Corrosion – POURBAIX Diagrams

Nicholas Grundy, Huahai Mao

Marcel POURBAIX

 Russian-born (1904 –1998) Belgian chemist and

pianist.
 Studied corrosion @ University of Brussels
 Biggest achievement is the derivation of Eh-pH
diagrams –a kind of electrochemical phase
diagram.
 1st Eh-pH diagram presented in 1949
 1st Edition "Atlas of Electrochemical Equilibria",
for all elements known at the time, published in
1963.
Marcel Pourbaix (1974): Atlas of Electrochemical Equilibria in Aqueous
Solutions, 2nd Ed, Houston, Tex., National Association of Corrosion Engineers.
Eh – pH Diagram

pE-pH, Eo-pH, or potential-pH diagram

Eh:
(standard hydrogen) electronic potential, represents the redox state,
derived based on Nernst equation.

 Eh = MUR(ZE)/RNF
where RNF is the Faraday constant (96485.3)

pH:
Acidity or concentration of
 pH = -log10[ACR(H+1,AQUEOUS)*AH2O]]
where AH2O is the molecular weight of the solvent H2O (55.5)
The Nernst Equation

For the electrochemical reduction reaction (cathodic reaction)

Ox + z e− → Red

ΔG = ΔG0 + RTlnQ Q is the reaction quotient.

ΔG= -zFE, F is the Faraday constant,
E the electrochemical potential.

The Nernst equation for an electrochemical half-cell is

POURBAIX Diagrams - Basics

Vertical lines:
No e- exchange  indep. of Eh
Fe3+  Fe2O3 or Fe2+  Fe(OH)2
Acid – Base reactions
POURBAIX Diagrams - Basics

Horizontal lines:
No H+ or OH- exchange 
independent of pH
Fe3+ + e-  Fe2+

Fe2+ + 2e-  Fe
Redox reactions
POURBAIX Diagrams - Basics

Slopes lines:
H+ or OH- and e- exchange
POURBAIX Diagrams - Basics
Including stability region of water
3 regions can be designated: Corrosion / Passivation / Immunity

Passivation
Corrosion

Immunity
POURBAIX Diagrams - Basics
Including stability region of water
3 regions can be designated: Corrosion / Passivation / Immunity

Passivation
Corrosion

Immunity
POURBAIX Diagrams - Basics

e-
H+
H +
Eh O2 dominated gas

H2 dominated gas H +

e -
pH
e -
Calculation of POURBAIX Diagrams with Thermo-Calc

Easy set-up in POURBAIX module: Q&A “wizard” SYS: GO POURBAIX

Required phases and databases

- AQUEOUS phase, REF_ELEC phase: AQS2, TCAQ3, PAQ2
- Alloy: TCFE9, SSOL6, …
- Phases resulting from chemical or electrochemical reaction (hydroxide, oxide,
sulphide, etc…): SSUB6, TCOX8
- Gas phase: SSUB6

Database descriptions
AQS2: larges number of elements, originally from TGG (Theoretical
Geochemistry Group, Prof. Saxena), applies the generalized HKF (Helgeson-
Kirkham-Flowers) model, valid to 1000°C and 5 kbar .

TCAQ3: Applies the SIT (Specific Ion Interaction Theory), valid up to 350°C and
100 bar.

PAQ2: Subset of TCAQ3 includes all phases necessary for calculations.

- For demonstration and simple systems.
- Does not require appending different databases.
To Calculate in Thermo-Calc

Defining the initial multi-component multi-phase electro-chemical

reaction/equilibrium system:
• With 1 kg of water as basis; retrieve AQUEOUS phase, REF_ELEC phase from
aqueous solution databases: PAQ2, TCAQ3, AQS2;
• Plus initial concentrated solutes (e.g., composition in sea water);
• Add initial amount of specific alloy or phases (e.g., 0.01 m stainless steel or BCC);
• Inclusion of various secondary phases (e.g. oxides, sulphides, hydroxides, etc.) that
would form from interactions;
• Usually include the gas phase
Two Calculation Strategies in Thermo-Calc

1. Ordinary TDB -> GES -> POLY -> POST Module - Routine:
• Command-Line-Driven user-interface, or GUI
• Flexible single equilibrium calculation, stepping, mapping
• Special requirements on proper definitions / settings (tips available via the
command database-information)
• example:TCEX53
Settings in the TDB – POLY – POST Sequence

 Redefine the componentsas follows:

DEF-COMP H2O H+1 ZeFe Ni NaClCl-1 S <& other components> ;
 appropriately define the equilibriumconditions, e.g.,
SET-COND P=1e5 T=300 B=1000 N(H+1)=0 N(Ze)=0 N(Fe)=1e-6 N(NaCl)=3...;
 set the necessary reference statesfor some components, e.g.,
SET-REFERENCE-STATE H2O AQUEOUS * 1E5 ;
SET-REFERENCE-STATE ZE REF_ELEC * 1E5 ;
SET-REFERENCE-STATE NaCl HALITE * 1E5 ;
SET-REFERENCE-STATE Fe BCC * 1E5 ;
 The pH and Eh are thus defined by entering the following functions:
ENT-SYM FUNC pH = -log10(ACR(H+1), AQUEOUS) ;
ENT-SYM FUNC Eh=MUR(ZE)/RNF ;
 The REF_ELECTRODE phase is the reference electrode which should ALWAYS be
included in a defined system involving aqueous solution for the purpose of calculating
electron potential [MUR(ZE)], while this phase must ALWAYS be SUSPENDED in all the
POLY calculations.
Two Calculation Strategies in Thermo-Calc

2. Advanced POURBAIX Module

• Question-Answer-Driven user-interface
• Easy set-up
• Multiple options for various mapping/stepping calculations
• Multiple choices for different post-processing purposes
• Automatic and straightforward definitions/settings
• example: TCEX40
POURBAIX Module

SYS: go POURBAIX_DIAGRAM
WELCOME TO THE POURBAIX MODULE
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
for Quick Calculations of Pourbaix Diagrams
===========================================
Pingfang Shi and Bo Sundman
Thermo-Calc Software AB
NorraStationsgatan93
SE-113 47 Stockholm, Sweden
(Version 7.0, Mar. 2014)
Need any instruction on the POURBAIX module? /N/:
Enforce a PAUSE after plotting when running a MACRO? /N/:
----------------------------------------------------------
| |
| 1. Start a completely new POURBAIX diagram calculation |
| 2. Open an old file & plot other property diagrams |
| 3. Open an old file & make another POURBAIX calculation |
| 4. Open an old file & make another STEPPING calculation |
| |
-----------------------------------------------------------
Select option /1/:
POURBAIX Module

Possible quantities for plotting property diagrams:

 T Temperature (°C or K)
 P Pressure (Pa)
 NP Stable Phase (mole/kg of water)
 BP Stable Phase (gram/kg of water)
 pH Acidity
 Eh Electronic Potential (V)
 Ah Electronic Affinity (kJ)
 pe Electronic Activity (log10ACRe)
 IS Ionic Strength
 TM Total Concentration (in molality)
 Aw Activity of Water
 Oc Osmotic Coefficient
 MF(AQsp) Mole Fractions of Aqueous Species
 ML(AQsp) Molalities of Aqueous Species
 AI(AQsp) Activities of Aqueous Species
 RC(AQsp) Activity Coefficients of Aqueous Species
Factors Affecting the Stability Region

The shape of a Pourbaix diagram of a complex multi-component alloy and the

stability relations of various secondary phases (oxides, hydroxides, sulfides,
sulfates, carbonates, nitrates, silicates, halides, or other forms) depend upon the
following important factors:

 Initial amount and composition of the alloy

 Initial amount and composition of the aqueous solution
 Model treatments on various phases
 Temperature and pressure conditions
Examples of POURBAIX Calculations in Thermo-Calc

Excluding GAS phase Including GAS phase

Examples of POURBAIX Calculations in Thermo-Calc

Lowering Fe content in aqueous phase

Examples of POURBAIX Calculations in Thermo-Calc

Adding SO2 (H2S has the same effect)

Examples of POURBAIX Calculations in Thermo-Calc

Different P-T conditions

Example of More Complex System

-1.0
1.5
Pourbaix Diagram For the heterogenous interaction
between 0.001 m of Fe-alloy (Fe-
-0.5 5Cr-5Ni mole%) and 1 kg of water
1.0 (and with 3 m NaCl), at 200oC and
100 bar.

AQUEOUS
)V( hE 0
Cr2 O + GAS (Oxiding)
0.5 3 Fe2 O
3
Fe
FeCr 2O
3 +N
2 O4 + iFe
Eh (V)

0.5 Fe O
2 3
2O
4
Cor Cr O
0 ros ion 2 3 + Fe
2 O3 + NiF
FeCr e2 O
1.0 2O
I mm 4 Cr O 4
unity Pass 2 3 + Fe
ivatio 2 O3 + NiF
-0.5 n e2 O
FeCr2O4 + Fe3O4 4

1.5
FeC FeC
FeCr2O4 + FCC r2 O r2 O
-1.0 4 + Fe O 4 + Fe3 O
3 4+
FCC 4 + NiFe O
2 4
GAS (Reducing)
THERMO-CALC (2003.02.25:11.33) : Pourbaix Diagram Calcula
-1.5
0 1 2 3 4 5 6 7 8 9 10

pH
Example of More Complex System
Fe-5at% Cr steel, 1kbar, 300°C in 1 kg water with NaCl and H2S
Example of More Complex System
Ni38Cr21Fe20Ru13Mo6W2 HEA water at 25°C and 1 atm

Lu et al., Scripta Materialia 152 (2018) 19-22

Limitations of Experimental Pourbaix Diagrams

• Pourbaix diagrams are fully-equilibrium phase diagrams. No information on

corrosion kinetics is provided by such thermodynamically-derived diagrams
• Pourbaix diagrams are derived for some selected T and P conditions
(normally 1 atm and 25°C.
• Pourbaix diagrams are derived for selected concentrations of ionic species
(e.g. 10-6 M of metal in 1kg of water).
• Most Pourbaix diagrams consider pure substances only (e.g. pure iron in
pure water only). Additional computations must be made separately if other
species are involved.
Advantages of CALPHAD-based Calculations

Complex Phases:  Alloy compound / solid solution

phases
 Oxide / Sulfide / Silicate / … solution
phases
 Aqueous solution phases
 Gaseous mixture phases.

Complex Environments:  Very wide P-T ranges

 Concentrated aqueous solutions

Multiple Functionality:  Many types of phase diagrams &

property diagrams
Modelling G of Aqueous Solutions

Temperature
Aqueous Models & Databases in Thermo-Calc

Thermodynamic models
 DHLL - Debye-Hückel Limiting Law Term
 SIT - Specific Interaction Theory Model
 HKF - Complete Revised HKF Model (Helgeson-Kirkham-Flowers)
 PITZ - Generalized Pitzer’s Formalism

Thermodynamic databases
 AQS2 - HKF model, valid to 1000°C, 5kbar and 6 molality
- includes 82 elements.
 TCAQ3 - developed in TCSAB, SIT model, valid to 350°C, 100bar & 3 mol
- includes 75 elements.
 PAQ2 - TCSAB demo database, subsets of TCAQ2 + SSUB4 + SSOL4.
- includes 11 elements (Fe-Co-Cr-Na-Ni-C-H-O-N-S-Cl)
Applications in Material Science and Engineering and Others…

 Hydro-Metallurgical Processes
 Hydrothermal Formation and Separation Processes
 High- / Low Temperature Corrosion Processes
 Recycling Processes
 Aqueous Chemistry
 Chemical Engineering
 Food, Medicine & Energy Production
 Geochemical Systems (Natural Resources)
 Environmental Protections of Water Resources
 Environmental Impact of Nuclear Fuel Waste
 Environmental Assessment of Industrial Pollution
--- and many more