip
electrode type
scaling. The parameter measured is the current flowing between line and golden
specimen, by means of a zero-ammeter. The sensitivity of the method is 0.05 ppm
of oxygen content (i.e., about 0.6 µm/year corrosion rate of mild steel) corre-
sponding to a current of 1 µA on a cathode with 20 cm2 as surface.
28.2.6 Potential Measurement
The potential measurement of a metallic structure is simple and provides infor-

mation about the degree of corrosion or protection of the metallic component. For
instance, the potential measurement is used to verify the cathodic protection of
metallic structures, as buried pipelines or tanks, to control the passive condition of
concrete reinforcements, or to measure the polarization of structures in zones
affected by stray currents. The potential measurement is closely related to the
corrosion rate if correctly interpreted. For instance, considering mild steel in
neutral-pH condition where it shows an active behaviour, a potential variation of
100 mV corresponds to a variation of corrosion rate of about one order of mag-
nitude, being the Tafel slope about 100 mV/decade.
The potential measurement is carried out by means of a high impedance volt-
meter and a reference electrode. An ideal voltmeter has infinite internal impedance,
meaning that it would draw zero current within the circuit, hence not affecting the
measurement. Truly, the current flowing in the measurement circuit is not zero,
instead is settled by the potential to the circuit resistance ratio, where the resistance
practically coincides with the voltmeter impedance. An impedance higher than
10 MX is recommended in order to avoid the polarization of the reference elec-
trode, as discussed in Chap. 19, Sect. 19.2.3.
Fig. 28.7 Scheme of Voltmeter

measurement of potential
+ -
Impedance Reference
Metal electrode
Solution (environment)
The reference electrode, connected to the negative pole of the voltmeter, shall
maintain its potential constant and it is placed in contact with the environment of
the structure, while the latter is connected to the positive pole (Fig. 28.7).
The reference electrode is composed of a metal strip immersed in an electrolyte.
On its surface there is an electrochemical equilibrium that determines a potential,
which remains constant provided there is no current circulation on its surface during
measurement. Table 28.1 lists the reference electrodes usually used to measure
potential in the laboratory and in the field:
• Ag/AgCl/seawater (SSC) and Zn/seawater (ZN) for seawater applications
• Cu/CuSO4 (CSE) for soil applications
• Manganese dioxide MnO2 (MN) and mixed-metal-oxide activated titanium
(MMO) for reinforced concrete structures.
Table 28.2 reports reference electrode equivalencies.
Potential measured through a reference electrode depends on electrode position
with respect to the structure and on the presence of circulating current. The presence
of ohmic drop into the electrolyte may affect the reading and its correct interpre-
tation, as in the case of CP monitoring: for details refer to Chap. 19.
28.2.7 Bio-probe
This device was introduced in early 1990s when it was realized that biofilm in
seawater, where pitting corrosion on common stainless steels is a threat, produces on
stainless steel an ennoblement of oxygen reduction cathodic process up to 300 mV
(i.e. a the reduction of the activation overvoltage) then exceeding pitting potential and
triggering pitting initiation (see Chap. 11, Sect. 11.1). The device consists of an
electrode made of stainless steel and a reference electrode (typically, in seawater iron
is used) for continuous measurement of potential: an increase in the reading indicates
the setup of biofilm and therefore the high probability of pitting initiation on sus-
ceptible stainless steels or a signal that biocide water treatment failed.
Table 28.1 Reference electrodes used for potential measurement

Type of electrode (electrode Potential Use and notes
reaction) at 25 °C (V vs SHE)
SCE Calomel E = 0.268 − 0.0591 log [Cl−] Used in
(Hg/Hg2Cl2; Cl−) KCl sat E ¼ 0:244 laboratory as
Hg2Cl2 + 2e− ! 2Hg + 2Cl− Temp. Coeff. = −0.65 mV/°C reference
electrode to
calibrate
reference
electrodes used
in field
SSE Mercury/sulphate of mercury E = 0.615 − 0.0295 log [SO42−] Used in
(Hg/Hg2SO4; SO42−) K2 SO4 sat: E ¼ 0:710 laboratory
Hg2SO4 + 2e− ! 2Hg + SO42−
SSC Silver/silver chloride E = 0.222 − 0.059 log [Cl−] Used in
(Ag/AgCl; Cl−) 0:1 M KCl E ¼ 0:288 seawater also
AgCl + e− ! Ag + Cl− 1 M KCl E ¼ 0:222 as fixed
Obtained by anodic behaviour in Seawater E ¼ 0:250 reference
a NaCl solution Temp. Coeff. −0.6 mV/°C electrode,
although
sensitive to
pollution and
unstable. It
requires
periodical
refreshment
(anodic
behaviour). In
brackish waters
reference value
must be
calculated (Cl−
concentration
dependence)
CSE Copper/copper sulphate E = 0.34 − 0.0295 log [Cu2+] Used in soils.
(Cu/CuSO4; Cu2+) Saturated CuSO4 E ¼ 0:318 Easy to
Cu2+ + 2e− ! Cu For practical use E ¼ 0:3 prepare. Very
Consisting of a copper rod stable.
immersed in a saturated CuSO4 Chlorides may
solution. The ionic contact is contaminate
achieved by saline bridge made the electrode,
of wood or porous ceramic hence its use in
seawater is not
recommended.
Used in soil as
fixed reference
electrode
(continued)

Type of electrode (electrode Potential Use and notes
reaction) at 25 °C (V vs SHE)
ZN Zinc/seawater E = −0.80 Used in
Free corrosion reaction (Zn free corrosion potential) seawater as
fixed reference
electrode. Also
used in soil as
fixed reference
electrode
MN Manganese dioxide E = 0.35 Used in
(MnO2; KOH electrolyte, pH concrete as
13) fixed reference
electrode
MMO Activated titanium E = 0.20 Used in
Titanium coated with mixed (embedded in concrete, pH ≅ 13) concrete and
metal oxides of noble metals (Ir, soils as fixed
Rh). Alkaline electrolyte at reference
constant pH and oxygen electrode
provided it is
encapsulated in
constant
electrolyte. At
constant pH it
may be used as
oxygen probe
Table 28.2 Equivalencies of common reference electrodes (mV)

SHE SSC SCE CSE ZN MN MMO
SHE 0 −250 −240 −300 +800 −350 −200
SSC +250 0 +10 −50 +1050 −100 +50
SCE +240 −10 0 −60 +1040 −110 +40
CSE +300 +50 +60 0 +1100 −50 +100
ZN −800 −1050 −1040 −1100 0 −1150 −1000
MN +350 +100 +110 +50 +1150 0 +150
MMO +200 −50 −40 −100 +1000 −150 0
Example Value vs CSE = value measured vs RE used + value of column CSE
28.2.8 Hydrogen Probe
It works in acidic solutions where cathodic process is hydrogen evolution if a

poison of atomic hydrogen recombination to form hydrogen molecule is present.
The principle is as follow: a high percentage of atomic hydrogen produced by the
cathodic process (i.e., by corrosion) enters steel because of the poison, typically
hydrogen sulphide, H2S. Atomic hydrogen diffuses into steel and is captured in a
Fig. 28.8 Hydrogen probe

(principle)
bar
H2 H2
H
H2
suitable trap. Within the trap, atomic hydrogen combines to form hydrogen
molecules, then producing an increase in pressure, which can be measured by a
pressure gauge; the rate of increase in pressure is proportional to the corrosion rate.
Figure 28.8 illustrates schematically what a hydrogen probe consists of: in practice,
it is made of a hollow cylinder made of mild steel, in which hydrogen accumulates.
There is another device, the patch pressure probe, which measures diffusing
hydrogen directly. It consists of an electrochemical cell, directly fixed to the
external surface of a line, where the line surface works as anode, the electrolyte is
an alkaline solution and the cathode is a metal with low overvoltage for hydrogen
evolution. As soon as diffusing atomic hydrogen reaches the cell, it is oxidized to
H+ by imposing a voltage between anode, i.e., external surface, and cathode, where
H+ is reduced to hydrogen: the current flowing in the cell measures the diffusing
hydrogen, or in other terms, corrosion rate.
Hydrogen probe is typically used in oil and gas industry to monitor corrosion in
H2S-containing process fluids, where electrical resistance probe does not work.
Rather than to measure corrosion rate, it is more often used to drive the dosage of
corrosion inhibitor.
28.3 Other Methods
Methods used in laboratory testing, such as electrochemical noise, electrochemical

impedance spectroscopy and acoustic emission, were proposed for field applica-
tions. Except for acoustic emission, the other two methods are still in a pioneering
stage.
28.3.1 Electrochemical Noise
The method consists of the continuous measurement of potential and current

exchanged between two identical coupons. It works better for passive metals,
because current fluctuation increases when passive film breakdowns as localized
corrosion starts. It can indicate when operating conditions change to trigger
localized corrosion. It has been used in water cooling circuits.
28.3.2 EIS (Electrochemical Impedance Spectroscopy)
This method was tested on plants with deluding results; therefore, it is still at an
experimental stage. It seems to be promising to monitor coating efficiency and
check the passive film breakdown and to measure corrosion rate and inhibitor
efficiency.
28.3.3 Acoustic Emission
It is used in hydro-testing of equipment operating at high pressure. The goal of the

test is to localize the presence of defects within the metal, which may grow if they
exceed the critical size. This is important because a defect can grow during testing
without leading to unstable rupture, which can happen later during operation. To
localize the growing defect, at least three sensors have to be used to allow trian-
gulation of signals. The size of the defect is successively obtained through ultra-
sonic testing to define if defect size is critical, then deciding its removal.
28.4 Plant Inspection
Inspection of plants includes:

• Visual inspection of exposed surfaces before and after a careful surface cleaning
(sandblasting would be necessary) to check the presence of any corrosion attack,
either generalized or localized, and cracking. Visual inspection is a preliminary
activity which is carried out before proceeding with others, with the aim to
optimize time and efforts
• Use of Non-Destructive Techniques (NDT) for residual thickness measurements
or detection of cracks by means of various methods as magnetic particles, dye
penetrant, X-ray or c-ray, ultrasonic testing, eddy currents.
28.4 Plant Inspection 647
The planning of inspections follows the Risk Based Inspection approach, which
consists of the evaluation of risk (technical and economical) associated to the
occurrence of a corrosion event. A so-called risk matrix is used to help prioritizing
the inspection types; the risk matrix consists of two axes, one for the probability of
the event (i.e., corrosion) occurrence and the second one to set the entity of con-
sequences if the considered event takes place.
28.4.1 Liquid Penetrant
The use of liquid penetrant is a possible way to improve visual inspection. After a
surface cleaning to remove oxides and solid contaminants, a solution with
surface-active and coloured liquid is sprayed to form a continuous film. The
sprayed solution penetrates inside all discontinuities open to the surface, as
porosity, cracks, shrinkage areas and laminations. Excess penetrant is removed
from the surface and the liquid, which has entered discontinuities, is made visible
by a developer. Different penetrants and different developers are used, in particular
there are visible penetrants which produce red contrast at visible light or fluorescent
penetrants that are normally green and that can be seen using ultraviolet light. The
liquid penetrant testing has a very high sensibility, showing cracks with width even
lower than 0.1 mm.
28.4.2 Magnetic Particles
Another method used to improve visual inspection is the Magnetic Particle

Inspection (MPI). It can only be applied to ferromagnetic materials and allows
detecting surface or sub-surface discontinuities. The tested component is magne-
tised to produce magnetic field on the surface. A surface or sub-surface disconti-
nuity, which lies in a direction transverse to the direction of the magnetic field,
creates a distortion of the magnetic field lines. The distortion can be made visible by
means of small magnetic particles sprayed over the material surface. A defect,
which lies transversally the magnetic field lines, causes a large distortion of the
lines and gives a strong signal.
28.4.3 Radiographic Testing
Radiographic testing is based on the property of high-energy electromagnetic waves

to penetrate thick materials. A source of X-rays or c-rays is placed on one side of
the material to be tested, a photographic film is placed on the other side. The
radiation is partially absorbed by the tested material and more radiation will pass
through a region where material is thinner or a cavity is present, less radiation

where material is thicker or a denser phase is present. The transmitted radiation is
recorded on the film that is developed as negative: then a darker area indicates more
incident radiation, i.e., thinner or less dense material, a lighter one indicates less
radiation, i.e., thicker or denser material.
X-ray and c-ray are used to detect both internal and surface defects, as blisters,
voids and welding defects.
28.4.4 Ultrasonic Testing
The most used NDT is the ultrasonic testing (UT) because it is easy, fast and
precise. Figure 28.9 illustrates the principle of the method and a practical example
of application. A beam of high frequency sound waves is introduced by an UT
transducer (the Transmitter) into the test material for the detection of surface or
internal flaws. The sound waves travel through the material with some loss of
energy (attenuation) and they are reflected at the interfaces. The reflected beam is
received by another UT transducer (the Receiver), displayed on a screen and then
analysed to define the presence and location of flaws or discontinuities.
The UT probe must be coupled to the test object surface with a coupling
medium, normally a liquid or a gel, which allows transmission of elastic waves
from the probe to the piece and vice versa. UT results can be visualized in different
ways: the simplest way, called A-scan, is the representation on a time axis of the
amplitude of reflected waves. The B-scan represents defects on a plane
thickness-probe travelling direction and it gives information on the position of a
defect in the specimen thickness.
High-speed automatic ultrasonic inspection systems have been developed to
improve UT performance in particular in welding control during plant construction
when the weld geometry is regular and repetitive, e.g., pipeline girth welds or plate
welding of storage tanks. Automated UT is faster and more reproducible and
reliable than manual UT and data can be recorded as well as processed in more
complex ways, like 3-D tomography.
(a) (b)
Probe Probe
R R
T T
Thickness Thickness
Fig. 28.9 a Principle of UT for thickness measurement; b example of thickness measurement by

UT
28.4 Plant Inspection 649
The inspection of pipelines is performed by the use of tailored tools, called

intelligent PIG (Pipeline Inspection Gauge), based on UT method or
electro-magnetic principle to measure continuously the thickness and check the
presence of cracks or corrosion attacks.
28.4.5 Eddy Current Method
Eddy current inspection is used in a variety of industries to detect surface and near
surface defects. In fact, on thin materials, as tubing and sheet stock, eddy currents
can be used to measure the thickness of the material. This makes eddy current a
useful tool for detecting corrosion damage and other damages that cause a thinning
of the material. The technique is typically used to make corrosion thinning mea-
surements in the tubing walls in heat exchangers. Eddy current testing is also used
to measure the thickness of paints and other coatings.
In eddy current testing, a circular coil carrying an AC current is placed in close
proximity to an electrically conductive specimen. The alternating current in the coil
generates a changing magnetic field, which induces eddy currents within the wall.
Variations in the phase and magnitude of these eddy currents can be monitored using a
second “search” coil, or by measuring changes to the current flowing in the primary
“excitation” coil. Variations in the electrical conductivity or magnetic permeability, or
the presence of any flaws, will cause a change in eddy current flow and a corresponding
change in the phase and amplitude of the measured current. This is the basis of standard
(flat coil) eddy current inspection, the most widely used eddy current technique.
• API 1104, Welding of pipelines and related facilities, American Petroleum

Institute, Northwest Washington, DC.
• API RP 579, Fitness-for-Service, American Petroleum Institute, Northwest
Washington, DC.
• BS 7910, Guide on methods for assessing the acceptability of flaws in metallic
structures, British Standard.
• EN 473 Non-destructive testing. Qualification and certification of NDT per-
sonnel, European Committee for Standardization, Brussels.
• EN 13455, Unfired pressure vessels. Part 5 - Inspection and testing, European
Committee for Standardization, Brussels.
• ISO 9712, Non-destructive testing. Qualification and certification of personnel,
• SNT-TC-1A, Recommended practice, personnel qualification and certification
in non-destructive testing.
28:1 Lists pros and cons of direct and indirect monitoring methods.
28:2 Which forms of corrosion do you monitor by corrosion coupons?
28:3 Describe the principle of the potential measurement. What devices do you
need? With what features?
28:4 The free corrosion potential profile of a buried pipeline, 5 km long, has been
measured, a reading every 200 m. Based on the profile, it is possible to
estimate the corrosion rate? Why? Make some numerical examples.
28:5 Imagine to calibrate an SCE electrode with an SSC (1 M KCl) electrode.
Which is the potential difference in absolute value? And between a CSE and
ZN electrode?
28:6 A corrosion inhibitor has been added in a pipeline. How LPR can be used to
check its efficiency and to optimise its dosage?
28:7 Both corrosion coupon and LPR are used to estimate corrosion rate. Which
are the main differences between the two methods? When LPR should be
preferred to coupon?
28:8 Lists the benefits of non-destructive testing.
28:9 Choose a non-destructive technique to verify internal defects in the welds.
Describe how it works and which information are detectable. Can penetrant
liquid be used? Why?
28:10 Why intelligent PIG are periodically used on pipelines transporting oil?
28:11 A 50 km long cladded pipe (base metal carbon steel, clad in alloy 625) is
used to convey a sour fluid from a platform to the onshore plant. All cir-
cumferential welds has to be checked. Which NDT would you suggest?
Why? Which information each technique is able to give?
28:12 The internal bottom of a carbon steel tank (40 m in diameter) suffered
generalized corrosion due to the presence of a corrosive liquid. How to
monitor the residual thickness? Has the measurement to be performed on the
entire internal surface? How to select the area to be analysed?
Bibliography
1. API RP 580, Risk-based inspection methodology. American Petroleum Institute, Washington,

DC
2. API RP 581, Risk-based inspection methodology. American Petroleum Institute, Washington,
DC
3. ASM Metals Handbook (2001) Non-destructive evaluation and quality control, vol 17. ASM
International, Northern New England
4. Hellier C (2003) Handbook of nondestructive evaluation, 2nd edn. McGraw-Hill Education,
New York
5. Lazzari L, Pedeferri P (2006) Cathodic protection. Polipress, Milan, Italy
6. Shull PJ (2001) Nondestructive evaluation. Marcel Dekker, New York, NY
Chapter 29
Testing
There’s something with these tears

Turning me to rust.
Echo & the Bunnymen
Abstract Corrosion tests are an important instrument used to clarify the mecha-
nisms of corrosion process, to develop new materials and new methods of protection,
to carry out quality control tests, to follow the behaviour of materials in operation
and, finally, when corrosion has occurred, to study the causes and the remedies. The
classification of corrosion tests adopted in this chapter provides the division in two
macro categories: exposure tests and electrochemical tests. This chapter wants to give
some examples of the many possibilities of existing corrosion tests.

https://doi.org/10.1007/978-3-319-97625-9_29
652 29 Testing
29.1 Test Classification
Corrosion tests can be classified in different ways as witnessed in the specific

bibliography which does not acclaim any univocal classification. The most general
classification distinguishes the tests according to form of corrosion, environments
(natural and industrial) or materials, or again in short, medium and long-term tests
(accelerated or in service tests). To validate the metal selection carried out in
design, exposure testing is often required. It consists of testing candidate metals in
process fluid, following two conditions: same process condition (in service) or
so-called accelerated conditions (Fig. 29.1).
The accelerated tests clearly contain the quality control tests and pass-fail tests.
The first type of test consists of standard tests required and carried out to check
compliance with acceptance criteria. Test conditions can be in accordance with
international standards, as CEN, ASTM, ISO, NACE, national regulation, as UNI in
Italy, or according to company standards. For example, the most common and
known are Huey Test, Strauss Test and Streicher Test for intergranular corrosion
susceptibility of stainless steels and nickel alloys, or FeCl3 tests for pitting corro-
sion. Many localized corrosion attacks, follows a behaviour described by a pdf of
Log N type or very close to it. This implies that the occurrence of the attack
happens during the first period of exposure (also said infant mortality) rather than
after long exposure time. In other words, should the attack take place, this does
occur very soon or never. Based on this behaviour, so-called pass-fail tests are
performed for a pre-determined fixed exposure time: test is passed if within the
exposure time no failures, or damage below a threshold, occurred.
The classification adopted in this chapter provides the division in two macro
categories: exposure tests and electrochemical tests. The exposure tests consist of
direct exposure of the metal to an environment that simulates real aggression
conditions, or makes it more severe. Exposure can take place in natural environ-
ments as well as artificial environments (for example climatic chamber, auto-
clave…), in immersion (continuous or intermittent) in natural or synthetic
(aggressive) solutions. Electrochemical test are the basic laboratory tests that pro-
vide the determination of basic corrosion-influencing parameters that are published
in journals and books: thermodynamic and kinetic parameters, as anodic and
cathodic characteristics, corrosion potential in referred electrolytes, tendency to
passivation, oxidant power. Since test conditions are rigorously controlled, results
show a high reproducibility.
This chapter far from being exhaustive describes the most important tests, their
purposes and the possible applications.
29.2 Accelerated Tests and Statistics 653
29.2 Accelerated Tests and Statistics
Aim of corrosion test is the achievement of a result in short time, if possible, and the
extrapolation to a longer time as design life or even greater. Figure 29.2 illustrates
the simplest meaning of an extrapolation from laboratory testing results to the
shorter time.
To accelerate the test, a corrosion-related parameter or factor is conveniently
increased. Extrapolation is possible, hence acceptable, if the following conditions fit:
• Corrosion mechanism is the same (for instance, same cathodic process)
• There is a relationship between rate (i.e., time) and varied parameter
• Probability density distribution of results is the same.
Last condition derives from reliability and is clearly represented in Fig. 29.3. In
normal operating, no failure is expected, instead by increasing an influencing
parameter failure occurs because resistance is overwhelmed. Arrhenius firstly rec-
ognized that in accelerated tests the relationship between time and the affecting
parameter is logarithmic as follows:
MTTF ¼ A eBðrCÞ ð29:1Þ
MTTF is generic time-to-failure (or testing time); A, B and C are experimental

constants and r is the affecting parameter. The plot in semi-logarithm scale,
ln MTTF versus r, is depicted in Fig. 29.2:
• Affecting parameter, r, varies in the range r > C
• When r = C, MTTF > A
• B is slope of the straight line.
ln MTTF
Operating condition
A
Laboratory
tests results
C
Affecting parameter (linear scale) σ
Fig. 29.2 Principle of extrapolation from testing results to operating conditions (from Lazzari
2017)
654 29 Testing
Operating Testing Failure
Probablility Density f(t)
Accelerated test
C
S-R
Fig. 29.3 Comparison of probability density distribution of failure-related parameters in testing

and operating (from Lazzari 2017)
MTTF is a distribution. In Fig. 29.2 the relevant value is plotted, as mean in case
of uniform distribution or most likely a minimum or maximum value given by the
extreme value statistics, generally Weibull or Gumbel. Statistics is described in
Chap. 30. For more details on the use and interpretation of accelerated tests, refer to
Lazzari (2017).
29.3 Exposure Tests
Tests are carried out by direct exposure of metal coupons to the environment, which
can be the same as in service or modified to increase aggressiveness (accelerated
tests).
Typical parameter measured is mass loss for uniform corrosion. In localized
corrosion related testing, other parameters are measured or controlled:
• In pitting corrosion tests: initiation time, critical chloride concentration, critical
pitting temperature (CPT), pit depth, pit density
• In crevice tests: percentage of sites attacked, depth of attacks, critical crevice
temperature (CCT)
• In intergranular tests: presence of attacks, checked by micrographic examination
and quantified by mass loss
• In SCC tests: presence of cracks or time-to-failure.
29.3 Exposure Tests 655
To test coating and painting performance, the standardized salt spray test (also
known as salt fog test) is often used for comparison or ranking, although its the-
oretical basis is doubtful.
29.3.1 Mass Loss
It is the simplest corrosion test. These tests is carried out by immersion in a

solution, in natural or artificial atmosphere and inside equipment or plants. It
consists in measuring the mass variation to determine the corrosion rate by the
exposure of a metallic coupon to an environment for a defined time. The sample is
weighed before and at the end of exposure after removing, usually by pickling, the
corrosion products. The mass loss of the sample, Δm, is then evaluated and, given
the exposure time (t) and the exposed surface of the sample (S), the mass loss rate
per unit area, Crate,m, and the thinning rate, Crate, are calculated with the formulas
seen in Chap. 1.
This test is standardized; in particular ASTM G1 is specific for preparing
specimens, for removing corrosion products after the test and for evaluating the
corrosion damage that has occurred. A complete set of tables shows the cleaning
procedure (chemical or electrolytic) to remove corrosion products without signifi-
cant wastage of base metal; for each class of metals is indicated the solution, the
temperature and the duration. This allows an accurate determination of the mass
loss of the metal or alloy that occurred during exposure to the corrosive environ-
ment. These procedures, in some cases, may apply to metal coatings. However,
possible side effects from the substrate must be considered.
ASTM G31 describes in details apparatus, sampling, test specimens and test
condition (composition, temperature, agitation aeration) and test duration to con-
duct immersion tests. As regards the latter parameter, as rule of thumb, the mini-
mum exposure time (in hours) should comply with the ratio 50/Crate (in mm/year) to
obtain reliable and measurable data. To reduce the test times, the aggressiveness of
the exposure environment can be increased: this is the case of the salt spray tests.
These tests are used as quality control tests, to quickly compare different materials.
Rarely, however, the results of these tests can be used to predict the actual beha-
viour of a metal (see Sect. 29.3.8).
29.3.2 Pitting Corrosion
In the presence of localized corrosion, mass loss is useless. Most commonly the
number of localized attacks (pits) per unit area or the pit depth are detected, or the
maximum penetration rate (obtained by dividing the maximum depth of the pit for
the exposure time) is calculated.
656 29 Testing
a) narrow, deep
b) elliptical
(a) (b) (c)
c) wide shadow
d) subsurface
e) undercutting
(d) (e)
f) microstructural orientation
(f)
Fig. 29.4 Variations in the cross-sectional shape of pits (according to ASTM G46)
ASTM G46 covers the procedures for the identification and examination of pits
and for the evaluation of pitting corrosion to determine the extent of its effect. The
standard specifies the type of the inspection, visual or non-destructive (radio-
graphic, electromagnetic, sonic and penetrants), how to determine the pith depth
and how to describe the pitting in terms of density, size, and depth. Examples of
analysis of pitting-related testing taken from ASTM G46 are reported in Figs. 29.4
and 29.5.
One of the well-known test of localized corrosion is represented by the ferric
chloride (FeCl3) test, ASTM G48, to determine the susceptibility to pitting (or
crevice) corrosion of stainless steels and nickel alloys, and in particular to define the
critical temperature of pitting and crevice.
The ASTM G48 standard provides the method to expose the material to a
concentrated oxidizing chloride-containing environment. The solution simulates the
chemical composition of the environment inside a pit in a stainless steel. The
standard describes six methods depending on the form of localized corrosion
(pitting or crevice) and on the metal (stainless steel or nickel-based and
chromium-bearing alloys). The specimen is exposed to a FeCl3 solution for a
relatively short time (72 h) at a certain temperature (function of the metal com-
position). The test must be performed with 3–5 specimens at least and at the end of
the test, both mass loss and localized attacks are checked. It is a comparative test:
no extrapolation can be done under different environmental conditions.
29.3.3 Crevice Corrosion
Also for crevice corrosion, mass loss measurements only are useless. For this form
of corrosion, it is necessary an apparatus that reproduces the operating conditions
that favor corrosion. Typically the device is generally called “crevice former” or
Fig. 29.5 Standard rating A B C

charts for pits (adapted from Density Size Depth
ASTM G46)
2.5 103 /m2 0.5 mm2 0.4 mm
5 104 /m2 8.0 mm2 1.6 mm
5 105 /m2 24.5 mm2 6.4 mm
“crevice assembly” (ASTM G48 reports some example). Examples of crevice

formers are shown in Figs. 29.6, 29.7 and 29.8.
The apparatus was originally developed by Anderson: it consists of two serrated
segmented washers, of inert material (PTFE), with 20 crevice sites (slot) created
beneath each washer. Two of this washers when attached with a nut and bolt to a
flat test specimen generate 40 individual crevice sites.
Since ASTM G48 has already been discussed, another example of crevice test
standard is here discussed. ASTM G78 standard describes the crevice corrosion test
for samples of different geometries (flat and cylindrical). Although the test is
suitable for seawater applications, it can be used in other aqueous
chloride-containing environments. This standard, in addition to different geometries
of specimens, describes the possible apparatus to create the gap, for example
coupons, strips, O-rings, blocks continuous and segmented washers. The severity of
the test can vary according to the crevice former, which differ in size and degree of
tightness. Metal samples are exposed to the environment for a standardized time,
typically 30 days. Susceptibility to crevice corrosion is assessed through three
parameters: mass loss, corroded area measurement and penetration depth.
Figures 29.9 and 29.10 show the result of a crevice testing on stainless steel in
seawater.
658 29 Testing
Fig. 29.6 Crevice former

designs
Fig. 29.7 Example of new

crevice former
Fig. 29.8 Example of

assembly of new crevice
former
Fig. 29.9 Example of a

result of crevice testing

on laboratory samples of
stainless steel AISI 316
29.3.4 Galvanic Coupling
The test method for galvanic corrosion consists in immersing the metallic coupling
in the environment of interest. Obviously, the material surface condition, the
environment and the geometry, above all the ratio between the cathodic and the
anodic areas (see Chap. 10) should simulate the real application. Particular attention
to the electrical connection should be given.
ASTM G71 covers conducting and assessing galvanic corrosion tests to describe
the behaviour of two different metals in electrical contact, in an electrolyte under
low-flow conditions. The body of the standard fully describes material and speci-
mens preparations as well as the environment (laboratory or field), the method of
exposure, the procedure and the method for evaluating the results. During the
660 29 Testing
exposure, galvanic current and potentials measurements have to be recorded. At the

end of exposure, if possible, mass loss and visual inspection are recommended.
29.3.5 Integranular Corrosion
Mass loss test is used also for intergranular corrosion tests combined with visual
observations. ASTM A262 standard practice for detecting susceptibility to inter-
granular attack in austenitic stainless steels is used to verify their susceptibility to
intergranular corrosion. The standard provides five test methods, each with a dif-
ferent solution (Table 29.1) and time of test ranging from few minutes to 10 days
depending on the composition of stainless steel examined. At the end of the test, the
weight loss is determined, the presence of corrosion attacks along the weld are
observed and the maximum depth of attack is measured.
ISO 3651 Part 1 and Part 2 concern the Huey test and the Strauss test,
respectively.
ASTM G28 covers the intergranular corrosion test for wrought, nickel-rich,
chromium-bearing alloys. Two practices are reported: method A, ferric
sulphate-sulfuric acid test; method B, mixed acid-oxidizing salt test. The solutions
are still boiling and the time of test is 24–120 h long, depending on the type of
metal. At the end of the test, weight loss is determined, metallographic examination
is observed if necessary, and the maximum depth of attack is measured.
Table 29.1 Description of the five practice, according to ASTM A262

Practice Test name Temperature Time
A Oxalic acid etch test for classification of etch Ambient 1.5 min
structures of Austenitic SS: “Screening Test”
B Ferric sulfate–sulfuric acid test for detecting Boiling 120 h
susceptibility to intergranular attack in austenitic SS:
“Streicher Test”
C Nitric acid test for detecting susceptibility to Boiling 48 h
intergranular attack in austenitic SS: “Huey Test” (5 times)
E Copper–copper sulfate–sulfuric acid test for Boiling 15 h
detecting susceptibility to intergranular attack in
austenitic SS: “Strauss Test”
F Copper–Copper sulfate–50% sulfuric acid test for Boiling 120 h
detecting susceptibility to intergranular attack in
molybdenum-bearing austenitic SS
To determine the susceptibility to SCC, different types of tests can be performed.

Tests are classified as follows:
• Constant load
• Constant strain
• Slow strain rate
• Fracture mechanics test (pre-cracked specimens).
Laboratory tests were developed to accelerate the SCC response of specific metals
and for developing solutions that simulate the exposure service conditions. ASTM
G36 is the most known standard. It describes the procedure for conducting stress
corrosion cracking tests in boiling magnesium chloride at about 155 °C. This
specific testing environment offers an accelerated method to classify the degree of
susceptibility to stress corrosion cracking in environments containing chlorides.
This test is applicable to stainless steels and susceptible alloys as castings, welded
and plastic worked products and is a method for detecting the effects of compo-
sition, heat treatment, surface finishing (Fig. 29.11).
Constant load test. A specimen, generally cylindrical in shape, is loaded by a

tensile test machine while exposed to the environment, at a constant nominal stress
level. Aim of the test is to determine the threshold stress level, below which SCC
does not occur, and the time-to-failure. Figure 29.12 shows a typical r-time plot.
Constant strain test. A pre-stressed specimen, to have a predetermined strain, is

immersed in the solution test for an agreed exposure time, generally one month.
Specimens are C-ring or U-bend or bend beam types. At the end, failure or presence
of cracks is checked. By a series of specimens, stressed at different levels, threshold
Fig. 29.11 Strauss test

662 29 Testing
σ
(MPa)
500
400 AISI 310, 314
300
AISI 305, 309

200 316, 347
AISI
100 304, 304L
1 10 102 103
Time (h)
Fig. 29.12 Time-to-failure as a function of the applied nominal stress for different austenitic
stainless steels in a boiling solution of magnesium chloride (42% by weight)
60°
Constant strain Constant load Notched C-ring
Fig. 29.13 Methods of loading C-rings (adapted from ASTM G38)
stress is determined. ASTM G38 standard deals with the design and processing
features, and the procedures for stressing, exposing and inspecting the specimens
(C-ring) to be subjected to stress corrosion. The standard includes the methods,
formulas and tables used for the determination of stress according to the imposed
deformation. Figure 29.13 shows examples of how to load the C-rings. ASTM G30
Fig. 29.14 Examples of

U-bends (adapted from
ASTM G30)
weld
covers techniques for making and using U-bend specimens. Usually, the U-bend
specimen is a stripe which is bent 180° around a predetermined radius and main-
tained in this constant strain condition during the test. Examples of configurations
of the U-bend samples are reported in Fig. 29.14. In H2S-containing environment,
pass-failed criterion is used. NACE TM0177 is an example of test method for
testing metals immersed in low-pH aqueous environments containing hydrogen
sulphide (H2S) and subjected to tensile stresses. The test method is one of the most
famous relatively to sulphide stress cracking (room temperature and pressure) and
stress corrosion cracking (elevated temperatures and pressures). It describes spec-
imens, test solutions and operating conditions, and test vessels and fixtures. Four
practices are reported: Method A—Tensile Test, Method B—Bent-Beam Test,
Method C—C-Ring Test and Method D—Double-Cantilever-Beam (DCB) Test.
Slow strain rate test. This test is similar to the one at constant load, while operated
dynamically by applying a constant strain rate in the range 10−7 to 10−4 s−1.
Stress-strain curves obtained in inert environment, generally in air or oil, and in
reference environment are compared through: maximum load, elongation and
reduction of cross surface area. A visual inspection checks fracture surface feature
and the presence of secondary cracks.
Fracture mechanics test. Previous tests utilize smooth specimens while this test is
based on notched specimens. The notch is generally a fatigue crack. Test is carried
out at constant load or constant strain; in the latter, specimen used is WOL or
WOL-modified (WOL means Wedge Opening Loaded), as shown in Fig. 29.15. At
the end of test, crack growth is measured, then allowing the calculation of KI-SCC: in
fact, crack growth stops as soon as KI lowers to KI-SCC.
664 29 Testing
Fig. 29.15 WOL specimen

for SCC test at constant strain
29.3.7 Erosion, Cavitation and Fretting
Many standards regarding erosion, cavitation and fretting wear exist, as ASTM
G32, ASTM G73, ASTM G76 and ASTM D4170. It is important to recognize the
mechanism and consequently the main factors that control the phenomenon in order
to select the proper test condition. Apparatus, test materials, sampling, procedure
and data analysis are carefully described in the standard. For example, in ASTM
G76 for conducting erosion tests, geometry and velocity of solid particles, specimen
orientation relative to the impinging stream, temperature of the specimen and
particles carrier gas and test duration are defined. The steady state erosion rate is
determined from the slope of the mass loss versus time plot. The average erosion
(mm3/g) is calculated by dividing erosion rate (mg/s) by the abrasive flow rate (g/s)
and then dividing by the specimen density.
29.3.8 Artificial Atmosphere—Cabinet Test
Since 1900, cabinet tests have been used to evaluate coatings performance and to
carry out accelerated corrosion tests. Cabinet testing takes its name from the closed
chamber in which tests are conducted and where the conditions of exposure are
controlled. This type of test is generally used for corrosion performance of metals
used in natural atmospheres as pass-fail test.
The environment produced inside the chamber combines usually: salt fog,
humidity, hot and low temperature, corrosive gases and ultraviolet exposure.
In order to correlate test results with service performance, it is necessary to
establish acceleration factors and to verify that the corrosion mechanisms are indeed
following the same paths.
The salt spray (or salt fog) test is one of the most widespread, long established
and standardized test method. Usually, coated metals are tested to verify the degree
of corrosion protection of the coating to the underlying metal. The appearance of

corrosion products (rust or other oxides) is evaluated after a pre-determined period
of time. Test duration depends on the corrosion resistance of the sample.
The apparatus for testing consists of a closed testing cabinet or chamber, where a
salt water (5% NaCl) solution is atomized by means of spray nozzles using pres-
surized air. A corrosive environment of dense salt water fog is produced in the
chamber, so that test samples exposed to this environment are subjected to severely
corrosive conditions. Chamber volumes vary from supplier to supplier. If there is a
minimum volume required by a particular salt spray test standard, this will be
clearly stated and should be complied with. There is a general historical consensus
that larger chambers can provide a more homogeneous testing environment.
ASTM B117 was the first internationally recognized salt spray standard,
originally published in 1939. Other important relevant standards are ISO 9227,
JIS Z 2371 and ASTM G85.
ASTM B117 reports apparatus, procedure and conditions required to produce
and maintain the Neutral Salt Spray test (often abbreviated to NSS); type of test
specimen, exposure periods or the interpretation of the results are specified or
mutually agreed between the purchaser and the seller. Results are represented
generally as testing hours in NSS without appearance of corrosion products.
ASTM G85 describes five modified salt fog tests: acetic acid-salt spray test
(ASS); cyclic acidified salt spray test; seawater acidified test, cyclic (SWAAT); SO2
salt spray test (cyclic test), dilute electrolyte cyclic fog dry test. The more severe
test is performed in acetic acid with copper chloride (CASS).
Humidity test and corrosive gas test are also conducted in cabinet according to
specific standards.
29.4 Electrochemical Tests
Electrochemical test are typically laboratory tests used to define the basic
corrosion-influencing factors, as thermodynamic and kinetic parameters, anodic and
cathodic characteristics, corrosion potential in referred electrolytes, tendency to
passivation, oxidant power. Since test conditions are rigorously controlled, results
show a high reproducibility.
Instrument used to plot the anodic and cathodic curves measure a total current
density, equal to the algebraic sum of the anodic and cathodic current densities. At the
free corrosion potential, the measured external current is zero (anodic current equals
cathodic current). At potential more noble than free corrosion potential, the anodic
current density exceeds the cathodic one, the opposite occurs at less noble potential.
When far from the free corrosion potential (at least 50 mV), measured current density
coincides with anodic or cathodic one, then following Tafel law (Fig. 29.16).
Polarisation curves can be obtained by two methods: galvanostatic (i.e., by
imposing the current) and potentiostatic (i.e., by imposing the potential).
Figure 29.17 shows the principle of the two methods. The galvanostatic method is
666 29 Testing
Fig. 29.16 E-Log i diagram of a corroding metal in acidic solutions (experimental curves and
Tafel straight lines)
Potenziostat
(a) (b) 1 2 3
S
R
I I
I I
E E
A A
ε ε
I I
W RE CE W RE CE
Fig. 29.17 Experimental set-up to obtain the characteristic curves: a galvanostatic mode;
b potentiostatic mode (W is working electrode; RE is reference electrode, CE is counter-electrode)
easy and requires simply a generator, an ammeter and a voltmeter: once fixed the
circulating current (i.e., the current density) the electrode potential is measured. The
measurement is carried out by increasing steps, often manually. The potentiostatic
method is more sophisticated since it requires a tailored instrument, which is the
potentiostat, introduced by Edeleanu at University of Cambridge, UK, in 1954. An
electronic circuit that allows to vary the potential independently from the circulating
current characterizes the potentiostat. The instrument works as depicted in
Fig. 29.18. The potential, E, of the so-called working electrode is continuously
increased and simultaneously compared to a floating pre-fixed value, EC, in order to
29.4 Electrochemical Tests 667
POTENZIOSTAT
Current
Ec ΔE Δ·ΔE I
generator
Amplifier Cell
(voltage
regulation) E
E
Fig. 29.18 Block scheme principle of a potentiostat
(a) (b)
E E
log i log i
Fig. 29.19 Active-passive curve obtained by: a galvanostatic mode; b potentiostatic mode
measure the difference E-EC; the potentiostat imposes a current which zeros con-
tinuously and dynamically the measured difference of the potentials. By this “trick”,
current can either increase or decrease.
The potential variation can be performed by steps (potentiostatic mode) or
continuously (potentiodynamic mode). In conclusion, potential is the variable and
current is the output.
The two methods, galvanostatic and potentiostatic, are not equivalent: to char-
acterize an active-passive behaviour, potentiostat method is more suitable. It should
be considered that by applying, step-by-step, galvanostatic method, the entire curve
cannot be obtained (Fig. 29.19a) because once reached the critical passivation
current, the potential jumps directly to transpassive zone, then losing the passive
interval and the passivity current density value. In other words, Log i-E plot is less
complete than E-Log i one; on the other hand, potentiostatic method acts as a
corrosion process, where driving voltage determines the corrosion current and not
the opposite (Fig. 29.19b).
Often, also in this textbook, Evans diagram is used with “log i” as abscissa,
although the variable is the potential, E (Fig. 29.20).
668 29 Testing
(a) (b)
E log i
log i E
Fig. 29.20 Evans diagram representation: a E-log i plot; b log i-E plot
When running a test, either galvanostatic or potentiostatic, attention should be

paid on ohmic drop contribution in high resistivity electrolytes. To minimize it,
Luggin capillary or a Piontelli probe are conveniently used. Furtherly, it must be
remembered that polarization curve depends on sweep/scanning rate; international
standards recommend a rate not higher than 20 mV/min.
Tafel extrapolation method. As shown in Fig. 29.16, from the anodic or cathodic
curves, often from one of them only, by extrapolating Tafel straight line to the
corrosion potential, Ecorr, corrosion rate, icorr, is obtained. Exchanged current
densities are easily obtained by extrapolation to the calculated equilibrium potential
according to the metal under corrosion of the cathodic predominant process. Tafel
slopes may be estimated directly from the graph. This method is simple, easy, quick
and accurate when single anodic and cathodic processes occur. Accordingly,
potential is scanned from −200 mV to +200 mV with respect the measured free
corrosion potential. No standards currently exist for this method.
Linear polarization resistance (LPR method). Also called Stern-Geary method.
The principle of the method is the following: a metal is polarized from its
free-corrosion potential, Ecorr, toward anodic or cathodic direction by imposing an
external current density, ie. The polarization ΔE (=|E − Ecorr|) is in the range of
maximum 20 mV. The ΔE/ie ratio, called polarization resistance, Rp (X m2), is
inversely proportional to the corrosion rate through the Stern-Geary equation
(see box):
B
icorr ¼ ð29:2Þ
Rp
where B is a constant, estimated as follow:
1 ba bc
B¼ ð29:3Þ
2:3 ba þ bc
ba and bc are the Tafel slopes of the anodic and cathodic process, respectively.
Constant B is typically 0.026 V/decade for active metals in acids
(ba = bc = 0.12 V/decade) and 0.052 for active metals in aerated solutions under
diffusion control (ba = 0.12 V/decade; bc = infinite).
As said, the method is reliable for small polarizations, i.e., ΔE 20 mV,
typically 10 mV. The method appears as more precise as corrosion rate is low, so it
is more attractive and useful than mass loss coupons, when long exposure time
would be required, or when on-time interventions is necessary as for inhibitor
dosage adjustment. Furthermore, it allows measurements without coupon retrieval
and the continuous monitoring on plants. It is applied in a variety of environments,
as process fluids, waters and concrete. Some conditions jeopardize the accuracy of
the measurements as corrosion potential too close to equilibrium potential, high
resistivity, i.e., high ohmic drop; however, rather than absolute values, variations in
time can be conveniently used. The most evident drawback of the method is that it
works for uniform corrosion, only.
ASTM G59 covers an experimental procedure for polarization resistance mea-
surements, which can be used for the calibration of instruments and verification of
experimental technique. The test method can provide reproducible corrosion
potentials and potentiodynamic polarization resistance measurements.
Stern-Geary Equation
To cause a small cathodic polarization, ΔEc, an external current density, ie, is
applied, which is given by ie = ic − ia, where ic and ia. are cathodic and
anodic current density, respectively.
From the figure, the following can be written:
CB ¼ OC=bc ; CB ¼ log ic log icorr ¼ logðic =icorr Þ ¼ DE c =bc

AC ¼ OC=ba ; AC ¼ log icorr log ia ¼ logðicorr =ia Þ ¼ DEc =ba
ic ¼ icorr 10DEc =bc ; ia ¼ icorr 10DEc =ba ; i ¼ ic ia ¼ icorr ½10DEc =bc

DE c =ba
10
Because ΔEc is small (about 10 mV) compare to bc and ba (higher than
100 mV) the following approximation is acceptable:
10x ¼ 1 þ ðlog 10Þx þ ðlog 10Þ2 x2 =2 þ ffi 1 þ ðlog 10Þ x

670 29 Testing
Fig. 29.21 Polarization curves to explain Stern-Geary extrapolation method of corrosion rate
therefore:

DEc DEc
i ¼ icorr 1 þ 2:3 1 þ 2:3
bc ba
1 ba b c I 1 ba bc 1
icorr ¼ ¼
2:3 ba þ bc DE 2:3 ba þ bc Rp
where ΔE is either cathodic or anodic and Rp is polarization resistance

(Fig. 29.21).
Electrochemical Impedance Spectroscopy (EIS). In 1960s I. Epelboin (1916–

1980) and his research group in Paris introduced the method with the aim to study
the processes occurring at the electrode interface. It consists of injecting an alter-
nating current between a working electrode and a counter electrode and plotting the
potential and the current measured at different frequency (from this the name
spectroscopy). Potential E(t) and current density i(t) are linked through impedance
Z(w), which are function of frequency, f (x = 2pƒ):
E ðtÞ ¼ Z ðxÞ I ðtÞ ð29:4Þ
where E(t) = Eo sin xt; I(t) = I0 sin (xt + h); x = 2pƒ; h is angle phase and ƒ is
frequency (hertz).
Anodic and cathodic processes occurring on surface electrode influence the
angle phase, h, which is important for the interpretation of the process. Circuit
impedance is a complex parameter, therefore composed of a real component Z′(x)

and an imaginary one Z″(x), in phase opposition:
j
ZðxÞ ¼ Z 0 ðxÞ þ Z 00 ðxÞ ¼ R ð29:5Þ
xC
It appears that electronic circuit, composed of resistances (real component) and

capacities (imaginary component), can simulate processes. The capacity can rep-
resent the delay, i.e. h, of the signal.
To ease the interpretation, Nyquist diagrams, Z″(x) against Z′(x) are used,
associated to an equivalent electronic/electrical circuit. Two simple typical case
studies are considered.
The first one is uniform corrosion where only activation overvoltage applies.
Equivalent electrical circuit is simply a resistor and a capacitor in parallel, repre-
senting the activation overvoltage, and a resistance in series, which represents
electrolyte resistance (proportional to resistivity). The circuit is known as equivalent
Randles circuit. Nyquist diagram is a semicircle (Fig. 29.22) where frequency
increase is anticlockwise. Either at high or at low frequency, imaginary component
Z″(x) zeros, then allowing the measurement of electrolyte resistance RX at high
frequency and RX + Rp at low frequency, where Rp is transfer charge resistance.
The second case study is a uniform corrosion process under diffusion control or
in the presence of coatings or scales. The equivalent electrical circuit contains
so-called Warburg impedance, W, revealed at low frequency by the presence of a
45° slope line (Fig. 29.23), which is a finger print of the type of process.
To carry out an EIS measurement a tailored instrumentation is required and
consisting of a feeding system in a wide range of frequency, a precision potentiostat
and a signal analyser. ASTM G106 standard covers an experimental procedure to
check instrumentation and technique for collecting and presenting electrochemical
C

-Z’’
R
Rp
R Rp+ R
Z’
Fig. 29.22 Equivalent electrical circuit and Nyquist diagram for a corrosion process driven by
activation overvoltage
672 29 Testing
C
45°

-Z’’
R
W
Rp
R Rp+ R
Z’
Fig. 29.23 Equivalent electrical circuit and Nyquist diagram for a corrosion process driven by
diffusion overvoltage
impedance data. It provides standard material, electrolyte and procedure for per-
forming EIS at the open circuit or free corrosion potential. This practice may not be
appropriate for collecting impedance information for all materials or in all
environments.
29.4.2 Pitting Potential and Repassivation Potential
To determine the susceptibility to pitting of stainless steels, a cyclic potentiody-

namic polarisation test is performed by imposing a potential scan from the free
corrosion potential (or a little more cathodic value) forward the anodic direction
until current density reaches 10 A/m2 (or other agreed value). Potential is then
reversed until passivity is again established. The two potentials are pitting potential
and repassivation potential, respectively (Fig. 29.24). Both potential scan rate and
current density threshold influence the result: pitting potential lowers as scan rate
decreases and repassivation potential lowers as current density threshold increases.
Accordingly, tests are performed following standards, as ASTM G61.
29.4.3 Galvanic Coupling
Two different metals are connected each other with a zero resistance ammeter and
immersed in the same solution. The galvanic corrosion rate is directly estimated as a
function of time. Calculated corrosion rate must be added to the corrosion rate in
free corrosion conditions. Standards do not exist for direct measurements of gal-
vanic current.
Pitting 1
Epit
Imperfect passivity 2
Erp
Perfect passivity 3
Activity
Eprot
Immunity
log i
Fig. 29.24 Pitting and repassivation potential measurement
29.4.4 Intergranular Corrosion
An electrochemical test, called EPR, Electrochemical Potentiokinetic Reactivation,

is used to check sensitization of stainless steel and nickel-based alloys. ASTM
G108 standard is typically used. After surface preparation of specimen, a potential
polarization +0.2 V SCE is imposed by a potentiostat in a 0.5 M H2SO4 + 0.01 M
KSCN solution at 30 °C. After that, a potential scan toward cathodic direction is
recorded as shown in Fig. 29.25. Test result is interpreted by comparison with
non-sensitized specimen behaviour: in general, the higher the nose area the more
sensitization degree.
E
(V SCE)
+0.2
Not
sensitized Sensitized
2
1
Ecorr
log i
Fig. 29.25 EPR test interpretation (according to ASTM G108)

674 29 Testing
For SCC by slip-dissolution mechanism, the critical intervals of potential can be

obtained by comparison of anodic polarization curves, respectively worked out at
low and high potential scan rate. The latter, i.e. high scan rate, shows the metal
behaviour when not yet completely covered by a film, while the former shows the
opposite. Critical intervals are easily found by comparison where anodic dissolution
rate in scan rate test exceeds the other one. Figure 29.26 shows an example for
carbon steel in carbonate/bicarbonate solution.
29.4.6 Other Electrochemical Techniques
Potentiostatic. Potentiostatic polarization can be used alternatively or in addition to

potentiodynamic polarization techniques, in cases where conditions of stable state
are desirable. It consists in applying through a potentiostat a constant potential at
the metal-solution interface and measuring the resulting current as a function of
time. Usually after obtaining a potentiodynamic polarization curve it may be
convenient to conduct potentiostatic tests at potentials of particular interest. For
example, where the value of the perfect passive potential is close to the free cor-
rosion potential, it is convenient to obtain long-term data in the region between the
perfect passivity potential and the pitting potential. In addition, to interpret
potentiodynamic polarization curves with anomalous trend it may be useful to have
data obtained with potentiostatic tests, which are certainly more reliable. The main
SCC
102 High
Current density (mA/cm2)
scanning rate
10-2
Low
scanning rate
10-4
-400 -600 -800

Potential (mV SCE)
Fig. 29.26 Potentiodynamic anodic curve of C-Mn steel in 1 N carbonate/bicarbonate solution, at

90 °C. Dotted zones are critical potential intervals for SCC
disadvantage of this technique is given by the long times required for the mea-
surement and by the number of tests to be carried out.
Cyclic voltammetry. In a cyclic voltammetry experiment, the working electrode
potential is ramped linearly versus time with a high potential scan rate. Once the set
potential is reached, the working electrode potential is reversed to return to the
initial value. Cycles of ramps in potential may be repeated as many times as needed.
The current at the working electrode is plotted versus the applied voltage to give the
cyclic voltammogram trace. Cyclic voltammetry is generally used to study the
electrochemical properties of electrolyte, to analyse the anodic and cathodic pro-
cesses, to determine the stability of reaction products, or the presence of interme-
diates in redox reactions.
• ASTM A262, Standard practices for detecting susceptibility to intergranular

attack in austenitic stainless steels, American Society for Testing of Materials,
• ASTM B117, Standard practice for operating salt spray (fog) apparatus,
• ASTM D4170, Standard test method for fretting wear protection by lubricating
greases, American Society for Testing of Materials, West Conshohocken, PA.
• ASTM G1, Standard practice for preparing, cleaning, and evaluating corrosion
test specimens, American Society for Testing of Materials, West Conshohocken,
PA.
• ASTM G4, Standard guide for conducting corrosion tests in field applications,
• ASTM G28, Standard test methods for detecting susceptibility to intergranular
corrosion in wrought, nickel-rich, chromium-bearing alloys, American Society
• ASTM G30, Standard practice for making and using U-bend stress-corrosion
test specimens, American Society for Testing of Materials, West Conshohocken,
PA.
• ASTM G31, Standard practice for laboratory immersion corrosion testing of
metal, 1American Society for Testing of Materials, West Conshohocken, PA.
• ASTM G32, Standard test method for cavitation erosion using vibratory appa-
ratus, American Society for Testing of Materials, West Conshohocken, PA.
• ASTM G36, Standard practice for evaluating stress-corrosion-cracking resis-
tance of metals and alloys in a boiling magnesium chloride solution, American
Society for Testing of Materials, West Conshohocken, PA.
• ASTM G38, Standard practice for making and using C-ring stress-corrosion test
specimens, American Society for Testing of Materials, West Conshohocken,
PA.
676 29 Testing
• ASTM G46, Standard guide for examination and evaluation of pitting corrosion,
• ASTM G48, Standard test methods for pitting and crevice corrosion resistance
of stainless steels and related alloys by use of ferric chloride solution, American
• ASTM G61, Conducting cyclic potentiodynamic polarization measurements for
localised corrosion, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G71, Standard guide for conducting and evaluating galvanic corrosion
tests in electrolytes, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G73, Standard test method for liquid impingement erosion using rotat-
ing. Apparatus, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G76, Standard test method for conducting erosion tests by solid particle
impingement using gas jets, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G78, Standard guidecrevice corrosion testing of iron-base and
nickel-base stainless alloys in seawater and other chloride-containing aqueous
environments, American Society for Testing of Materials, West Conshohocken,
PA.
• ASTM G85, Standard practice for modified salt spray (fog) testing, American
• ASTM G59, Standard test method for conducting potentiodynamic polarization
resistance measurements, American Society for Testing of Materials, West
Conshohocken, PA.
• ASTM G78, Standard guide for crevice corrosion testing of iron-base and
nickel-base stainless alloys in seawater and other chloride-containing aqueous
environments.
• ASTM G102, Standard practice for calculation of corrosion rates and related
information from electrochemical measurements, American Society for Testing
of Materials, West Conshohocken, PA.
• ASTM G106, Standard practice for verification of algorithm and equipment for
electrochemical impedance measurements, American Society for Testing of
Materials, West Conshohocken, PA.
• ASTM G108, Standard test method for electrochemical reactivation (EPR) for
detecting sensitization of AISI type 304 and 304L stainless steels, American
• ASTM G150, Standard test method for electrochemical critical pitting temper-
ature testing of stainless steels, American Society for Testing of Materials, West
Conshohocken, PA.
steels—part 1: austenitic and ferritic-austenitic (duplex) stainless steels—cor-
rosion test in nitric acid medium by measurement of loss in mass (Huey test),

steels—part 2: ferritic, austenitic and ferritic-austenitic (duplex) stainless steels
—corrosion test in media containing sulfuric acid, International Standard
• ISO 6509-1, Corrosion of metals and alloys—determination of dezincification
resistance of copper alloys with zinc—part 1: test method, International
• ISO 6509-2, Corrosion of metals and alloys—determination of dezincification
resistance of copper alloys with zinc—part 2: assessment criteria, International
• ISO 9227, Corrosion tests in artificial atmospheres—salt spray tests,
• ISO 11845, Corrosion of metals and alloys. General principle for corrosion
testing, International Standard Organization, Geneva, Switzerland.
• ISO 17475, Corrosion of metals and alloys—Electrochemical test methods—
Guidelines for conducting potentiostatic and potentiodynamic polarization
measurements, International Standard Organization, Geneva, Switzerland.
• NACE TM0177, Laboratory testing of metals for resistance to sulphide stress
cracking and stress corrosion cracking in H2S, NACE International, Houston,
TX.
• NACE TM0284, Evaluation of pipeline and pressure vessel steels for resistance
to hydrogen-induced cracking, NACE International, Houston, TX.
29:1 Design an accelerating testing for carbon steel operating in fresh water at
40 °C, fluid velocity 1 m/s and oxygen content 0.1 ppm. Calculate the
intensification index.
29:2 Explains the philosophy behind corrosion tests.
29:3 Describe the typical parameter measured in exposure test. Differentiates for
the main forms of corrosion.
29:4 Which is the most famous test for pitting corrosion? Why that solution is
used?
29:5 Salt spray fog is used to compare coatings. How test results can be used?
29:6 Explain the principle of Stern-Geary method. Is the method applicable to
study the corrosion of passive metals?
29:7 What do you get from the Tafel extrapolations method?
29:8 Explain the difference between potentiodynamic, potenziostatic and cyclic
voltammetry electrochemical techniques.
29:9 EPR test runs by the application of a potentiodynamic scan from passive
interval downward less noble, i.e., cathodic, potentials. Does the application
678 29 Testing
of cathodic protection, for example by means of a galvanic anode (for

instance pure iron) reveal the same behaviour? Explain.
29:10 How do you study the susceptibility of a stainless steel to pitting? Explains
both exposure and electrochemical tests and the variables that influence the
results.
29:11 An AISI 304 stainless steel tank has to store a chloride-containing solution.
Which test do you recommend to verify the metal-solution compatibility?
29:12 A pharmaceutical plant has to convert the production to a new medicine.
Which test do you recommend to check the metal compatibility with the new
reagents?
29:13 Which tests are mandatory to qualify a carbon steel pipe for sour service
condition?
29:14 A new welding procedure for an austenitic AISI 316 has been put in place.
Which test would you recommend to check is the procedure is correct form a
corrosion point of view?
29:15 Suggest and develop a series of tests to verify the localised corrosion
resistance of three stainless steels to a commercial syrup.
Bibliography
Baboian R (2004) Corrosion tests and standards: application and interpretation. ASTM
International, West Conshohocken
Electrochemical Techniques for corrosion Engineering (1986) Baboir Editor. NACE International,
Houston, TX
Corrosion (EFC) Series, vol 68. Woodhead Publishing, London
Stern M (1958) A method for determining corrosion rates from linear polarization data. Corrosion
14:60
Stern M, Geary AL (1957) Electrochemical polarization. A theorical analysis of the shape of
polarization curve, J Electrochem Soc 104:56
Chapter 30
Statistical Analysis of Corrosion Data
The plates [of the ship] were pitted till the men that were paint,
paint, painting her, laughed at it.
R. Kipling, The Day’s Work, Bread upon Waters.
Abstract Statistical analysis—from data sampling to interpretation of results—is

fundamental to all branches of science and engineering, as well as in the field of
corrosion. Once corrosion data are obtained from testing (i.e. laboratory and/or field
investigation), monitoring and inspection activities, statistical analysis can be very
helpful to interpret such results, providing a rational, engineering approach.
Nowadays, the amount of corrosion data has continuously increased. In spite of
this, the statistical approach is not widely used in corrosion science and engineering
even if proper methodologies are available to organize corrosion information and to
improve industrial plant design and maintenance. In this chapter, the basic concepts

https://doi.org/10.1007/978-3-319-97625-9_30
680 30 Statistical Analysis of Corrosion Data
of corrosion probability and statistical treatment of corrosion data are discussed.

The chapter does not cover detailed description of statistical methods, rather con-
siders a range of approaches with applications in corrosion testing.
30.1 Fundamentals of Statistics
30.1.1 Mean and Variability of Data Distribution
When measuring values associated with the corrosion of metals, as corrosion rate or
time-to failure of a corroded component, several factors act to produce a scattering
of data. The pattern in which data are scattered is called distribution. Usually, these
factors, mainly related to environmental and metallurgical properties, act in a
random way so that the average of several values approximates the expected value
better than a single measurement. Generally, the need for a statistical treatment of
data is felt especially for localized corrosion phenomena (Fig. 30.1), as pitting
corrosion and stress corrosion cracking (SCC), which are characterized by an ini-
tiation (or incubation) period and by a propagation time. Statistical analysis can be
applied to both of them, although the interest on the initiation time remains pre-
dominant from an engineering point of view.
When working with a large and discrete data set, it can be useful to represent it
with a single value that describes the “middle” or “average” value of the entire set.
In statistics, this single value is called the central tendency and mean, median and
mode are the ways to describe it. In corrosion, average values are generally useful
in characterizing corrosion rates. In cases of corrosion penetration due to pitting and
cracking, failure is defined as the first through-penetration and average penetration
rates or mean times have poor meaning. In these cases, extreme value analysis is
used. The variability of a data distribution can be defined by some parameters; the
most used are discussed in the following.
Mean. The mean, l, or expected value, is calculated by summing all data points,
xi, and dividing by the total number of data points, N:
PN
i¼1 xi
l¼ ð30:1Þ
N
Median. The median is the middle value in a set of data. It can be found by
ordering all data points and selecting the one in the middle of the rank. If there are
two middle numbers, the median is the mean of them.
Mode. The mode is the value that occurs the highest number of times.
Standard deviation. It is a measure used to quantify the variation or dispersion of
a set of data. A low standard deviation indicates that the data points tend to be close
30.1 Fundamentals of Statistics 681
to the mean of the set, while a high standard deviation indicates that the data points
are spread out over a wider range of values. Standard deviation, r, measures the
variation of a set of data around the mean value, l, and it is given by:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
PN 2
i¼1 ðxi lÞ
r¼ ð30:2Þ
N1
Variance. It is the expectation of the squared deviation of a random variable from

its mean. It measures how far a set of data are spread out from their average value.
The variance, r2, is the square of the standard deviation (Eq. 30.2).
Coeffıcient of variation. The coefficient of variation is defined as the standard
deviation divided by the mean (C.V. = r/l). This measure of variability is partic-
ularly useful in cases where the size of the errors is proportional to the magnitude of
the measured value so that the coefficient of variation is approximately constant
over a wide range of values.
Range. The range is defined as the difference between the maximum and minimum
values in a set of replicate data values. The range provides an indication of sta-
tistical dispersion and it is measured in the same units as the data.
Precision, repeatability and reproducibility. Precision is closeness of agreement
between randomly selected individual measurements or test results. The standard
deviation of the error of measurement may be used as a measure of imprecision.
Repeatability is the ability of one investigator or laboratory to reproduce a mea-
surement previously made at the same location with the same method. Another
aspect of precision concerns the ability of different investigators and laboratories to
reproduce a measurement. This aspect is called reproducibility.
30.1.2 Statistical Distributions of Scatter Data
The scatter of a data distribution is often displayed through a histogram, by dividing

the range of data obtained from testing into equal intervals. As reported on ISO
14802 Corrosion of metals and alloys—Guidelines for applying statistics to
analysis of corrosion data, the number of intervals, k, is proportional to the number
of data, N:
k ¼ 1 þ 3:32 log N ð30:3Þ
where 3.32 is the logarithmic base 2 of 10. In a frequency distribution plot, each bin
contains the number of values that lie within the range of values that define the bin.
In a cumulative distribution, each bin contains the number of values that fall within
or below the bin.
Histograms provide a discrete analysis of data; the corresponding continuous
function, which represents data distribution best-fit, is the probability density
function, f(x), which provides the probability of the random variable falling within a
particular range of values. Accordingly, the cumulative distribution function, F(x),
is defined as:
Zx
FðxÞ ¼ f ðuÞdu ð30:4Þ
1
30.1.3 Reliability and Hazard Functions
Reliability, R(x), is defined as the ability of a system to perform its required

functions under stated conditions for a specified time. It is related to the cumulative
density function, Eq. 30.4, as follows:
Zx Z1
RðxÞ ¼ 1 FðxÞ ¼ 1 f ðuÞdu ¼ f ðuÞdu ð30:5Þ
1 x
The hazard function, h(x), represents the probability of a failure incident to take
place corresponding to an instant x. The cumulative hazard function, H(x), is related
to reliability, R(x), and F(x) as follows:
f ðxÞ
hðxÞ ¼ ð30:6Þ
RðxÞ
RðxÞ ¼ 1 FðxÞ ¼ eHðxÞ ð30:7Þ
The hazard function ranges from 0 (when R = 1) to +∞ (when R = 0).
30.2 Probability Distributions Observed in Corrosion
A variety of distributions are observed in corrosion (Shibata 2000), as the normal

distribution (pitting potentials), lognormal (SCC failure time), exponential (induc-
tion time for pit generation), Poisson distribution (two-dimensional distribution of
pit), and extreme-value statistics, Gumbel and Weibull distributions (maximum pit
depth, SCC failure time, corrosion fatigue crack depth).
30.2 Probability Distributions Observed in Corrosion 683
Some example of fundamental distribution for corrosion phenomena (obtained

from empirical observations by several authors in literature) are reported in
Table 30.1 (Kowaka 1994). Moreover, in the last years, an effort has been done by
introducing statistical treatment of corrosion data in the international standard ISO
14802 Corrosion of metals and alloys—Guidelines for applying statistics to
analysis of corrosion data, in order to share recent progresses and provide a
guideline for operators in the field of corrosion. Nevertheless, this standard only
deals with basic and rough aspects of statistical analysis of corrosion data.
30.2.1 Normal (Gaussian) Distribution
Normal distribution is bell-shaped and symmetrical with respect to the mean value,
l, which is at the same time mode and median of the distribution, as defined in
Sect. 30.1.1. The normal distribution is non-zero over the entire real line. It follows
that it may not be a suitable model for variables that are inherently positive or
strongly skewed. Such variables may be better described by other distributions,
such as the lognormal distribution. The probability density function of normal
distribution is:
1 ðxlÞ2
f ðxÞ ¼ pffiffiffiffiffiffi e 2r2 ð30:8Þ
r 2p
Table 30.1 Examples of fundamental distribution for corrosion phenomena obtained from
empirical observations by several authors in literature (Kowaka 1994)
Fundamental Example
distribution
Poisson – Number of pits
distribution
Exponential – Time to failure of H-charged 0.9% C steel under constant load
distribution – Incubation period for pitting and crevice initiation of stainless steels in
NaCl solution
Normal – Pitting potential of AISI 304 stainless steel in 3.5% NaCl solution
distribution – Pit depth for carbon steel in fresh water supply pipe
– Rate of activation for sensitized AISI 304 stainless steel in
electrochemical potentiodynamic reactivation test
– Intergranular SCC depth of sensitized AISI 304 stainless steel in high
temperature pure water
Lognormal – Time to SCC failure of Al alloys in 3% NaCl solution
distribution – Time to SCC failure of sensitized stainless steels in high temperature
pure water
– Time to SCC failure of AISI 310 stainless steel in MgCl2 solution
– Time to SCC failure of carbon steel wire in Ca(NO3)2 + NH4NO3
solution
The area under the curve provides the probability of occurrence, calculated by the
cumulative probability function, F(x):
Zx Zx
1 ðxlÞ2
FðxÞ ¼ f ðxÞdx ¼ pffiffiffiffiffiffi e 2r2 dx ð30:9Þ
r 2p
1 1
Since cumulative probability cannot be calculated analytically for each normal

distribution, it is common practice to convert a normal to a standard normal dis-
tribution and then use the standard normal table to find probabilities. A standard
normal table, also called Z-table, is used to find the probability that a statistic is
observed below, above, or between values of the standard normal distribution, with
zero mean and a unitary standard deviation. If x is a random variable with mean l
and standard deviation r, its Z variable is calculated as follows:
xl
Z¼ ð30:10Þ
r
An example in corrosion of a normal distributed variable is pitting potential of

stainless steel in chloride-containing solution.
Example. Consider a data set of pitting potentials of an austenitic stainless steel in
seawater, normally distributed with mean value +0.460 V SCE and standard
deviation 0.055 V. Data were obtained from laboratory tests. In seawater, due to the
presence of microbiological activity, free corrosion potential is +0.350 V SCE.
What is the probability for pitting corrosion to occur?
Pitting corrosion initiation occurs if Epit < Ecorr. The probability to have pitting
corrosion corresponds to the probability P (x < +0.350 V SCE), where x is pitting
potential, normally distributed. The standard variable Z is calculated according to
Eq. 30.10: Z = (x − 0.460)/0.055 = (0.350 − 0.460)/0.055 = −2.00.
It follows that the probability P (x < +0.350 V SCE) can be converted to P (Z <
−2.00). From the standard probabilities table, easily available in any statistical
book, it follows that the pitting probability is lower than 2%.
Example. Consider the same data set of pitting potential reported in the previous
example (l = +0.460 V SCE; r = 0.055 V). Calculate the potential corresponding
to a corrosion probability lower than 5%.
From the standard probabilities table, a cumulative standard probability of 5%
corresponds to a Z value of −1.64. The corresponding normally distributed pitting
potential is x = l + r Z = +0.460 + 0.055 (−1.640) = +0.370 V SCE. In other
words, corresponding to a free corrosion potential of +0.370 V SCE, the pitting
corrosion probability is 5%.
30.2.2 Lognormal Distribution
A lognormal distribution is a continuous probability distribution of a random

variable, x, whose logarithm is normally distributed. Considering the exponential
function x = exp (W), if W is normally distributed, then ln(x) is normally distributed,
as ln(x) = W. A log normally distributed variable takes only positive real values.
The probability density function, for x > 0, is:

1
ðln ðxÞhÞ2
f ðxÞ ¼ pffiffiffiffiffiffi e 2x2 ð30:11Þ
xx 2p
Mean value, l, and standard deviation, r, are:
x2
l ¼ eh þ 2 ð30:12Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
r ¼ e2h þ x2 ðex2 1Þ ð30:13Þ
where h and x are the mean value and standard deviation of W = ln(x). The
conversion with the standard normal distribution of the variable Z (Eq. 30.10) is
possible for the random variable W normally distributed. An example in corrosion
of a variable lognormal distributed is SCC failure time.
Example. Consider a data set of SCC failure time (x) for stainless steel in boiling
MgCl2 at 154 °C (Shibata 2000). Mean value is 114 min and standard deviation is
25 min. The mean value and standard deviation of W = ln(x) are 4.7 and 0.2,
respectively. What is the probability that the failure time is higher than 100 min?
The probability to have failure in times higher than 100 min is P (x > 100 min) =
P (ln(x) > ln(100)) = P (W > ln(100)) = 1 − P (W ln(100)) = 1 − P (W 4.6).
Being W normally distributed, the standard variable Z is calculated according to
Eq. 30.10: Z = (W − 4.7)/0.2 = (4.6 − 4.7)/0.2 = −0.5. It follows that the proba-
bility is P (x > 100 min) = 1 − P (W ln(100)) = 1 − 0.308 = 69%.
30.2.3 Poisson and Exponential Distributions
The Poisson distribution expresses the number of times an event occurs in an

interval of time or space. The probability function of the Poisson distribution gives
the probability that a discrete random variable is equal to a value x, where x > 0:
ea ax
f ðxÞ ¼ ð30:14Þ
x!
where a is mean value of events in the interval. The standard deviation of the
distribution, r, is a0.5. Poisson distribution is considered an appropriate model when
the occurrence of one discrete event does not affect the probability that a second
event will occur, that is, events occur independently, and when the rate at which
events occur is constant.
Mears and Brown, and then Shibata (1996), reported that a Poisson distribution
could describe the distribution of pits on the metal surface. Considering a mean rate
of pit generation, k(s−1), the expected mean value of pits on the surface after a time
t is a = kt:
ekt ðktÞx
f ðxÞ ¼ ð30:15Þ
x!
where x is the number of pits generated after the time t. The survival probability
represents the reliability of the system, R(t), calculated by imposing x = 0, i.e. no
corrosion attacks on the surface:
Rðx ¼ 0; tÞ ¼ ekt ð30:16Þ
Thus, the exponential distribution defined by Eq. 30.16 is the distribution of pit
generation time, t, when random pit generation occurs. Equation 30.16 can be
written as:
ln RðtÞ ¼ kt ð30:17Þ
where the meaning of symbols is known. The corresponding hazard cumulative

function, H(t), can be calculated according to Eqs. 30.7 and 30.17:
HðtÞ ¼ ln RðtÞ ¼ kt ð30:18Þ
As expected, the reliability of the system increases as the pit generation rate
decreases, which is considered constant and independent on the operating time of
the system (the process is “without memory”). Nevertheless, in a macrocell cor-
rosion phenomenon, as pitting corrosion, the occurrence of a localized corrosion
attack on the metal surface affects the probability that a second event will occur,
because of the presence of the macrocell current with creation of anodic and
cathodic zones, so that k cannot be strictly considered constant with time and
independent on the position on the metal surface, unless in the initial period. The
Mean Time To Failure (MTTF) is calculated as follows:
1
MTTF ¼ ð30:19Þ
k
Example. Let’s assume that the initiation time of pitting corrosion of carbon steel
bars of a marine reinforced concrete structure follows an exponential distribution.
From previous experience, the mean initiation time is 105 h (about 11 years). What
is the reliability after 7 years of service life? And what is the time before the first
maintenance service considering a minimum allowed reliability of 90%?
The mean rate of pit generation is considered constant and equal to k = 10−5 h−1.
Reliability after 7 years (0.6 105 h) can be calculated by Eq. 30.16:
Rð7yÞ ¼ ekt ¼ eð0:6 10 105 Þ

5
¼ 0:55 ¼ 55%
To assure the specified reliability (90%), the minimum time of monitoring and
maintenance is:
ln R ¼ lnð0:9Þ ¼ kt ¼ 0:1

0:1 101
t¼ ¼ 5 ¼ 104 h ffi 1 year
k 10
This approach considers a constant mean rate of pit generation and that reliability
decreases as time increases. Conversely, pitting initiation can be better described by
a distribution in which the failure rate decreases with time (infant mortality), as
30.2.4 Generalized Extreme Value Statistics
Extreme value theory deals with the stochastic behaviour of the extreme values in a
process. In corrosion engineering, extreme value statistics provides a powerful
method for analyzing localized corrosion data, and especially for estimating pit
depth or minimum time-to-failure. Indeed, from a practical point of view, the
maximum pit depth is more important than the average pit depth because the
deepest pit causes perforation.
The extreme value theory is defined by the so-called generalized extreme value
distribution, GEV, which is a family of continuous probability distributions
developed to combine the Gumbel, Fréchet and Weibull distributions also known as
type I, II and III.
Introducing the location parameter, a, and the scale parameter, b, the cumulative
distribution function of the GEV distribution is:
1 !
x a c
FðxÞ ¼ exp 1 þ c ; c 6¼ 0 ð30:20Þ
b

xa
FðxÞ ¼ exp exp ;c ¼ 0 ð30:21Þ
b
where c is the shape parameter, which governs the tail behavior of the distribution.
The sub-families defined by c = 0, c > 0 and c < 0 correspond, respectively, to the
Gumbel, Fréchet and Weibull distributions. Type I distribution for the largest
values and Type III distribution for the smallest values are the most observed in
corrosion and are discussed in the following.
30.2.5 Gumbel Extreme Value Statistics
Extreme value statistics using Gumbel distribution (type I) is recommended for

estimating the maximum corrosion depth, as described by Gumbel (1958). For
pitting corrosion, a standardized procedure has been proposed in order to analyse
the maximum pit depth distribution. Gumbel’s cumulative function, Eq. 30.21, can
be re-written as:
1 a
lnð lnðFðxÞÞÞ ¼ x ð30:22Þ
b b
The cumulative probability, F(x), can be plotted as a straight line on Gumbel

probability plot, which reports the values of cumulative probabilities on the vertical
axis and the maximum penetration depths, x, on horizontal axis. The cumulative
probability can be calculated as:
i
Fi ¼ ð30:23Þ
1þN
where i is the ith position of the ordered value of x, in ascending order, and N is the
total number of samples. The scale parameter, b, and the location parameter, a, can
be calculated by the slope and the intercept of the straight line in the Gumbel
probability plot, according to Eq. 30.22. The mean value and standard deviation of
Gumbel distribution are calculated as follows:
l ¼ a þ 0:58 b ð30:24Þ
r ¼ 1:28 b ð30:25Þ
where 0.58 is the Eulero-Mascheroni constant.

For the pit depth distribution, the return period provides an estimation of
maximum pit depth over the entire surface from the information obtained for minute
area of sampling, providing that the environmental and metallurgical conditions are
the same over the surface (Kowaka 1994). The return period, T, is a measurement of
the average recurrence interval over an extended period of time and it is defined as:
1
T¼ ð30:26Þ
1 FðxÞ
By introducing Eq. 30.23 and considering the average rank method, the return
period can be written as:
1þN 1
T¼ ¼ ð30:27Þ
1þN i 1 f
where f is the confidence. For example, to achieve a confidence of 90%, at least 11

samples are required. The value of x (pit depth) at a given T is the maximum pit
depth, xmax, for the T times larger surface area, S, compared with the small sample
area, s.
Example. The piping system of a cruise ship is made of AISI 304 stainless steel.
After few months from delivery, frequent pitting corrosion attacks occurred on pipe
joints due to the application of a lubricant containing chlorides. In order to evaluate
the corrosive state of the piping system, a corrosion investigation has been carried
out on 37 pipe joints removed from the ship after 24 months. The joints were
analyzed by OES (Optical Emission Spectroscopy) in order to measure the number
of pits and the depth of corrosion attacks. Calculate the probability to find corrosion
attacks at 24 months deeper than the maximum acceptable threshold (800 lm).
Table 30.2 reports the maximum pit depth of samples extracted from the field
after 24 months. Data are ordered in ascending order and the Gumbel cumulative
probability is calculated by means of Eq. 30.23. A Gumbel probability curve is
plotted by reporting the cumulative probability and the maximum pit depth,
x (Fig. 30.2).
The scale parameter, b, and the location parameter, a, are calculated by the slope
and the intercept of the regression line in the Gumbel probability plot:
1
0:0039 ¼ ) b ¼ 256 lm
b
a
0:847 ¼ ) a ¼ 217 lm
b
The mean value (Eq. 30.24) and standard deviation (Eq. 30.25) of Gumbel distri-
bution are:
l ¼ a þ 0:58 b ¼ 217 þ 0:58 256 ¼ 365 lm
r ¼ 1:28 b ¼ 1:28 256 ¼ 328 lm
Considering a maximum acceptable thickness reduction of 800 lm, defined by

mechanical resistance requirements, the reliability function that a pit has a depth
over this threshold is:
Table 30.2 Maximum pit Sample Max. pit Fi = i/(1 + N) −ln(−ln(Fi))

depth of AISI 304 samples depth (lm)
extracted after 24 months
from field and calculation of 1 0 0.03 −1.29
Gumbel cumulative 2 0 0.05 −1.08
probability 3 0 0.08 −0.93
4 0 0.11 −0.81
5 0 0.13 −0.71
6 0 0.16 −0.61
7 100 0.18 −0.53
8 150 0.21 −0.44
9 150 0.24 −0.36
10 150 0.26 −0.29
11 150 0.29 −0.21
12 200 0.32 −0.14
13 200 0.34 −0.07
14 250 0.37 0.00
15 250 0.39 0.07
16 250 0.42 0.15
17 300 0.45 0.22
18 300 0.47 0.29
19 300 0.50 0.37
20 300 0.53 0.44
21 300 0.55 0.52
22 350 0.58 0.60
23 350 0.61 0.69
24 350 0.63 0.78
25 350 0.66 0.87
26 400 0.68 0.97
27 500 0.71 1.07
28 500 0.74 1.19
29 500 0.76 1.31
30 600 0.79 1.44
31 700 0.82 1.59
32 700 0.84 1.76
33 800 0.87 1.96
34 800 0.89 2.20
35 800 0.92 2.50
36 800 0.95 2.92
37 1210 0.97 3.62
Fig. 30.2 Regression line of 5

Gumbel cumulative y = 0.0039x - 0.847
probability versus maximum R2 = 0.97
pit depth of data reported in 4
Table 30.2
3
y = -ln(-ln(F))
2
-1
0 250 500 750 1000 1250 1500
Maximum pit depth (μm)
Rðx ¼ 800 lmÞ ¼ 1 Fðx ¼ 800 lmÞ

800 217
R ¼ 1 exp exp ffi 10%
256
30.2.6 Weibull Extreme Value Statistics
The cumulative distribution function of the Weibull distribution (type III) for the
smallest value is:
1! !
x a c xa d
FðxÞ ¼ 1 exp ¼ 1 exp ð30:28Þ
b b
where a is the location parameter, b is the scale parameter and d = −c−1 is the shape
parameter. Frequently, the location parameter, a, is not used, and the equation
reduces to the two-parameter Weibull distribution. The Weibull distribution is
widely used in reliability and life data analysis due to its versatility related in
particular to the shape parameter, d, also known as Weibull slope, which defines the
failure rate, i.e. failure events for unit time, k(x):

d x a d1
kðxÞ ¼ ð30:29Þ
b b
where the variable x assumes the meaning of operating time and the other symbols
are known. In reliability engineering, the cumulative distribution function corre-
sponding to a bathtub curve may be analysed using a Weibull chart where the value
of the parameter d controls the failure rate with time (Fig. 30.3):
• d < 1 for the early failures, where the failure rate decreases with time (infant
mortality)
• d = 1 for the random failures, where failure rate is constant, k = 1/b, during
“useful life”
• d > 1 for the wear-out failures, where the failure rate increases with time at the
end of the design lifetime.
In other words, in the early life of a component adhering to the bathtub curve, the
failure rate is high but rapidly decreases. In the mid-life, the failure rate is low and
constant. In the late life of the component, the failure rate increases rapidly.
Estimation of the Weibull parameters. The estimation of the parameters of the
Weibull distribution can be found graphically via probability plotting paper, or
analytically. Only the graphical method is discussed because it provides a better
understanding of how data are distributed. To better illustrate this procedure,
consider the following example of initiation time of localized corrosion of ten
reinforced concrete samples exposed to laboratory tests to reproduce the exposure
condition of concrete structure in the splash zone of a marine environment. From
previous experience, the accelerated testing conditions are characterized by an
intensification index (Lazzari 2017) of 3, which means that the expected initiation
times in field are three times those measured in laboratory tests. The free corrosion
potential of each concrete bar has been measured periodically in time in order to
monitor corrosion initiation.
As a first step, corrosion initiation times are listed in ascending order, as reported
in Table 30.3. For each time-to-corrosion, the median rank is calculated using the
following equation:
i 0:3
FðiÞ ¼ ð30:30Þ
N þ 0:4
Early failures
δ<1 Wear-our failures
Failure rate, λ(x)
Failure rate, λ(x)
Failure rate, λ(x)
δ>1
Random failures
δ=1
x, time x, time x, time
Fig. 30.3 Failure rate, k(x), with time as a function of the shape parameter, d
Table 30.3 Initiation time of localized corrosion, xi, of ten reinforced concrete samples exposed
to chloride-containing solution to reproduce the splash zone of a concrete structure
i xi (days) ln(xi) Fi = (i − 0.3)/(N + 0.4) Ri = 1 − Fi ln(ln(1/Ri))
1 525 6.26 0.067 0.933 −2664
2 546 6.30 0.163 0.837 −1723
3 560 6.33 0.260 0.740 −1202
4 590 6.38 0.356 0.644 −0822
5 609 6.41 0.452 0.548 −0509
6 620 6.43 0.548 0.452 −0230
7 630 6.45 0.644 0.356 0033
8 640 6.46 0.740 0.260 0299
9 650 6.48 0.837 0.163 0594
10 670 6.51 0.933 0.067 0993
Equation 30.28 can be rewritten (considering a = 0) by introducing the reliability,

R = 1 − F, as follows:
d !
x
RðxÞ ¼ 1 FðxÞ ¼ exp
b
ð30:31Þ
1
ln ln ¼ d lnð xÞ d lnðbÞ
RðxÞ
In a Weibull plot (Fig. 30.4), which reports ln(ln(1/Ri) as a function of ln(x),

Eq. 30.31 is represented by a straight line with slope d and intercept −d ln(b),
where the scale parameter, b, represents the initiation time corresponding to which
R is equal to 37%.
The linear regression of the data set provides the values of the Weibull slope, d,
and of the scale parameter, b:
d ¼ 13:8
b ¼ 610 days
According to Fig. 30.3, the failure rate increases with time for d > 1, and the
corresponding failure mechanism is the wear-out failure at the end of the design
lifetime. In this example, initiation time of localized corrosion depends strongly on
the penetration rate of chlorides through the cover concrete by diffusion and other
transport phenomena. Then, once chloride content at the rebar reaches the critical
threshold, corrosion propagates by a macrocell mechanism. Considering a relia-
bility (a survival probability) of 99%, the corrosion initiation time is 437 days,
obtained by Eq. 30.31 by introducing the calculated parameters of Weibull distri-
bution. Being the intensification index equals to 3, which means that the expected
Fig. 30.4 Weibull 1.5

probability paper of data y = 13.8 ln(x) - 88.5
reported in Table 30.3 1.0 R2 = 0.98
0.5
y = -ln(-ln(1/R))
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
-3.0
6.25 6.30 6.35 6.40 6.45 6.50 6.55
ln(x)
initiation times in field are three times the times measured in laboratory tests, it is
possible to conclude that in field reliability is maintained higher than 99% for times
lower than about 4 years.
30.3 Sample Size and Curve Fitting
30.3.1 Sample Size
Sample size determination assumes a crucial role in a statistical analysis of data and
represents the number of observations or replicates to include in a data set. The goal
of selecting the proper sample size is to make inferences about a population from a
sample. In corrosion testing, it is essential to select a, the area of each sample, and
N, the number of samples, carefully. While small a and N make measurement easy,
the error margin is increased. Otherwise, larger sample sizes generally lead to
increased precision when estimating unknown parameters.
30.3.2 Curve Fitting
Once data are obtained from laboratory testing or field investigations, it is desirable
to determine the best algebraic expression to fit the data set by minimizing the
variance between the measured value and the calculated value. The regression
equations, including linear, polynomial and multiple-variable regression equations,
30.3 Sample Size and Curve Fitting 695
can be sometimes used, with some constrains, for extrapolations that refer to the use
of a fitted curve beyond the range of the observed data.
Linear regression. Data are fitted to a linear relationship, y = mx + b. The best fit
is given by:
P P P
N xy x y
m¼ P P ð30:32Þ
N x2 ð xÞ 2
1 hX X i
b¼ xm y ð30:33Þ
N
where m and b are the slope and y-intercept of the estimated line and N is the
number of observations on x and y.
Polynomial regression. This analysis is used to fit data to a polynomial equation
of the following form:
yðxÞ ¼ a þ bx þ cx2 þ ð30:34Þ
where a, b, c, etc. are the constants used to fit the data set. Polynomial regression
fits a nonlinear relationship used to describe nonlinear phenomena.
Multiple regression. This analysis is used when data sets involve more than one
independent variable. In case of a linear regression, the best fit is given by the
general equation:
y ¼ a þ b1 x 1 þ b2 x 2 þ b3 x 3 þ ð30:35Þ
where a, b1, b2, b3, etc. are the constants used to fit the data set; x1, x2, x3, etc. are
the observed independent variables.
For instance, the international standard ISO 9223 Corrosion of metals and
alloys. Corrosivity of atmospheres, Classification, determination and estimation
reports an estimation of the corrosivity of atmospheres based on corrosion rate
calculated from environmental data or from information on environmental condi-
tions and exposure situation.
In particular, the proposed functions for four standard metals (carbon steel, zinc,
copper, aluminium) describe the corrosion rate (Crate, lm/year), after the first year
of exposure in open air as a function of SO2 deposition (Pd, mg/(m2 d)), chloride
deposition (sd, mg/(m2 d)), temperature (T, °C) and relative humidity (RH, %).
Regression equations are generally not linear; for carbon steel, the multiple
regression equation is:
Crate ¼ 1:77 P0:52

d expð0:020 RH þ fSt Þ þ 0:102 S0:62
d expð0:033 RH þ 0:040 TÞ
ð30:36Þ
where fSt is a function of temperature.

30.4 International Standard
• ASTM G 16—Standard guide for applying statistics to analysis of corrosion

data
• ISO 14802—Corrosion of metals and alloys—Guidelines for applying statistics
to analysis of corrosion data.
Bibliography
Gumbel EJ (1958) Statistics of extremes. Columbia University Press, New York

Kowaka M (ed) (1994) Introduction to life prediction of industrial plant materials: application of
the extreme value statistical method for corrosion analysis, Allerton Press, New York
(originally published in Japanese by The Japan Society of Corrosion Engineers, 1984)
Shibata T (1996) W.R. Whitney award lecture: statistical and stochastic approaches to localized
Corrosion. Corrosion 52(11):813–830
Shibata T (2000) Corrosion probability and statistical evaluation of corrosion data. In: Revie RW
(ed) Uhlig’s corrosion handbook, 2nd edn. Wiley, Hoboken, NJ, pp 367–392
Glossary
Accelerated corrosion testing Corrosion test carried out by imposing more severe
test parameters to reduce substantially its duration.
Acidic corrosion Corrosion attack in acidic solutions for which cathodic process is
hydrogen evolution.
Active (1) The high tendency of a metal to react. (2) A state of a metal that is
corroding.
Active metal A metal which is active and has a tendency to react (or corrode).
Aerobic Presence of air or oxygen as dissolved gas.
Aerobic environment An environment with oxygen.
Ammeter Instrument that measures the intensity of electric current, in A, char-
acterized by very low internal impedance.
Ampere (A) Unit of measurement of electric current in the International System of
Units (SI).
Amphoteric metal A metal that is susceptible to corrosion in both acid and
alkaline environments.
Anaerobic Free of air or oxygen.
Anaerobic environment An environment free of oxygen or air.
Anion A negatively charged ion.
Anode The electrode on which oxidation takes place releasing electrons.
Anodic current Current flowing across the metal-electrolyte interface from the
metal surface to the electrolyte, causing an anodic polarisation.
Anodic oxidation Formation of an oxide film at a metal surface (usually alu-
minium and titanium) by an electrochemical process.
https://doi.org/10.1007/978-3-319-97625-9
698 Glossary
Anodic polarisation Or anodic overvoltage. The change of the electrode potential

in the noble (positive) direction caused by an anodic current.
Anodic protection Electrochemical technique to protect active-passive metals by
supplying an anodic current.
Anodic reaction Oxidation reaction that produces cations, generally metallic ions,
releasing electrons.
Atmosphere The mass of air that surrounds the Earth, composed by roughly 78%
N2, 21% O2, 0.3% Ar, 0.33% H2O and 0.04% CO2.
Austenitic stainless steel A stainless steel with austenitic micro-structure at room
temperature.
Auxiliary electrode See Counter Electrode.
Backfill Material used around galvanic anodes and impressed current anodes to
reduce anode-soil resistance.
Barrier effect The property of coatings or layers with low permeability to liquids
and gases.
Bimetallic corrosion See Galvanic Corrosion.
Bimetallic coupling See Galvanic Coupling.
Biocide Chemical substance that destroys or inhibits the growth or activity of
living organisms, used to eliminate microbiological degradation processes.
Biofilm A formation of a bacteria-enriched layer on a metal surface immersed in
seawater.
Blast-furnace cement Cement obtained by mixing ground granulated blast furnace
slag and Portland cement.
Blended cement Cement obtained by adding substances with pozzolanic activity
to Portland cement.
Blistering Swelling of paint, or formation of a blister inside steel due to hydrogen
ions diffusion and recombination within the metal to form hydrogen molecules,
creating high internal pressure.
Boundary element method (BEM) A numerical technique for solving field
equations based on imposing the constrains on anodic and cathodic surfaces.
Brackish water Water with content of salts higher than 2 g/L.
Brittle cracking Cracking with limited or no plastic deformation.
Buffer A substance that prevents pH changes when present in the electrolyte.
Calamine Layer of mixture of iron oxides formed at the surface of steel at high
temperature or in poorly aerated environments.
Glossary 699
Calcareous deposit A calcium carbonate scale formed in hard freshwater or

deposited on a metallic surface in seawater when cathodic protection is applied.
Carbon steel (CS) Steel containing basic elements only, as carbon and
manganese.
Carbonation Loss of alkaline pH of concrete due to carbon dioxide reaction with
calcium hydroxide in concrete and mortars.
Cation A positively charged ion.
Cathode The electrode on which a reduction reaction takes place by gaining
electrons.
Cathodic current Current flowing across the metal-electrolyte interface from the
electrolyte to the metal surface, causing a cathodic polarisation.
Cathodic disbonding Destruction of adhesion between coating (or paint) and
metal surface due to products of cathodic reactions (hydrogen evolution).
Cathodic polarisation Or cathodic overvoltage. The change of the electrode
potential downward caused by a cathodic current.
Cathodic prevention (CPrev) Electrochemical technique as Pietro Pedeferri
(1938–2008) named to protect passive metals from pitting consisting on
applying a cathodic current before passive film breakdown.
Cathodic protection (CP) Electrochemical technique to protect metals, consisting
on lowering the metal potential by supplying a cathodic current.
Cathodic protection by immunity Cathodic protection condition which brings
metals to immunity.
Cathodic protection by passivity Cathodic protection condition which brings and
maintains metals to passive state.
Cathodic protection by quasi immunity Cathodic protection condition which
brings metals to negligible corrosion rate (below 10 lm/yfor carbon steel and
cast iron in waters and soil).
Cathodic reactant Chemical species whose reduction provides the complementary
process to the metal anodic dissolution.
Cathodic reaction Reduction reaction that gains electrons released by the anodic
reaction.
Caustic brittleness Stress corrosion cracking of steel in hot alkaline solutions.
Cavitation Damage to a metallic material under conditions of severe turbulent
flow.
Cell See Electrochemical Cell and Macrocell.
700 Glossary
Cement Hydraulic binder; finely ground inorganic material that forms with water a
paste that hardens thanks to hydration processes.
Chemical equivalent Atomic or molecular mass of an element divided by its
valence.
Clad, cladding material Layer of a corrosion resisting metal used as corrosion
prevention for vessels and pipelines; backing metal is typically carbon and low
alloy steel.
Clay Finely grained natural rock contained in soils with high capacity to retain
water.
Coating Physical barrier to separate the metal surface from the environment.
Coating efficiency See Efficiency.
Complexing species Chemical species that forms stable complex (for example
cyanides) or insoluble products with metal ions (for example oxides, hydroxides
or sulphides) decreasing ions concentration in solution.
Concentration cell An electrochemical cell composed of two identical electrodes
immersed in two electrolytes that differ by their concentration.
Concentration polarisation Overvoltage contribution produced by concentration
changes in the electrolyte.
Concrete Construction material obtained by mixing in suitable proportions
cement, water and stone aggregates.
Conductivity Quantitative expression of the attitude of a conductor to allow the
flow of an electric current, measured in S/m. It is the inverse of resistivity.
Conductor Medium that makes ions or electrons available as charge carriers,
which can migrate under the action of an electric field.
Corrosion Deterioration of a material, usually a metal, by a chemical or electro-
chemical reaction with its environment.
Corrosion allowance Extra wall thickness which can be consumed by corrosion
without affecting the integrity and resistance to a tensile load or a pressure.
Corrosion coupon Piece of material of the same metal alloy of the plant, exposed
to the same environment, in order to monitor corrosion and protection
conditions.
Corrosion current density The corrosion rate expressed in A/m2 (for iron 1 A/m2
corresponds to 1.17 mm/year thickness loss).
Corrosion inhibitor A chemical substance that prevents corrosion or reduces the
corrosion rate.
Glossary 701
Corrosion fatigue Fatigue-type cracking of metal caused by repeated or fluctu-

ating stresses in a corrosive environment.
Corrosion potential See Free Corrosion Potential.
Corrosion rate The rate at which corrosion proceeds, usually expressed as
lm/year.
Corrosion resistance Ability of a material to withstand corrosion in a given
system.
Corrosion resistant alloy (CRA) Alloy consisting of combination of metals such
as iron, chromium, molybdenum, nickel, cobalt, titanium, with increased cor-
rosion resistance with respect to carbon steel.
Corrosion tubercle Bulges on a metal surface due to the accumulation of corro-
sion products on small localized corrosion cavities.
Corrosiveness The tendency of an environment to cause corrosion.
Coulomb Unit of measurement of electric charge in the International System of
Units (SI), measuring the quantity of charge transported by a 1 A current flowing
for 1 s.
Counter electrode Electrode used to impose current to the working electrode.
Also called auxiliary electrode.
Crevice corrosion Localized corrosion of an active-passive metal at a shielded
surface from full exposure to the environment (typically in a gap).
Crevice critical gap size (CCGS) Minimum interstice that allows the aggressive
environment to enter but impedes the diffusion of oxygen.
Critical crevice temperature (CCT) Maximum temperature without crevice
attack for each gap size.
Critical pitting chloride concentration (CPCC) Threshold below which pitting
does not initiate.
Critical pitting temperature (CPT) Maximum temperature at which stainless
steel resists pitting attack, once fixed potential and environmental conditions.
Crystal grain Portion of metal consisting of a single crystal, originated during
metal formation, in particular, during its solidification.
Cupronickel Copper alloy that contains nickel, plus iron and manganese as
strengthening elements, used in seawater applications for its high corrosion
resistance.
Current Flow of an electric charge, carried either by electrons in a conductive
material or by ions in an electrolyte.
702 Glossary
Current density The current to or from a unit area of an electrode surface, usually
expressed in mA/m2.
Depolarisation The reduction of overvoltage contributions.
Dezincification Selective corrosion of zinc in brass.
Differential aeration cell An electrochemical cell where the same metal is in
contact with different oxygen concentration.
Diffusion Displacement of atoms and ions under the effect of a concentration
gradient, governed by Fick laws.
Diffusion limiting current density The current density that corresponds to the
maximum transport rate that a particular species can sustain because of the
limitation of diffusion (often referred to as limiting current density).
Double layer The interface between a metal and an electrolyte where an electrical
charge separation takes place (the simplest model is represented by a parallel
plate condenser).
Drainage Drainage of electric current from a structure in contact with an elec-
trolyte, by means of a metallic conductor (natural drainage) or an impressed
current or galvanic anodes (forced drainage).
Drinking water See Potable Water.
Driving voltage The difference in potential which measures the metal’s tendency
to oxidise or more generally the energy available for a reaction to occur (also
difference in potential between two metals).
Efficiency (of coating) Ratio of surface area of a metal covered by a coating layer
to the bare metal surface.
Efficiency (of inhibitor) Percent decrease in corrosion rate caused by a corrosion
inhibitor.
Electric field Zone of electrolyte where electric forces act, generated by the cir-
culation of current.
Electrical continuity Ability of a structure composed of different metals to con-
duct electricity through electrical connections.
Electrical resistance Tendency of a conductor to oppose resistance to the passage
of current when subjected to a voltage, measured in X. It causes the conductor
heating.
Electro-osmosis The phenomenon of water diffusion through a coating or a porous
media promoted by the passage of current.
Electrochemical cell A cell consisting of two electrodes, an anode and a cathode,
immersed in an electrolyte; anode and cathode can be different metals or dif-
ferent areas on the surface of a single metal.
Glossary 703
Electrochemical reaction A chemical reaction characterised by a gain or loss of

electrons at electrode surfaces.
Electrical resistance probe (ER probe) Metal coupon of the same material of the
monitored structure, which allows the calculation of corrosion rate by measuring
its electrical resistance variation.
Electrochemistry Scientific discipline that studies the reactions taking place at the
surface of a conductor exchanging current with an electrolyte, involving ionic
and electronic species.
Electrode An electron conductor by means of which electrons are provided for, or
removed from, an electrode reaction.
Electrode potential The potential of an electrode measured against a reference
electrode.
Electrodeposition Electrochemical technique by which a metallic coating is
obtained from the reduction of metal ions.
Electromotive force (EMF) Potential difference expressing the variation of elec-
trical energy associated to a corrosion reaction, calculated from Gibbs free
energy.
Electronic conductor Conductor in which the current is carried by electron
migration.
Electrolysis The forced passage of electricity through a cell that produces chemical
changes at the electrodes.
Electrolyte A solution containing ions that migrate in an electric field.
Enamel Smooth, glossy and durable coating made by a thin layer of glass or
ceramic.
Equilibrium potential The electrode potential of a reversible electrode when it is
not polarised. It is calculated by Nernst equation.
Erosion-corrosion A conjoint action involving corrosion and a mechanical action
(erosion) in the presence of a moving corrosive fluid leading to accelerated loss
of material.
Evans diagram (E-i) Diagram of potential–current density proposed by U.R.
Evans (1889–1980) mostly used to represent corrosion processes.
Exfoliation Special type of intergranular corrosion typical of aluminium alloys
which proceeds through preferential intergranular paths, usually parallel to the
direction of extrusion or rolling, causing the metal to delaminate.
Exchange current density The rate of exchange of positive or negative charges
between the metal-electrolyte interface of an electrode at its equilibrium
potential.
704 Glossary
Extreme value statistics It deals with the extreme deviations from the median of
probability distributions. It aims to assess, from a given ordered sample of a
given random variable, the probability of events that are more extreme than any
previously observed.
Faraday A quantity of electric charge, equal to 96,485 C, required to oxidise or
reduce one chemical equivalent.
Faraday law Fundamental law of electrochemistry stating that the mass formed or
consumed in an electrochemical process is proportional to the circulated charge
through the electrochemical equivalent.
Fatigue Mechanical phenomenon leading to failure under repeated and cyclic
stresses lower than the material tensile strength.
Ferrite Body-centered cubic crystalline phase of iron-based alloys.
Ferritic steel A steel whose microstructure at room temperature consists pre-
dominantly of ferrite.
Finite element method (FEM) A numerical technique for solving field equations
based on imposing the constrains on anodic and cathodic surface and the dis-
cretization of the domain.
Free corrosion potential The potential of a metal in an electrolyte under
open-circuit conditions (also known as open-circuit potential or corrosion
potential).
Fick laws Field equations which describe diffusion phenomenon.
Filiform corrosion Special type of crevice corrosion that occurs beneath paints or
lacquers on a coated metal surface.
Flade potential Defined by Friedrich Flade (1880–1916). See Passivity Potential.
Fouling Deposits including accumulation and growth of marine organisms,
beneath which biofilm can form.
Freshwater Water characterized by a low salinity level (< 2 g/L).
Fretting Wear damage induced under load in presence of repeated micrometric
slips between two surfaces.
Fretting-corrosion A conjoint action involving corrosion and fretting between two
metallic surfaces, triggering fatigue cracks.
Galvanic anode Metal or alloy used to obtain cathodic protection of more noble
materials.
Galvanic cell See Electrochemical Cell.
Glossary 705
Galvanic corrosion Accelerated corrosion of a metal because of an electrical

contact with a more noble material (a metal or a non-metallic conductor) in a
corrosive electrolyte (also called bimetallic corrosion).
Galvanic coupling A pair of dissimilar metals or conductive nonmetals in elec-
trical contact in an electrolyte (also called bimetallic coupling).
Galvanic current The electric current in a galvanic cell.
Galvanic series Ranking of metals and alloys according to their free corrosion
potential in a given electrolyte.
Galvanized steel Carbon steel coated with a protective zinc layer.
Galvanostat Instrument that feeds an electrochemical cell with constant current.
Galvanostatic Refers to a technique for maintaining a constant exchanged current
on an electrode.
Gaussian distribution See Normal Distribution.
Graphitization Selective corrosion of grey cast iron, consisting in the etching of
iron and consequent increase in the surface content of graphite.
Gumbel distribution It is one of most used Extreme Value Statistics, often used
for localized corrosion analysis (for instance, maximum pit depth).
Hardness (of metal) Measure of the resistance to localized plastic deformation
induced by either mechanical indentation or abrasion.
Hardness (of water) Water content of Ca2+ and Mg2+ ions, i.e. ions that contribute
to the formation of limestone deposits.
Heat affected zone (HAZ) Portion of metal that did not melt during welding, but
underwent microstructural modification.
High strength steel Steel subjected to heat treatments or mechanical treatments to
reach high tensile resistance.
High strength low-alloy steel (HSLA) Low-alloy steel that is heat treated to reach
high tensile resistance.
Huey test Test evaluating susceptibility to intergranular attack of stainless steel by
immersion in boiling nitric acid.
Hydrogen embrittlement Loss of ductility of a metal resulting from the diffusion
in the metal of atomic hydrogen.
Hydrogen induced cracking (HIC) Internal damage as small cracks (stepwise
type) caused by atomic hydrogen recombining inside carbon steel with high
sulphur content.
Hydrogen overvoltage Overvoltage associated with the reaction of hydrogen
evolution.
706 Glossary
Immunity A metal state that corresponds to an electrode potential more negative

than the equilibrium potential.
Imperfect passivity A passivity condition of an active-passive metal in which
pitting cannot start but can propagate, if already initiated.
Impressed current An electric current supplied by a device employing a power
source that is external to the electrode system.
Impressed current anode An anode used in impressed cathodic protection sys-
tems. It stands an anodic reaction as metal dissolution, oxygen or chlorine
evolution.
Initiation time Time needed for corrosion conditions to onset, and hence for
corrosion to start propagating.
Intergranular corrosion Type of localized corrosion attack occurring at grain
boundaries of sensitized alloys, typically stainless steels.
Ion An electrically charged atom or complex of atoms.
Ion activity The molar concentration of an ion multiplied by the ion activity
coefficient.
Ionic conductor Conductor in which current is carried by ions migration.
IR drop See Ohmic Drop.
IR-free potential Potential measured without the voltage error caused by the
ohmic drop due to the protection current or any other flowing current.
Knife-line attack Special intergranular corrosion attack occurring to welds, limited
to a few crystalline grains parallel to the weld bead and penetrating steel
thickness up to cut off the weld.
Langelier saturation index (LSI) Indicator of the degree of saturation of calcium
carbonate in water. It is calculated as pH–pHS (actual pH minus saturation pH of
calcium carbonate). Positive values indicate scaling tendency.
Linear polarisation resistance (LPR) Electrochemical technique used to measure
the instantaneous corrosion rate of a metal in an electrolyte. It employs three
electrodes: a working electrode, a reference electrode and an auxiliary electrode
(or counter electrode).
Localized corrosion Corrosion attack occurring on a small portion of the exposed
surface of metal.
Lognormal distribution A continuous distribution in which the logarithm of a
variable has a normal distribution.
Low-alloy steel Steel containing intentional alloying element additions with a
content less than 5%.
Glossary 707
Low-carbon steel Steel with carbon content less than 0.3% and no other inten-
tional alloying element.
Luggin probe A small tube or a capillary filled with electrolyte, terminating
closely to the metal surface of an electrode to eliminate ohmic drop during
potential measurements.
Macrocell Electrochemical cell setting up by the separation of anodic and cathodic
surfaces.
Macrocouple Couple of two metals with different practical nobility.
Macrocouple current Current flowing from the anode to the cathode in a
macrocouple.
Magnetite Iron oxide with chemical formula Fe3O4 showing electrical conduc-
tivity and magnetic properties.
Manganese-oxidizing-bacteria (MOB) Bacteria of Leptothrix strain type which
ennobles the corrosion potential, then inducing pitting attack on low-grade
stainless steels in fresh water.
Martensite Steel structure consisting of a carbon oversaturated solid solution with
needle-like microstructure, high hardness and brittleness.
Martensitic stainless steel A stainless steel with martensitic microstructure at
room temperature.
Mesa corrosion Corrosion occurring in presence of CO2 at temperatures below 80
°C, typical of oil and gas facilities.
Microbiologically-induced corrosion (MIC) Corrosion attack promoted by the
presence of specific bacteria, also known as microbial corrosion or biological
corrosion.
Mobility Velocity of an ion in a given electrolyte divided by the electric field
intensity, in [m2 (s V)−1].
Monitoring (of corrosion) Inspection and control program followed to verify
conditions of corrosion and protection of a structure.
Muntz alloy Brass with 60% copper 40% zinc and traces of iron used for corro-
sion resistant machine parts and boat hulls.
Nernst equation An equation that expresses the equilibrium potential of an elec-
trochemical reaction.
Noble Expresses a low tendency to react or the positive direction of electrode
potential.
Noble metal Metal with a low tendency to react (or corrode), such as gold or
platinum. Its equilibrium potential is highly positive.
708 Glossary
Noble potential A potential towards the positive end of a scale of electrode

potentials.
Non-destructive testing (NDT) Techniques used to monitor the characteristics of
components (e.g. material thickness, presence of cracks) without causing
damage.
Normal distribution The most common distribution function for independent,
randomly generated variables. Normal distribution is bell-shaped and symmet-
rical with respect to the mean value.
Off potential In cathodic protection, potential of a protected structure measured by
switching the current off.
Ohm (X) Unit of measurement of electric resistance in the International System of
Units (SI).
Ohmic drop Potential difference resulting from the passage of current inside a
conductor. It depends on current intensity, electrode or electrolyte resistivity and
path length.
Open-circuit potential The potential of an electrode in the absence of an external
current flow. See also Free Corrosion Potential.
Overvoltage The change in potential of an electrode when current is exchanged
with the electrolyte (see Polarisation).
Oxidation (1) An electrochemical reaction in which electrons are released.
(2) Corrosion of a metal that is exposed to an oxidizing gas typically at elevated
temperatures.
Oxygen limiting current density The current density that corresponds to the
maximum transport rate of oxygen by diffusion to the metal surface (see
diffusion).
Oxygen scavenger Substance used to reduce the oxygen content in a solution by a
chemical reaction with dissolved oxygen. Most used compounds are sodium
bi-sulphite and idrazine or its derivates.
Painting cycle Series of paint layers consisting of a primer in contact with the
metal, an intermediate coat and a finishing coat in contact with the environment,
each with different composition and function.
Passivation The thermodynamic condition (E, T, pH) of stability of metal oxides
and hydroxides in Pourbaix diagrams.
Passive A state of passivity of a metal.
Passivity Kinetic condition of stability of metal oxides and hydroxide formed on a
metal surface that leads to a practical halt of corrosion.
Glossary 709
Passivity potential The lowest value of the passive range, also called Flade
potential.
Pedeferri diagram (E-% Cl) A diagram potential–chloride content proposed by
Pietro Pedeferri (1938–2008) to represent graphically the regions for occurrence
or prevention of pitting of passive metals.
Perfect passivity A passivity condition of a metal in which localized corrosion
(pitting and crevice) cannot initiate nor propagate.
pH A measure of acidity or alkalinity of an aqueous electrolyte. pH value is the
negative logarithm of the hydrogen ion activity (–log[H+] where [H+] =
hydrogen ion activity).
Piontelli probe Device for IR-free potential measurements developed by Piontelli
characterized by a capillary with a lateral channel with the aim to reduce the
shielding effects (see Luggin capillary).
Pipeline Series of straight pipes welded together over a long distance, used to
convey fluids (liquids and gases) from one location to another.
Pipeline inspection gauge (PIG) Pipeline inspection tool based on ultrasonic or
electromagnetic principles to measure continuously surface thickness and check
cracks or localized corrosion attacks.
Piping Complex network of pipes within the boundaries of a plant.
Pitting Localized corrosion of an active-passive metal that takes the form of
cavities called pits. Surface area surrounding pits remains passive.
Pitting potential The lowest value of potential at which pits nucleate and grow.
Pitting resistance equivalent number (PREN) Index of stainless steels calculated
from their composition, used to define the resistance to localized corrosion.
Poisson distribution Discrete distribution used to model the number of events
occurring within a given time interval.
Polarisation The change of potential caused by a current flow across the
electrode/electrolyte interface.
Polarisation curve A plot of current density versus electrode potential for a
specific electrode/electrolyte combination.
Polarisation resistance The slope (dE/di) at the corrosion potential of a potential
(E)-current density (i) curve. Corrosion rate is inversely proportional to the
polarisation resistance (see Linear Polarisation Resistance).
Pole Extremity of a galvanic chain. The positive pole is the one with higher
potential, the negative pole the other one.
Portland cement Cement obtained by grinding and heating a mixture of calcium
carbonate, clay and sand (clinker) with small additions of gypsum.
710 Glossary
Post-welding treatment Weld heating and cooling aimed at obtaining desired

microstructure and mechanical properties of weld bead and heat affected zone.
Potable (or drinking) water Water with limited amount of specific salts and
restrictions on bacteria and dangerous chemicals, according for example to the
Council Directive 98/83/EC of the European Commission.
Potential Electrode potential with respect to a reference electrode.
Potentiodynamic It refers to a technique wherein the potential of an electrode with
respect to a reference electrode is varied at a selected rate by application of an
external current.
Potentiostat An instrument for automatically maintaining a constant electrode
potential.
Potentiostatic It refers to a technique for maintaining a constant electrode
potential.
Pourbaix diagram (E-pH) A graphical representation of thermodynamic stability
of species for metal/electrolyte systems proposed by M. Pourbaix (1904–1998).
Practical nobility Free corrosion potential of a metal in a specific environment.
Precipitation hardening Heat treatment to increase mechanical resistance of a
metallic alloy.
Primary passivation potential Minimum potential above which a stable oxide
forms on a metal surface.
Protection current density The current density necessary to obtain cathodic
protection of a metal in an environment. It equals the rate of cathodic processes
taking place at the protection potential.
Protection potential Potential below which corrosion is controlled and pits do not
propagate.
Quasi-immunity A state of metal when its potential is slightly more positive than
the equilibrium potential so that corrosion rate is negligible.
Reduction An electrochemical reaction in which a species gains electrons.
Reference electrode An electrode with stable potential used as a reference to
measure the potential of another electrode.
Reinforced concrete Composite material made of concrete and steel
reinforcements.
Relative humidity The ratio, expressed as a percentage, of the amount of water
vapor present in a given volume of air at a given temperature to the amount
required to saturate the air at that temperature.
Resistivity Tendency of a material or of an electrolyte to oppose resistance to the
passage of current, also called specific electrical resistance, measured in X m.
Glossary 711
Rust Corrosion product of iron and steel consisting of various iron oxides and
hydrated iron oxides.
Ryznar stability index Indicator of the degree of saturation of calcium carbonate
in water. It is calculated as 2pHs–pH (two times the saturation pH of calcium
carbonate minus actual pH). Values below 6 indicate scaling tendency.
Salinity Total content of salts dissolved in an aqueous solution.
Sampling Procedure to minimize bias errors in selecting elements from a popu-
lation for testing. Types of sampling are: random, systematic, stratified, cluster.
Sandblasting Technique for preparation of the surface of a metal before the
application of a paint.
Scaling (1) The formation of thick corrosion-product layers on a metal surface.
(2) The deposition of water-insoluble constituents on a metal surface.
Seawater A brackish-type water with average salinity of 34–36 g/L.
Selective corrosion Corrosion affecting some metallic alloys in which one com-
ponent is preferentially dissolved.
Sensitization (sensitized alloy) Sensitization of a stainless steel and nickel alloys
is the presence of a chromium-depleted zone around the chromium carbides
precipitated at grain boundaries.
Service life The time in which a structure (or equipment) can ensure all functions it
was designed for, without extraordinary maintenance interventions.
Soil Complex agglomeration of solid particles, entrapping an aqueous solution,
originated from the fragmentation of rock during environmentally induced
physical, chemical and biological processes, mainly consisting of coarse parti-
cles, sand, clay and silt.
Solubilisation treatment Heat treatment of stainless steels and nickel alloys
aiming to dissociate carbides and dissolve carbon in the metal matrix.
Solution Condensed phase with multiple constituents, whose properties can be
varied by varying mass ratios of constituents.
Solid solution Atomic scale intermixing of more than one atomic species in the
solid state.
Sour corrosion Corrosion in a production fluid of oil and gas industry containing
H2S.
Stabilized stainless steel Addition of stabilizers such as niobium or titanium
avoids the chromium carbides precipitation during welding, then impeding
sensitization.
Stainless steel (SS) Ferrous alloy with a minimum chromium content of 12% by
mass to obtain a passive film on the surface.
712 Glossary
Standard electrode potential The reversible potential for an electrode process

when all products and reactions are at unitary activity on a scale in which the
potential for the standard hydrogen reference electrode is zero.
Stent Endovascular prosthesis.
Strauss test Test evaluating susceptibility to intergranular attack of stainless steel
by immersion in a boiling Cu/CuSO4—sulphuric acid mixture.
Stray current External current interfering a metallic structure.
Stress corrosion cracking (SCC) Cracking of a material produced by the com-
bined action of corrosion and tensile stress (residual or applied).
Stress intensity factor (K) Describes the intensification of the stress state at a
crack tip, it is used to establish failure criteria in fracture mechanics.
Sulphate reducing bacteria (SRB) Anaerobic bacteria thriving in anoxic envi-
ronment whilst not dying in the presence of oxygen. They catalyse the reduction
of sulphate to sulphide then leading to corrosion conditions of iron.
Sulphide stress corrosion cracking (SSC) Form of Stress Corrosion Cracking
(SCC) which proceeds by hydrogen embrittlement mechanism in the presence of
hydrogen sulphide.
Surface preparation (before painting) Treatment of the metal surface before
painting consisting of removal of dirt, oxides and any deposits. The most used
technique is sandblasting.
Sweet corrosion Corrosion in production fluid of oil and gas industry containing
CO2 but not H2S.
Tafel law Linear relationship between the overvoltage and the logarithm of current
density.
Tafel slope The slope of the Tafel law in a potential—logarithm of current density
plot.
Tap water Water in domestic piping; it generally meets the requirements of
potable water.
Total dissolved solid (TDS) Amount of salts dissolved in a water.
Thermal treatment Heating and cooling of a metallic material aimed at obtaining
desired mechanical properties.
Throwing power Distance at which macrocell current vanishes. In cathodic pro-
tection, it is the distance from the anode to the point of the cathodic surface still
in protection.
Time of wetness Fraction of time in which an electrolyte wets a metal surface.
Glossary 713
Transport number Ratio between current density due to the movement of one ion
and current transported by all ions present in the electrolyte.
Ultimate tensile strength (UTS) Maximum tensile stress that can be borne by a
material.
Ultrasonic testing (UT) High frequency sound waves introduced in the material to
detect hidden surfaces or internal flaws.
Uniform corrosion Corrosion that is distributed more or less uniformly over the
surface of a metal.
Valence Number of electrons released or gained by an atom or a molecule.
Volt (V) Unit of measurement of electric potential in the International System of
Units (SI).
Voltmeter Instrument to measure electrical potential, in V, characterized by very
high internal impedance (>10 MX).
Water cut Percentage of water phase in oil and gas production fluids.
Water hardness See Hardness.
Weathering steel Steel alloy containing small amounts of chromium, copper,
phosphorus and nickel, which forms a protective patina of corrosion products
after several years of exposure to the environment.
Weibull distribution It is one of most used Extreme Value Statistics, often used
for localized corrosion analysis (for instance, lowest time-to-failure in SCC).
Weight loss Loss of mass of material caused by corrosion.
Weld decay Corrosion of welded zone occurring particularly on stainless steels.
White sandblasted surface Surface free of oxides, rust, rolling scale, corrosion
products, or any other substance for at least 98% of the whole surface (see
sandblasting).
Working electrode The test or specimen electrode in an electrochemical cell
subjected to an exchange of current.
Yield strength Stress at which the material shows a clear deviation from the linear
stress-strain relationship (for metals, equivalent to the stress causing a 0.2%
residual deformation).
Index
A Austenitic stainless steel, 137, 203, 212, 229,

Accelerated corrosion testing, 664 249, 254, 255, 280, 300, 310, 311, 684
Acidic corrosion, 284 Auxiliary electrode, 336
Active metal, 104–107, 112, 113, 116, 135,
136, 140, 150, 152, 155, 188, 329, 348, B
370, 467, 469, 669 Backfill, 393, 394, 396, 397, 415
Aerobic, 131, 132, 377, 386, 448, 458, 459 Barrier effect, 128, 135, 350–353, 360
Aerobic environment, 132, 458, 459 Bimetallic corrosion, 7, 184, 452
Ammeter, 20, 22, 127, 641, 666, 672 Biocide, 363, 377, 379–381, 642
Amphoteric metal, 62, 63, 126, 337 Biofilm, 130, 132, 133, 211, 218, 221, 222,
Anaerobic, 131, 132, 157, 385, 386, 425, 429, 236, 242, 379, 380, 642
432, 439, 440, 448, 458, 459 Blast-furnace cement, 526
Anaerobic environment, 131, 132, 458 Blended cement, 526
Anode, 18–21, 23, 24, 31, 34, 75, 76, 81, 82, Blistering, 7, 275, 278, 279, 287, 288, 359
87, 105, 108, 109, 127, 128, 169, 170, Boundary Element Method (BEM), 390
172–174, 176, 177, 179–181, 184, 192, Brackish water, 217, 229, 330, 424, 437, 443,
203, 215, 216, 238, 281, 298, 329, 333, 498, 607, 643
336, 384, 388–390, 392–398, 404–408, Brittle cracking, 578
415, 416, 452, 454, 455, 464, 469, 476, Buffer, 335
536, 543, 545, 582, 594, 645, 678
Anodic current, 18, 28, 29, 31, 32, 79, 95, 184, C
188, 190, 282, 383, 387, 396, 404, 413, Calamine, 184, 356
415, 665, 669 Calcareous deposit, 236, 249, 387, 389,
Anodic oxidation, 5, 112, 339, 341–343 404–407, 425, 426, 430, 432, 440
Anodic polarisation, 18, 19, 31, 48, 74, 80 Carbonation, 468, 509–511, 513–516, 519,
Anodic protection, 122, 123, 383, 407–410, 521, 526, 527, 531, 536, 538–542,
414, 416, 616 544–546
Anodic reaction, 18, 25, 31, 40, 45, 54, 58, 92, Carbon steel, 4, 5, 10, 32, 46, 55, 56, 92, 131,
99, 129, 281, 365, 369, 388, 389, 395, 140, 146, 147, 149, 152, 165, 166, 181,
408, 463, 469, 525, 556, 594 187, 197, 201–203, 208, 210, 218, 220,
Atmosphere, 479–508, 568, 569, 594–596, 222–224, 229, 236, 237, 244, 245, 249,
601, 605, 606, 618, 622, 627, 631, 655, 255–257, 264, 278–280, 284, 288, 289,
664, 677, 695 314, 315, 328–330, 334, 336, 343, 344,

https://doi.org/10.1007/978-3-319-97625-9
716 Index
354, 356, 364, 367, 379, 382, 385–387, Conductor, 75, 101, 171, 172, 462
392, 395, 402, 409–411, 415, 416, Corrosion allowance, 4, 166, 444
430–434, 439–441, 443, 444, 450, 454, Corrosion coupon, 400, 402, 477
455, 459, 463, 464, 473, 474, 476, 477, Corrosion fatigue, 7, 265, 267, 323, 325, 441
481, 482, 484, 487, 488, 490, 491, 494, Corrosion inhibitor, 4, 357, 360, 365, 371, 374,
496, 507, 508, 516, 532, 533, 536, 539, 375
546, 554, 556–560, 562, 563, 565–570, Corrosion rate, 8–10, 103–117, 145–162, 197,
572, 573, 607, 608, 612, 614, 616, 617, 216, 430, 439, 449, 457, 462, 514,
624, 625, 632, 633, 638, 650, 674, 677, 518, 557
678, 683, 686, 695 Corrosion resistance, 12, 91, 98, 121, 135, 137,
Cathode, 18–21, 23, 24, 31, 34, 53, 54, 75, 76, 271, 297, 316, 319, 325, 333, 335, 337,
81, 82, 87, 105, 108, 109, 127, 128, 169, 338, 341, 435, 441
170, 172–174, 179, 181, 184, 192, 201, Corrosion Resistant Alloy (CRA), 558, 572
203, 215, 216, 281, 298, 314, 335, 336, Corrosion tubercle, 432, 450
384, 390, 408, 409, 411, 412, 450, 455, Corrosiveness, 380, 423, 425, 451, 455, 457
459, 464, 543, 594, 640, 641, 645 Counter electrode, 412
Cathodic current, 18, 32, 79, 80, 89, 112, 176, Crevice corrosion, 7, 135, 228, 231–237,
178–180, 184, 185, 188, 190, 192, 198, 239–242, 379, 442
225, 307, 386, 387, 416, 473, 474, 544, Crevice Critical Gap Size (CCGS), 231, 232
665 Critical Crevice Temperature (CCT), 241
Cathodic disbonding, 239, 390 Critical Pitting Chloride Concentration
Cathodic polarisation, 294, 420, 464 (CPCC), 223
Cathodic Prevention (CPrev), 228, 413, 535, Critical Pitting Temperature (CPT), 223, 228
536 Crystal grain, 297, 303
Cathodic Protection (CP), 86, 130, 171, 228, Cupronickel, 181
267–269, 291, 384–386, 390–392, 395,
398, 401–404, 411, 413–415, 455, 466, D
471, 473, 474 Depolarisation, 407
Cathodic protection by immunity, 415 Dezincification, 196, 307, 308, 311, 435
Cathodic protection by passivity, 96, 190, 191, Differential aeration cell, 126–130, 169, 231,
194 567
Cathodic protection by quasi immunity, 386 Drainage, 132, 448, 457, 469, 471, 476
Cathodic reactant, 425, 426 Drinking water, 230, 366, 423, 432, 435
Cathodic reaction, 17, 18, 26, 27, 32, 40, 58, Driving voltage, 38, 39, 41, 53, 73, 78, 99, 105,
60, 82, 83, 116, 127, 129, 132, 150, 153, 108, 109, 129, 156, 175, 178, 179, 181,
154, 156, 166, 175, 181, 187, 195, 197, 193, 195, 197, 198, 216, 217, 221, 225,
221, 222, 307, 329, 330, 365, 369, 386, 235, 252, 385, 391, 393, 395, 406, 415,
404, 409, 433, 452, 459 452, 465, 468, 469, 476
Cation, 129, 130, 140
Cavitation, 7, 313, 314, 317–321, 324, 325 E
Cement, 223, 224, 366, 468 Efficiency (of Coating), 181, 389, 646
Clad, cladding material, 333, 505, 608, 612, Efficiency (of Inhibitor), 293, 374, 382, 646
621 Electrical continuity, 22, 351, 352
Coating, 32, 201, 239, 283, 317, 327–334, Electrical resistance, 108, 173, 349, 393
336–338, 340, 341, 351, 352, 354, 359, Electrical Resistance Probe (ER Probe), 637,
361, 387–389, 400, 402, 403, 414, 435, 639, 640, 645
452–454, 461, 470, 472, 473, 476 Electric field, 171, 205, 216, 390, 453, 456,
Coating efficiency, 181, 389, 414 461, 464, 474
Concentration polarisation, 76, 85, 87 Electrochemical cell, 24, 40, 76
Concrete, 509–536 Electrochemical reaction, 19, 31, 43, 49, 50,
Conductivity, 10, 20, 92, 95, 100, 108, 52, 59, 61, 63, 76, 77, 79
124–126, 135, 171, 184, 195, 198, 208, Electrochemistry, 9, 12, 20, 25, 116, 141, 142,
212, 329, 330, 335, 339, 349, 391, 394, 172, 206, 339
411, 435, 439, 443, 449
Index 717
Electrode, 19, 20, 28, 30–32, 37, 41, 42, 51, G

52, 54, 55, 75–79, 82, 87–89, 103, 108, Galvanic anode, 176, 392, 393, 415
127, 133, 172, 173, 179, 222, 283, 373, Galvanic cell, 41, 42, 85, 87, 94
384, 392, 396, 415, 456, 459, 460, 475 Galvanic corrosion, 7, 130, 169, 175, 176, 181,
Electrodeposition, 333, 334, 336, 337 183–186, 196, 199–204, 307, 308,
Electrode potential, 666, 675 328–331, 335, 392, 402, 435, 452, 453,
Electrolysis, 379 455
Electrolyte, 9, 18, 19, 21, 23, 25, 31, 60, Galvanic coupling, 11, 181, 184, 185,
73–76, 85–88, 90, 93, 95, 106, 108, 187–198, 200–204, 206, 217, 218, 222,
112, 119, 120, 125, 128, 129, 136, 140, 236, 241, 242, 291, 319, 328, 384, 432,
169, 170, 172, 173, 175, 177–179, 181, 437, 447, 452, 457, 476
183, 184, 192, 195, 198, 199, 203, 212, Galvanic current, 184, 185, 200, 418, 419
213, 216, 218, 221, 224, 229, 238, 280, Galvanic series, 100, 586, 626
330, 336, 365, 383, 390, 393–396, Galvanized steel, 32, 223, 239, 330, 354,
398–400, 409, 411, 415, 470 359–361, 368, 378, 431–433, 435, 474
Electromotive force (EMF), 39, 87, 88, 129 Galvanostat, 665, 667, 668
Electro-osmosis, 544 Galvanostatic, 241
Enamel, 343 Gaussian distribution, 683
Equilibrium potential, 40–50, 52–56, 58–61, Graphitization, 309
63, 64, 75–77, 79, 80, 89, 99, 103–105, Gumbel distribution, 688, 689
110, 115, 119–122, 150, 154, 156, 158,
160, 162, 190, 195, 213, 385, 399 H
Erosion-corrosion, 7, 313, 314, 317, 324, 325, Hardness (of metal), 319, 322, 325, 337
441 Hardness (of water), 249
Evans diagram, 103–105, 109, 115, 116, 119, Heat Affected Zone (HAZ), 94
127, 136, 137, 140, 150, 156, 166, 183, High Strength Low-Alloy Steel (HSLA), 245,
189–192, 203, 311, 360, 415, 452, 453, 291, 565
476, 547, 632, 667, 668 High strength steel, 184, 246, 286, 390, 509,
Exchange current density, 76, 78–81, 84, 90, 520–522, 569, 617
106, 115, 116, 122, 123, 151, 152, 156, Huey test, 307, 310
160, 398, 474 Hydrogen embrittlement, 7, 122, 123, 184,
Exfoliation, 297, 306, 307 244, 246, 252, 272, 275, 294, 295, 330,
Extreme value statistics, 654, 687, 688, 691 356, 369, 387, 390, 511, 520, 564
Hydrogen Induced Cracking (HIC), 275, 276,
F 278, 279, 287–289, 293, 562, 563
Faraday law, 17, 28, 31, 33, 34, 88, 100, 392 Hydrogen overvoltage, 83–85, 121, 122
Fatigue, 8, 14, 243, 244, 247, 253, 262–271,
276, 286, 313, 318, 321–324 I
Ferritic steel, 244, 258, 286, 293, 300 Immunity, 12, 46, 57, 58, 60, 61, 63, 64, 67,
Fick laws, 88, 157, 516, 517, 539 70, 73, 95, 190, 319, 385, 386, 415, 420
Filiform corrosion, 239–241 Imperfect passivity, 14, 220, 224
Finite Element Method (FEM), 169, 176, 178, Impressed current, 291, 384, 391, 395, 405
179, 198, 390 Impressed current anode, 291, 384, 395
Flade potential, 106 Initiation time, 208, 212, 229, 250, 264
Fouling, 130, 157, 232, 351, 355, 409, 417, Intergranular corrosion, 5, 11, 297, 298, 300,
425, 439 301, 303, 304, 306, 307, 309–311
Free Corrosion Potential, 104, 218, 650, 665, IR Drop, 400–402, 464, 467
668, 672, 674, 684, 692 IR-Free Potential, 399–401, 472
Freshwater, 115, 132, 133, 141, 225, 380, 381,
384, 423, 424, 426, 431, 443 K
Fretting, 313, 322–325 Knife-line attack, 297, 303, 310
Fretting-Corrosion, 7, 313, 321–323, 325, 577,
578, 580, 581, 631
718 Index
L 160, 161, 172, 173, 175, 184, 195, 197,

Langelier Saturation Index (LSI), 426–428, 225, 281, 288, 329, 335–337, 339, 350,
430 365, 368–370, 390, 393, 399–401, 457,
Linear Polarisation Resistance (LPR), 540, 464, 465, 474
639–641, 650, 668 Oxidation, 12, 17–21, 25, 29, 30, 33, 58, 60,
Localized corrosion, 5, 7, 11, 121, 126, 132, 61, 81, 82, 96, 110, 116, 132, 240, 281,
145, 148, 155, 162, 184, 207, 208, 217, 314, 321, 323, 338, 339, 341, 344, 347,
225, 226, 228, 229, 231, 232, 238, 297, 358, 383, 418–420, 441, 449, 450, 459
423, 429, 430, 432, 439, 441, 443, 449, Oxygen limiting current density, 89, 90, 92,
450, 458 106, 116, 158–163, 166, 180, 198, 203,
Lognormal distribution, 683, 685 216, 225, 229, 238, 269, 387, 404, 405,
Luggin probe, 668 416, 449, 452
Oxygen scavenger, 379, 381, 432, 434
M
Macrocell, 126, 169, 170, 172, 174–176, P
179–181, 184, 192, 197, 207–209, 215, Painting cycle, 353, 357, 360, 361
216, 224–226, 231, 235, 238, 246, 431, Passivation, 11, 57–59, 61, 62, 64, 65, 68, 70,
450 452, 457 71, 74, 91, 92, 95, 97, 98, 109, 116, 122,
Macrocouple, 184 124, 128, 136, 137, 156, 162, 163, 184,
Magnetite, 135, 184–186, 197, 356, 364, 365, 211, 225, 247, 254, 255, 364, 365, 370,
397, 431, 434 371, 389, 393, 408, 410–413, 441
Manganese-Oxidizing-Bacteria (MOB), 132, Passivity, 12, 20, 59, 68, 70, 73, 91–95, 97, 99,
133 108, 121, 123, 131, 134, 136, 137, 155,
Martensite, 565 156, 162, 188, 190, 209, 213, 218, 224,
Mesa corrosion, 146, 556 225, 234–236, 255, 298, 300, 307, 350,
Microbiologically-Induced Corrosion (MIC), 370, 371, 385, 386, 398, 407, 408, 410,
130–133, 211, 377, 404, 439, 456, 474 411, 413–415, 441, 464, 468, 469
Mobility, 593, 600 Passivity Potential, 95, 97, 122, 124, 136
Monitoring (of corrosion), 14, 26, 260, 383, Pedeferri Diagram (E-%Cl), 73, 207, 220, 224,
398, 402, 612, 631, 635, 636, 642, 679 535, 544
Muntz alloy, 308, 316 Perfect passivity, 220, 224
pH2, 11, 12, 20, 23, 25, 28, 41, 44, 46–48, 52,
N 55–71, 85, 90, 95, 97, 99, 115, 119,
Nernst equation, 43, 44, 46, 48–50, 52, 58–61, 124–126, 130, 131, 146, 150–157, 160,
77, 150, 221, 222, 399 204, 209, 215, 217, 218, 221, 223, 224,
Noble metal, 113, 121, 122, 129, 162, 181, 226, 234–236, 244, 248, 271, 281, 283,
183–185, 187–192, 194, 195, 200, 241, 288, 291, 292, 335–338, 340, 344, 347,
308, 384, 397, 419, 452 352, 363–365, 367–369, 371, 376, 377,
Non-Destructive Testing (NDT), 271, 272, 379–382, 385, 404, 409, 416, 419, 420,
649, 650 424–428, 432–437, 439, 443, 448–452,
Normal distribution, 214 459, 460, 468, 474, 475
Piontelli probe, 668
O Pipeline, 176, 178, 179, 245, 294, 359, 402,
Off potential, 401, 403, 466 403, 415, 443, 452, 459–462, 464, 469,
Ohm (X), 33, 100, 108, 171, 336, 393, 400 470, 472, 473, 475, 476
Ohmic drop, 73, 75, 76, 86, 103, 105, 110, 115, Pipeline Inspection Gauge (PIG), 649, 650
116, 173, 175–180, 184, 188, 192–195, Piping, 10, 71, 131, 166, 200, 229, 236, 244,
198, 216, 235, 238, 329, 336, 390, 391, 297, 324, 382, 415, 474, 475
396, 398–402, 406, 416, 455, 456, 464, Pitting, 7, 11, 95, 97, 121, 132, 133, 135, 155,
465, 470 162, 169, 176, 179, 181, 207–229, 232,
Overvoltage, 48, 73, 76–90, 105, 106, 108, 235, 236, 240, 241, 250, 255, 257, 264,
109, 116, 121, 122, 129, 130, 150, 157, 379, 408, 415, 434–437, 442
Index 719
Pitting Potential, 213, 218, 642, 672, 674, Rust, 23, 32, 67, 71, 99, 103, 146, 231, 321,
682–684 327, 331, 357, 363, 431
Pitting Resistance Equivalent Number (PREN), Ryznar stability index, 426, 428
207, 217, 218, 220, 221, 223, 226, 227,
229, 232, 234, 236, 437, 438, 441, 443 S
Poisson distribution, 682, 683, 685, 686 Salinity, 157, 248, 365, 389, 424, 425, 429,
Polarisation, 103, 173, 398, 402, 405, 418 438, 439, 444, 448
Polarisation curve, 665 Sampling, 401
Polarisation resistance, 635, 639 Sandblasting, 351, 353, 357, 358, 360
Portland cement, 518, 526, 542 Scaling, 153, 363, 364, 369, 425–428, 430,
Post-welding treatment, 303 432, 438, 443
Potable (or Drinking) water, 424, 438 Seawater, 32, 51, 55, 71, 72, 92, 98, 99, 115,
Potentiodynamic, 213, 214, 228, 241, 665 132, 133, 157, 166, 175, 181, 187, 190,
Potentiostat, 12, 281, 383, 412 192, 195–198, 200, 201, 203, 216–218,
Potentiostatic, 214, 228, 241, 408 222, 224, 225, 229, 230, 232–236, 241,
Pourbaix Diagram (E-pH), 58 242, 248, 264, 266, 267, 269, 291, 316,
Practical nobility, 130, 162, 183, 184, 320, 324, 325, 330, 345, 346, 366, 367,
195–199, 203, 328 384–389, 391, 396, 397, 400, 404, 405,
Precipitation hardening, 298 409, 414, 415, 423–425, 437–444, 452,
Primary passivation potential, 95, 97, 137, 408 474
Protection current density, 387–389, 395, 396, Selective corrosion, 5, 124, 297, 308, 311
404–406, 414–416, 469, 472 Sensitization (Sensitized Alloy), 260, 297–300,
Protection potential, 242, 268, 383, 386, 387, 302–305, 307, 310, 673, 676
393, 401, 404, 405, 412, 415 Soil, 7, 9, 11, 26, 32, 33, 55, 67, 71, 72, 115,
127, 128, 146, 166, 181, 313, 385–388,
Q 391, 393, 394, 396–398, 415, 416, 424,
Quasi-Immunity, 385, 386, 415 447–452, 454–457, 459–465, 467, 469,
472–476
R Solubilisation treatment, 301
Reduction, 10, 18, 19, 21, 22, 26–28, 30, 32, Sour corrosion, 549, 561
38, 41, 45, 47–49, 53, 54, 58, 60, 61, 64, Stainless steel, 11, 12, 14, 30, 92, 97, 115,
81, 83, 85, 87, 89–91, 95, 99, 106, 110, 133–137, 146, 149, 165, 166, 181, 186,
115, 125, 127, 130–132, 136, 150, 153, 190, 195–197, 201–203, 207, 209–211,
154, 156, 157, 161, 166, 175, 180, 181, 217–226, 229, 232–236, 241, 242, 248,
184, 191, 195, 197, 208, 216, 218, 221, 255, 257, 258, 260, 261, 272, 280, 297,
222, 225, 234, 235, 255, 260, 261, 269, 303, 310, 315, 319, 325, 329, 333, 382,
280, 283, 286, 293, 300, 307, 315, 323, 386, 403, 407–409, 411, 413, 432, 435,
329, 331, 333, 334, 336, 337, 340, 341, 437, 438, 441, 443, 444, 454, 455, 464
344, 349, 363, 369, 375, 385, 400, 405, Standard electrode potential, 37, 41, 53
409, 413, 423, 429, 451, 452, 458, 459, Stent, 581–584
463, 470 Strauss test, 307, 310, 652
Reference electrode, 37, 41, 46, 50, 55, 76, 77, Stray current, 7, 218, 391, 398, 447, 448, 461,
86, 108, 170, 222, 398, 400–402, 412, 462, 466, 467, 475
416, 460, 470, 472, 641, 643–644 Stress Corrosion Cracking (SCC), 7, 8, 121,
Reinforced concrete, 3, 15, 166, 344, 384, 390, 243–251, 253–262, 265, 267, 269–272,
391, 395, 417, 431, 476 290, 293, 295, 338, 661
Relative humidity, 11, 239, 357, 358, 439 Stress Intensity Factor (K), 12, 64, 78, 251,
Resistivity, 73, 128, 171, 173, 175–181, 198, 252, 260, 261, 263, 270, 289, 291, 375,
199, 203, 216, 225, 229, 252, 269, 336, 438, 441
390, 391, 393–395, 397, 400, 405, 406, Sulphate Reducing Bacteria (SRB), 131, 132,
411, 424, 425, 429, 430, 439, 443, 140, 377, 379, 380, 385, 404, 429, 439,
449–452, 455–458, 461, 465, 472, 475 440, 457–461
720 Index
Sulphide Stress Corrosion Cracking (SSC), Uniform corrosion, 5, 8, 9, 54, 146–148, 155,
222, 292, 293, 392 156, 166, 169, 170, 300, 369, 430, 435,
Surface preparation (before painting), 360 440, 449, 457
Sweet corrosion, 549, 561
V
T Voltmeter, 50, 76, 398, 401, 416, 641
Tafel Law, 73, 78, 79, 82, 83, 85, 89, 111, 150,
151, 386 W
Tafel slope, 78, 81, 83, 85, 90, 115, 116, 150, Water cut, 325
151, 156, 175, 415, 416, 467, 476 Water hardness, 425, 426, 443
Thermal treatment, 348, 564, 621, 626 Weathering steel, 494–496, 508
Throwing power, 170, 173, 175–181, 197, 198, Weibull distribution, 682, 687, 688, 691–693
216, 224, 229, 238, 335, 336, 338, 411, Weight loss, 307, 322
412, 414 Weld decay, 302
Time of wetness, 479, 481, 482, 485, 488, 489 White sandblasted surface, 347
Total Dissolved Solid (TDS), 125, 126, 166, Working electrode, 50, 640
427–429, 444, 551
Y
U Yield strength, 251, 259, 286, 287
Ultimate tensile strength, 564
Ultrasonic Testing (UT), 646, 648

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More information about this series at http://www.springer.com/series/4288

In Cooperation with Marco Ormellese, Andrea Brenna,

ISSN 1612-1317 ISSN 1868-1212 (electronic)

Library of Congress Control Number: 2018950812

© Springer Nature Switzerland AG 2018

Milan, Italy Luciano Lazzari

1 General Principles of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

3 Thermodynamics of Aqueous Corrosion . . . . . . . . . . . . . . . . . . . . . 37

5.4.2 Total Oxygen Overvoltage . . . . . . . . . . . . . . . . . . . 89

8 Uniform Corrosion in Acidic and Aerated Solutions . . . . . . . . . . . . 145

10.5.4 Electrolyte Resistivity . . . . . . . . . . . . . . . . . . . . . . . 198

12.7.1 Corrosion Under Insulation . . . . . . . . . . . . . . . . . . . 238

14 Hydrogen-Induced Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

16.1.2 Cavitation Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 317

17.4.8 Painting Maintenance . . . . . . . . . . . . . . . . . . . . . . . 358

19.4 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414

21.4.6 Alternating Current Interference . . . . . . . . . . . . . . . . 471

23.7 Additional Protections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529

24.7.8 High Temperature Sulphidation . . . . . . . . . . . . . . . . 570

26.9 Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606

28 Monitoring and Inspections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635

29.4.5 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . 674

… ‘I see that water, nay, I see

Born “valtellinese”, adopted “milanese”, with heart

Pietro Pedeferri was a Full Professor in Corrosion and

valve metals and relevant chromatic effects. His

aMz þ Activity (or concentration) of ions of metal M in a solution (mol/L)

Ecorr Free corrosion potential (V)

i0; O2 Exchange current density of oxygen (mA/m2)

You are dust and to dust you shall return.

© Springer Nature Switzerland AG 2018 1

1.1 Corrosion as Metallurgy in Reverse

Materials exposed to aggressive environments may undergo chemical and physical

EFC Deﬁnition of Corrosion

1.2 The Economic Impact of Corrosion

Corrosion involves industry, infrastructure and cultural heritage concurrently. No

The entity of corrosion damage is impressive. It is well summarized by a sign

applications lead to artistic or creative corrosion, as was common in the Middle

1.3 Corrosion Forms

1.3.1 Uniform or Generalized Corrosion

Is Corrosion Really a Cost?

as a direct cost because it is most likely necessary in order to ensure reliability

Fig. 1.3 Figure showing typical corrosion forms occurring on metals

1.3.2 Localized Corrosion

Localized corrosion takes place on speciﬁc sections of an exposed surface because

1.3.3 Stress Corrosion Cracking

For speciﬁc material-to-environment couplings and under an enduring tensile load,

1.4 Corrosion Rates

Regardless of the morphology of an attack, corrosion leads to a loss in mass. In this

1.4.1 Uniform Corrosion

where Dm is mass loss in time, t, and S is exposed surface area.

1 mdd ﬃ 5 lm=year 1 mmh ﬃ 1 lm=year ð1:3Þ

1.4.2 Localized Corrosion

1.5 Corrosion Mechanisms

Metal corrosion follows two different mechanisms: high temperature corrosion

1.6 Questions and Exercises

1:1 A zinc plate with a surface area of 1 m2 is exposed to an aggressive solution

1:10 Why is corrosion considered “metallurgy in reverse”?