Verification and Validation

Issues in Advanced Numerical

Modeling: Pitting Corrosion

NITHYANAND KOTA,1 SIDDIQ QIDWAI,2

A L E X I S L E W I S 2, V I R G I N I A D E G I O R G I 2
1S C I E N C E
APPLICATIONS INTERNATIONAL CORPORATION
ARLINGTON, VA, USA
2U S N A V A L R E S E A R C H L A B O R A T O R Y

WASHINGTON, DC, USA

NITHYANAND.KOTA.CTR.IN@NRL.NAVY.MIL
 Motivation

Pitting corrosion
■ Localized corrosion
■ Insidious!
Corrosion- Navy’s perpetual problem ! ■ Can cause catastrophic
failures
Credit: © PIM SCHALKARIJK, HARD RAIN PICTURE LIBRARY

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 Pitting & Microstructure
Variations in Pit Shapes Due to 3D Microstructural Rendering
Metallurgical & Environmental Conditions* of a Stainless Steel

Intergranular Growth Pit growth and shape are

*Source: D. A. Jones, Principles and Prevention
related to microstructure.
of Corrosion, Macmillan Publishing Company,
New York, NY, 1992.

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 Microstructural Influences
Preferential Grain Boundary Attack in Metastable and Stable Pitting at MnS
Coarse-Grained 301LN Stainless Steel Inclusion in 304 SS

Source: A. S. Hamada, et al., Materials Science and Source: T. Suter, et al., Journal of the
Engineering A, 431, 211-217, 2006. Electrochemical Society, 148(5), B174-B185, 2001.

Intergranular and Pitting Corrosion in

AA5083 due to b-Phase at Grain Features of Interest
Boundaries and Grain Aspect Ratio ■ Molar concentration variations:
o Constituent migrations (precipitates)
o Secondary particles or phases
■ Grain boundaries
■ Grain shape (aspect ratio)
■ Crystallographic plane orientation
Source: S. Jain et al., Corrosion Science, 59, 136-147, 2012.

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 Effect of Crystallographic
Orientation
Micro-Pit Density Variation with Crystal Pitting on the Surface of Single Crystal
Orientation in 316LVM Steel Beryllium in Specific Directions

Source: A. Shahryari, et al., Corrosion Science, 51, 677-682, 2009. Source: S. Lillard, Los Alamos National Laboratory, 2002.

Polarization Behavior of Al Single Crystal Polarization Behavior of Oriented Planes of

Oriented in Principal Directions 310 Stainless Steel

○ (111)
◊ (110)
♦ (100)
● Poly

Source: G. Treacy & C. Breslin, Electrochimica, 43(12-13), 1715-1720, 1998. Source: A. Sato et al., Materials Transactions, JIM, 37(4), 729-732, 1996.

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 Objective

Determine the effect of crystallographic orientation

on stable pit growth by incorporating realistic
microstructure in computational models.

Notional Pit Growth

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 Electron Back Scatter Diffraction
(EBSD/OIM)

Kikuchi Pattern Indexing

Schematic of EBSD

■ EBSD patterns are observed when a focused

electron beam is positioned on a tilted specimen
■ Diffraction from lattice planes produces Kikuchi
patterns on phosphor screen
■ Patterns indexed against known structures.
Microstructure Map
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 The Physics of Pitting Corrosion
Dissolution and Diffusion in the Stable Pit:
The Fully Coupled Phenomenon

■ Electrochemical reactions at the corrosion front

and chemical reactions throughout the pit.
■ Species available for reactions are being
transported in the pit.
■ Corrosion front moving outward due to
dissolution of metal.
■ Activation-controlled metal dissolution: rate
based on electrochemical conditions--
concentrations, potentials—at the front.
■ Diffusion-controlled metal dissolution: rate
based on mass transport.
Fe  Fe +2e
2+ -

Fe2+ +H 2O  FeOH + +H + Ionic Di

Flux: J i  Di ci  zi F  ci   ci v
Examples of species, ci: Fe2+,FeOH+, Cr3+, RT
CrOH2+, OH-, H+, Cl-, Na+ Transport by Transport by Transport by
Potential:  diffusion electromigration convection

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 Research Approach

■ Use Comsol software to simulate and analyze stable pitting at the

microstructural scale: ease of multiphsyics implementation.
■ Incorporate actual microstructure through Orientation Image Microscopy
data into the computational (discretized) models.
■ Track corrosion front movement through advanced ALE meshing Perform
modeling from simpler to complex coupling with corrosion front
movement:
o Laplace equation (maximum corrosion rate),
o Mass transport (electrochemical equilibrium, activation/diffusion-controlled),
o Electrochemical-mass transport.
■ Develop methods for verifying and validating the simulations
o Indirect verification for simplified simulations.
o Experimental techniques for evaluating the effect of microstructure.

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 Laplace Equation
Conditions for Maximum Pitting
■ Assumptions:
o Rapid mixing of electrolyte
o Solvent is incompressible
o Solution is electro-neutral.
ci  D 
t
    Di ci  zi i F  ci    ci v   Ri 2  0
 RT 

■ Solve for electric potential

distribution in the electrolyte:
■ Dissolution current density (i) at the corrosion front—Tafel approximation (from
empirical data):


i Vcorr ,     c  n   c zFAdiss exp zF Vcorr   Vapp  Vcorr    / RT  Presence of the
solid is felt here!

i Vcorr ,  
Vn 
■ Corrosion front velocity (~dissolution rate): zFcsolid

Corrosion potential is a function of crystal orientation.

Pit front velocity is a function of corrosion potential.
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 Corrosion Potential &
Microstructure
■ Corrosion potential depends on
the crystal direction seen at the
pit front
■ Depends on both crystal orientation
at the pit front position (specified by
3 Euler angles of the grain), and pit
front normal.

1 , , 2 : Euler angles (x, y)

COMSOL COMSOL
Laplace Module ALE Module
() (x, y, nx, ny)

Local corrosion
OIM grid data
potential Matlab function
(x, y, Euler angles)
(Vcorr at x,y)

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 Corrosion Potential Variation
[1 1 1] V[001]  V[011]  V[111] [1 1 1]
V001 : 1  0.5* variation  *Vcorr
avg

N
avg
Vcorr   Vcorr
CDi
N  0.24V
i 1

V CD
corr : V[001]  s 1   001 CD 

[0 0 1] [0 0 1] [0 1 1]
[0 1 1]
5% variation 10% variation

Vcorr (V)

Assumption 1: The corrosion parameters of 316 SS are similar to those of 304 SS in 1M NaCl solution.
Assumption 2: Corrosion potential of FCC 316 SS varies the same way as that of FCC Aluminum.

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 Stable Pit Growth:
Boundary Conditions and Constraints
Laplace equation Moving mesh

Grounded (Zero Potential) Fixed

Constrained
Zero Flux
Allows expansion

Gradient of Flux: Normal velocity

Tafel Approximation
f  
Vn 
f   zFAdiss exp  zF (Vcorr   Vapp  Vcorr   ) / RT  zFcsolid
  n  
c c
■ Expansion of pit along x-axis
accommodated using a linear scaling of
velocity at the edge the pit.
NOTE: Multiple views of the same domain.
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 Galvanic Corrosion
Sample Problem w/o Microstructure

Electrolyte (seawater)
=0V

Metal 1 Metal 2
Source: Deshpande KB. Corrosion Science 2010;52:3514.
M
Vn   n
zF 
Simpler problem from the literature to
immediately verify the implementation of
ALE meshing technique.
 Verification

■ Verification of the method by comparing with galvanic corrosion

results in literature.

Our result
Source: Deshpande KB. Corrosion Science 2010;52:3514.

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 Pit growth Simulation

100 mm

Pit Growth in Homogeneous Steel

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 Verification

■ Verification through comparison of homogenous case with activation controlled pitting

simulations.

Scheiner and Hellmich, Comput.

Methods Appl. Mech. Engrg., 2009

■ Parameter differences exist, qualitative comparison for verification

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 Effect of Microstructure

Location 1

Location 2

[1 1 1]
Location 4

Location 3

[0 0 1] [0 1 1]
NOTE: Ten locations are simulated.
 Pit shapes: 5% variation (Vcorr)

Location 1 Location 2

Vcorr  g (CD)

Location 3
t  180s Location 4

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 Pit shapes: 10 % variation (Vcorr)

Location 1 Location 2

Vcorr  g (CD)

Location 3
t  180s Location 4

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 Evolution of Pit

t  0s t  30s t  60s

t  90s t  120s t  150s

Location 3
10 % variation

t  180s

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 Why Pit Shapes

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 Pit Statistics Calculations
Simulation results

Edge Detection and Perimeter calculation

Domain assignment and Area Calculation

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 Effect of Location
and Potential Variation

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 Validation Considerations
■ Realistic pit growth is controlled by diffusion (along with
activation)

■ Effect of Operating Transport Mechanisms & Interface

Conditions:
o Activation-controlled rate based on electrochemical conditions at the front.
o Diffusion-controlled rate based on mass transport in the pit.
o Transport due to diffusion, electromigration or both.
o Interaction of the mechanisms and interface conditions  changed rates of
growth.

Electromigration & Diffusion Activation- Diffusion-

Controlled Growth controlled controlled
c j   i Vcorr ,   Jn
    D j c j  z j j F  c j   
D
Vn  Vn 
t  RT  zFcsolid csolid  csat

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 Validation Considerations
■ Experimental Orientation-Based Masked Individual Grains

Polarization Behavior:
o Selective masking through photolithography (SMP)
technique.
o Obtain polarization behavior for 4-6 crystal
directions.
o Use interpolation to obtain corrosion potential as a
function of crystal orientation.

■ Observing pit growth in individual grains

can serve towards validating numerical
models.

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 Summary and Conclusions

■ Actual microstructure is incorporated in the modeling of pitting corrosion.

■ ALE meshing method is adopted to simulate the evolution of the pits.
■ Variation in corrosion potential as a function of crystallographic orientation is utilized.

o Strong effect of the crystallographic orientation

on pit shapes and growth is demonstrated.
o Small variation in corrosion potential accounts
for complex shape evolution.
o The tortuous shapes may give rise to stress
concentrations under mechanical loading.

■ Novel validation efforts in progress .

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Additional Slides
 Material & Model Properties

Variation of Pitting Corrosion for Aluminum

Source: M. Yasuda et al., J. Electrochem. Soc., 137(12), 3708-3715, 1990.

Source: S. Scheiner & C. Hellmich, Comp. Methods. Appl.

Mech. Eng. 198(37-40), 2898-2910, 2009.

Assumption 1: The corrosion behavior of 316 SS is similar to that of 304 SS in 1M NaCl solution.
Assumption 2: Corrosion potential of FCC 316 SS varies the same way as that of FCC Aluminum.

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 The Math Behind the Physics
■ The rate of change of species ci in an Dissolution and Transport in the Stable Pit
open mass system is equal to the net
mass of ci leaving the system and the
mass of ci generated within:

ci
Balance of Species:    J i  Ri
t

Ionic Di
Flux: J i  Di ci  zi F  ci   ci v
RT
Transport by Transport by
diffusion convection
Transport by
electromigration
■ Species generation can be defined through first-order reaction terms.
The reaction rates, ki, in turn may depend
Species Generation: upon the species concentrations, ci, and the
(Chemical Reactions)
Ri : ki f creactants  kibcproducts potential difference across the interface
rendering the physics fully coupled.

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 Movement of the Corrosion Front
■ Charge Neutrality:
Approximation: ci zi  0

■ Corrosion front velocity, VI, is naturally

defined as a function of concentration
and flux jumps.
Interface
Condition:
𝐉𝑖𝐼 − 𝑐𝑖 𝐕𝐼 ∙ 𝐍 = 0

■ Species flux at the front, JIi, could be

defined through Tafel relations
(activation-controlled) or mass ∙ ≔ ∙ − ∙
solid liquid
transport (diffusion-controlled).

ii  A exp b Vapp  Vcorr   

Tafel
Approximation:

NOTE: There is no diffusion or any other process in the solid!

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 Diffusion-Controlled Growth
■ Corrosion rate is controlled by diffusive
Pit Growth in Bi-Material (Two Grains)
transport conditions in the electrolyte
only: At t = 0 s
csteel
    Dc 
t
■ Steel is modeled as summation of atomic-
weighted component concentrations: Grain
Boundary

csteel :  ci M i M , i  Fe2 , Cr 3 , Ni 2 .
i

■ Assumption: Saturated layer on the

fluid side of the interface: At t = 150 s

fluid
csteel  csat  constant,
solid
csteel  cleft & csteel
solid
 cright .
Asymmetric Growth of Front
■ ALE meshing is used to track corrosion Due to Concentration Differences
front:
J n   csat  cmetal Vn  0.
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Coupled Electrochemistry-Mass Transport

Coupled Problem Relevant Field Equations

ci  D 
Concentration
Balance
    Di ci  zi i F  ci     Ri
of Species: t  RT 

Species Generation: Ri : ki f creactants  kibcproducts

Solution
Tafel Approximation: iin  A exp b Vapp  Vcorr   

No flux
Normal flux based on
Tafel approximation Pit
Coupling of this electrochemical-mass
transport problem with corrosion front
movement will result in complete
corrosion simulation capability.
■ Fully-coupled electrochemical-mass
transport problem.
■ Solve for 8 species concentrations and
electric potential: Fe2+,FeOH+,
Cr3+,CrOH2+,OH-, H+, Cl-, Na+, .
■ Tafel approximation based flux BC.
■ No interface movement!
Source: Malki B, Souier T, Baroux B. Journal of the
Electrochemical Society 2008;155

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