Chapter 17:

Corrosion and Degradation of

Materials
ISSUES TO ADDRESS...
• How does corrosion occur?
• Which metals are most likely to corrode?
• What environmental parameters affect
corrosion rate?
• How do we prevent or control corrosion?

Chapter 17 - 1
 THE COST OF CORROSION
• Corrosion:
-- the destructive
electrochemical
attack of a material.
-- Ex: Rusting of

© EHStock/iStockphoto
automobiles and
other equipment

• Cost:
-- 4 to 5% of the Gross National Product (GNP)*
-- in the U.S. this amounts to just over $400 billion/yr**

* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction
to Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc.,
1985.
**Economic Report of the President (1998).
Chapter 17 - 2
 ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction: Zn ® Zn2+ + 2e-
-- reduction reaction: 2H+ + 2e- ® H2 (gas)
H+
Oxidation reaction
Zn Zn2+ H+
H+ Acid
Zinc flow of e- 2e-
in the metal H+ + solution
H
H+
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution
O2 + 4H+ + 4e- ® 2H2O O2 + 2H2O + 4e- ® 4(OH)-
Chapter 17 - 3
 STANDARD HYDROGEN ELECTRODE
• Two outcomes:
-- Corrosion -- Electrodeposition

e- e- e- e-
H2(gas) H+ 2e -
ne - 2e - ne -
H+
Platinum

Platinum
Mn+

metal, M
Mn+ H+
metal, M

ions ions
H+
H2(gas)
25°C 25°C
1M Mn+ sol’n 1M H + sol’n 1M Mn+ sol’n 1M H+ sol’n
-- Metal is the anode (-) -- Metal is the cathode (+)
o
Vmetal <0 (relative to Pt)
o
Vmetal >0 (relative to Pt)

Standard Electrode Potential

Chapter 17 - 4
 STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic

Cu +0.340 o o
Pb - 0.126 V Cd < V Ni  Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Fe - 0.440
more anodic

Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2+ solution Ni 2+ solution
Na - 2.714
Data based on Table 17.1, Fig. 17.2, Callister & Rethwisch 10e.
K - 2.924 Callister 10e.
Chapter 17 - 5
CORROSION IN A GRAPEFRUIT
Cu (cathode) Zn (anode)
+ -
H+
H+ Zn 2+

reduction reactions 2e - oxidation reaction

H+
H+
Acid H+
H+ H+

Chapter 17 - 6
 EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
RT X
VNio -VCd
o
= 0.153 V VNi -VCd = VNio -VCd
o
- ln
- + - + nF Y

n = #e-
per unit
oxid/red
Cd 25°C Ni Cd T Ni reaction
(= 2 here)
F=
1.0 M 1.0 M XM YM Faraday's
Cd 2+ solution Ni 2+ solution Cd 2+ solution Ni 2+ solution constant
• Reduce VNi - VCd by = 96,500
C/mol.
-- increasing X
-- decreasing Y
-- increasing T Chapter 17 - 7
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive) Table 17.2, Callister &
Nickel 200 (passive) Rethwisch 9e.
Source is Davis, Joseph R. (senior
Copper editor), ASM Handbook, Corrosion,
Volume 13, ASM International, 1987, p.
Nickel 200 (active) 83, Table 2.
Tin
more anodic

Lead
316 Stainless Steel (active)
(active)

Cast Iron/Low-carbon Steel

Aluminum Alloys
Cadmium
Zinc
Magnesium
Chapter 17 - 8
 FORMS OF CORROSION
• Stress corrosion
Corrosion at crack tips
• Uniform Attack when a tensile stress • Erosion-corrosion
Oxidation & reduction is present. Combined chemical attack and
reactions occur uniformly mechanical wear (e.g., pipe
over surfaces. elbows).
• Selective Leaching • Pitting
Preferred corrosion of Forms Downward propagation
one element/constituent of small pits and holes.
of
[e.g., Zn from brass (Cu-Zn)]. Fig. 17.17, Callister &
corrosion Rethwisch 10e. (Photograph
• Intergranular courtesy of Rick Adler/Adler
Engineering LLC of Wyoming
Corrosion along USA)

grain boundaries,
often where precip. • Galvanic • Crevice Narrow and
particles form. Dissimilar metals are confined spaces.
g.b. physically joined in the Rivet holes
prec. presence of an
electrolyte. The
attacked Fig. 17.15, Callister & Rethwisch 10e.
zones more anodic metal (Courtesy LaQue Center for Corrosion
Technology, Inc.)
Fig. 17.18, Callister & corrodes.
Chapter 17 - 9
Rethwisch 10e.
 CORROSION PREVENTION (i)
• Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
-- Use metals that passivate
Metal oxide
- These metals form a thin, Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.
• Lower the temperature (reduces rates of oxidation and
reduction)
• Apply physical barriers -- e.g., films and coatings

Chapter 17 - 10
 CORROSION PREVENTION (ii)
• Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.

• Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
Galvanized Steel Using a sacrificial anode
Zn 2+ Cu wire
e-
zinc zinc steel Mg Mg 2+
2e - 2e - pipe anode
steel Earth
e.g., zinc-coated nail e.g., Mg Anode
Chapter 17 - 11
 SUMMARY
• Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction
• Metals and alloys are ranked according to their
corrosiveness in standard emf and galvanic series.
• Temperature and solution composition affect corrosion
rates.
• Forms of corrosion are classified according to mechanism
• Corrosion may be prevented or controlled by:
-- materials selection
-- reducing the temperature
-- applying physical barriers
-- adding inhibitors
-- cathodic protection

Chapter 17 - 12