Cathodic Protection

STP 1154
Computer Modeling in Corrosion
Raymond S. Munn, editor
ASTM PubllcaUon Code Number (PCN)

04-011540-27
1916 Race Street

Phdadelphla, PA 19103
Copyright by ASTM Int'l (all rights reserved); Tue Feb 10 09:33:27 EST 2015
Downloaded/printed by
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agre
Library of Congress Cataloging-in-Publication Data
Computer modehng m corrosion / Raymond S Munn, ed

(STP 1154)
Includes blbhographlcal references and index
ISBN 0-8031-1473-7
1 Corrosion and ant]-corroswes--Computer simulation I Munn. Raymond
S II Series ASTM specml techmcal pubhcatlon, 1154
TA462C618 1992
620 1'1223'0113--dc20 92-12525
CIP
Copynght 9 1992 AMERICAN SOCIETY FOR TESTING AND MATERIALS, Phdadelphla, PA All
rights reserved This matenal may not be reproduced or copied, in whole or in part, in any printed,
mechan0cal, electron0c, film, or other dlstnbut~on and storage media, without the wntten consent of the
publisher
Photocopy Rights
Authonzat=on to photocopy items for internal or personal use, or the internal or personal use of
specific clients, is granted by the AMERICAN SOCIETY FOR TESTING AND MATERIALS for users
registered with the Copyright Clearance Center (CCC) Transactional Reporting Service, provided that
the base fee of $2 50 per copy, plus $0 50 per page =spaid directly to CCC, 27 Congress St, Salem,
MA 01970, (508) 744-3350 For those organtzabons that have been granted a photocopy license by
CCC, a separate system of payment has been arranged The fee code for users of the Transactional
Reporting Service is 0-8031-1473-7 92 $2 50 + 50
Peer Review Policy
Each paper published m this volume was evaluated by three peer reviewers The authors addressed
all of the reviewers' comments to the satisfaction of both the technical editor(s) and the ASTM
Commtttee on Publications
The quality of the papers in this publication reflects not only the obvious efforts of the authors and
the technical editor(s), but also the work of these peer reviewers The ASTM Committee on
Pubhcat=ons acknowledges with appreciation their dedication and contnbution to time and effort on
behalf of ASTM
Printed in Chelsa, MI
July 1992
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further
Foreword
The ASTM Symposmm on Computer Modehng for Corrosion was held on 12-13 November
1990 m San Antomo, Texas. ASTM Committee G-1 on Corrosion of Metals and Its Subcommit-
tee G01 03 on Computers in Corrosion sponsored the event Raymond S M u n n of the U S.
Naval Underwater Systems Center served as symposmm chazrman and is also editor of this
pubhcatlon
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursua
Contents
Overview
SURFACE PHENOMENA AND LOCALIZED CORROSION
Equivalent Electronic Circuits Computer Generated from Alternating-Current

Impedance Data--EARL L PYE AND KAMRANGOLESTANEH
Atomistic Computer Simulation of Alloy Corrosion--R C NEWMAN, Q. SONG,

R A COTTIS, AND K SIERADZKI 17
Discussion 26
Thermal Modeling of Crevice Corrosion and Its Interaction with Fretting in

Confined Geometries--M HELMIATTIA 28
Computer Simulation of Stress Corrosion Cracking Behavior of Reactor Pressure

Vessel (RPV) Steels in Light W a t e r Reactor (LWR) Environments in Slow
Strain Rate Tests (SSRT)--TETSUO SHOJI, SHIN-ICHIMORIYA,
AND KEN-ICHI YOSHIDA 44
Discussion 65
Modeling of Electrode Processes and Surface Chemistry in Carbon Dioxide

Containing S o l u t i o n s - - s TUROOOSE, R A CO.IS, AND K LAWSON 67
Discussion 81
The Use of Computer Modeling in the Interpretation of Filming Inhibitor

MechanismS--ANDREW F PALUS AND CYNTHIA A NIENART 82
DIscussion 91
CORROSION DATA FITTING AND MODELING OF ELECTRODE KINETICS AND IMPEDANCE
Computation of Corrosion Macrocell Current Distribution and Electrochemical

Impedance of Reinforcing Steel in Concrete--s c KRANCAND A A SAGUES 95
Discussion 1! 1
Microcomputer-Based Corrosion Modeling Applied to Polarization C u r v e s - -

K R TRETHEWEY AND J S KEENAN 113
Discussion 125
Modeling Electron Transfer, Diffusional Effects, Passivation, and Ohmic Loss in

Multi-Reaction Polarization Curves--OWEN V DEVEREUXAND KOOKsUN YEUM 126
Discussion 141
Modeling Polarization Curves and Impedance Spectra for Simple Electrode

S y s t e m s - - u BERTOCCIAND R E RICKER 143
Evaluation of Corrosion Data: A RevieW--DAVID B ANDERSON 162

Discussion 173
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No
VI COMPUTER MODELING IN CORROSION
Software for Quantitative Analysis of Polarization Curves--H SHIH

AND F MANSFELD 174
Discussion 184
Software for Simulation and Analysis of Electrochemical Impedance Spectroscopy

(EIS) D a t u - - F MANSFELD,C H TSAI, AND H SHIH 186
Discussion 196
Analyzing Electrochemical Impedance Corrosion Measurements by the Systematic

Permutation of Data Points--p R ROBERGE 197
SPATIAL CORROSION MODELING
A Review of the Development of Computational Corrosion Analysis for Spatial

Corrosion Modeling Through Its Maturity in the Mid-1980s--
RAYMOND S MUNN 215
Computer Modeling of Offshore Cathodic Protection Systems: Method and

Experience--ROE D STROMMEN 229
DIsCussion 247
Computer Modeling of Corrosion Using the Boundary Element Method--

R A ADEYANDS M NIKU 248
Discussion 263
Numerical Simulation of Impressed Current Cathodic Protection (ICPP) Systems

Using Boundary Element M e t h o d s - - v GENSHEIMERDE GIORGI,
E DAIL THOMAS II, AND ALEXIS I. KAZNOFF 265
Discussion 275
On the Effect of Some Critical Parameters in Cathodic Protection Systems: A

Numerical/Experimental Study--SIMONE LOUISEDELARUECARVALHO,
JOSI~ CLAUDIO DE FARIA TELLES, AND LUIZ ROBERTO MARTINS DE MIRANDA 277
Author Index 293
Subject Index 295
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to Licen
STP1154-EB/Jul. 1992
Overview
The advent and increased availabihty of computers has revolutionized the worlds of science,
englneenng, and business since their introduction 50 years ago and their explosion in the last
decade to include sizes from personal computers through supercomputers In the field of corro-
sion, computers are used for field monitonng, data collection and storage, cathodic protection
system control, and modeling of corrosion phenomena and effects The last area of modeling
was the subject of an ASTM Symposium on Computer Modeling in Corrosion held in San
Antonio, Texas, on 12-13 November 1990 The symposium was sponsored by ASTM Commit-
tee G-1 on Corrosion of Metals and Subcommittee G01 03 on Computers Most of the papers
presented at the symposiums are published in this volume
The papers were divided into three sections based upon their topics The papers in the section
covenng Surface Phenomena and Localized Corrosion descnbe the modeling of microscopic
corrosion phenomena The first paper, by Pye and Golestaneh, describes the representation of
corroding systems by vanous equivalent electric circuits and their companson using Nyquist
plots for their ac-response behavior Newman et al investigated dealloylng by computer simula-
tion of the behavior of individual atoms in the crystal lattice, determining certain rules which
affect its dissolution probability Attta discusses work on the synergism of crevice and fretting
corrosion mechanisms with thermal considerations Shofl et al modeled the stress corrosion
cracking phenomena of matenals m liquid water reactors Palus and Ntenart used polanzation
measurement techniques and computer modeling to investigate the effect of filming inhibltors
The microscopic processes and chemistry on electrodes in carbon dioxide-saturated solutions
was modeled by Turgoose et al
The second section presents papers on Corrosion Data Fitting and Modeling of Electrode
Kinetics and Impedance The computation of corrosion macrocell current dlstnbution and elec-
trochemical impedance of reinforcing steel in concrete is discussed by Kranc and Sagues Papers
by Tretheway and Keenan and by Devereux and Yeum each used computational techniques to
model polarization behaviors of metal/electrolyte systems, the former extending such to scale
modeling and painted metals, the latter concentrating on the contributing reactions and using
numerical regression to determine the contributions of each to total current density Bertocct and
Rtcker also modeled polarization behaviors but using an impedance representatmn of the phe-
nomena Anderson used computer methods to store and evaluate data of corroding systems
Mansfeld and Shth presented two papers to describe computer software for evaluating corrosion
phenomena and coating effectiveness using electrochemical impedance spectroscopy (EIS)
Methods for analyzing EIS data computanonally were developed by Roberge using computa-
tional probabfllstlc models to predict long-term localized corrosion phenomena
The final section describes work in Spatial Corrosion Modeling Munn presents an overview of
the historical development of computational techniques to predict corrosion states throughout a
macroscopic galvanic system Strammen described the application of computational methods to
the design of cathodic protection systems for fixed offshore structures The specifics of one such
spatial corrosion modeling techmque, the boundary element method, was presented by Adey and
Ntku DeGtorgt et al described their apphcation to impressed current cathodic protection system
designs for ships Carvalho et al investigated computatmnally and experimentally the relative
effect of certain parameters on the effectiveness of cathodic protection systems.
It was the intent of the symposium to bnng together for an interchange of experiences corro-
sion practitioners who were using computational modehng to meet their responsibilities in prod-
uct or installation design, failure analysis, education, or pure science Although the symposium
was divided into three sessions by topical nature, it was clear by the discussions that the technical
Copyright 9 1992 by ASTM International www.aslm.org
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agr
2 COMPUTER MODELING IN CORROSION
exchange across these arbitrary dwtslons will certainly be of benefit to those who attended This
Special Techmcal Pubhcatlon presents most of the papers offered m the symposmm, and Its
purpose Is to more widely &ssemmate their content The computational hardware and software
avadable today provide considerable power to the practicing corroslomst to perform design,
analysis, and research more qmckly and completely than was possible before computers
The e&tor would hke to gratefully acknowledge the contribution of the symposmm session
chairman A VanOrden, W Eggers, and H Hack, who also served as primary reviewers of the
STP papers, as well as the authors who peer-reviewed others' papers, the ASTM symposia and
pubhcaUons staffs, the Naval Underwater Systems Center for partial support ( W VonWmkle,
D Vlcclone), and especially the authors for their contributions to the purposes of the symposmm
and STP
Raymond S. Munn
Naval Underwater Systems Center
New London, Connecticut,
Symposmm Chairman and E&tor
Surface Phenomena and
Localized Corrosion
Earl L. Pye 1 a n d K a m r a n Golestaneh 1
Equivalent Electronic Circuits Computer

Generated from Alternating-Current
Impedance Data
REFERENCE: Pye, E L and Golestaneh, K, "Equivalent Electronic Circuits Computer Gen-
erated from Alternating-Current Impedance Data," Computer Modehng m Corrosion, ASTM STP
1154, R S Munn, Ed, American Society for Testing and Materials, Phfladelphm, 1992, pp 5-16
ABSTRACT: A simple but powerful method is presented for the computer generatmn of equiva-
lent clrcmts using CAE/CAD software The effect Is shown of various component values, of the
relatwe separation of component values, and of the frequency range A comparison is made of
Nyqmst plots for Volgt, Maxwell, and Ladder equivalent clrcmts
KEY WORDS: alternating-current impedance, alternating-current Impedance spectroscopy, im-

pedance spectroscopy, corrosmn, kinetics, electrode kinetics, electrochemistry
The use of alternating-current impedance spectroscopy (ACIS) to evaluate corrosion rates

and related electrochemical parameters has increased perhaps exponentially over the past ten
years among electrochemlsts, corrosion scientists, and engineers ACIS can give insight into
corrosion mechanisms [ 1 ]
Mansfeld [2] provides a review of the background and apphcatlon techniques of ACIS for
electrochemical processes emphasizing corrosion cells Mansfeld et al [3] contmued with a
presentation and discussion of expenmental methods for obtaining ACIS data on corroding
electrodes
An important aspect of the electrochemical corrosion process is the role of the complex charge
transfer Other processes are both physical and chemical in nature [4] Corrosion processes
frequently are controlled kInetIcally by interfacial charge transfer Transport of the reactant/
product from the electrode surface is another kinetic factor For example, diffusion to the elec-
trode may be rate controlling in some corroding systems An exhaustive theoretical analysis of
ACIS is given by Macdonald [5 ]
Comphcatlons in plctunng the corrosion mechanism result from the nature of the electrode/
electrolyte interface In contrast to the simplistic, idealized model that we tend to picture ini-
tially, the interfaces are not smooth, but rather are jagged and filled with structural defects The
results are electncal circuits that are often shorted, opened, and changed as the processes pro-
ceed Furthermore, "foreign" chemical substances are adsorbed and influence the electrode
response and in turn comphcate our search for an electrochemical reaction mechanism
In spite of these complications, the nature of the electrochemical processes at an interface
frequently can be approximated with an equivalent circuit The equivalent circmt is composed of
Professor of Chemistry, Department of Chemistry, and Chemist, Technical Staff, respectwely,Cahforma

State Polytechmc University, Pomona, CA 91768
Copyright9 1992 by ASTM International www.aslm.org
6 COMPUTERMODELING IN CORROSION
C2 L2
C1
R1
C3 L3
C~ 1_,4 R7
FIG l--General equtvalent ctrcutt for analysts with our computer program ( CPI ) The components can be
g~ven values or omttted as desired
capacitors (C), resistors (R), and perhaps inductors (L) The RC circmt shown in Fig 1 is an
example
One common characteristic of the electrode/electrolyte interface and its equivalent orcult ~s
its tendency to oppose or restrict the flow of charge as a funcuon of the frequency of the applied
current or voltage ACIS can be defined as the study of the resistance to current flow m terms of
its reactive (imaginary) and ohmic (real) components as a function of frequency An equivalent
circuit exhibits an impedance response that can be resolved into its real and imaginary compo-
nents These components can then be plotted in various formats to reveal information about the
circuit [ 1 ]
Measuring Impedance
The a-c impedance (Z) is analogous to the resistance (R) ofa d-c circuit The measurement of
impedance (Z) can be determined by means of an a-c bndge similar in nature to a Wheatstone
bndge used to determine d-c resistance However, that method is cumbersome and rarely used
Rather, electromc-mstrumental methods are used These include a phase-sensitive detector (a
C1
I I_ C2
+OUT OUT
I
+IN
(3 -IN
FIG 2--Circuit for analysts by CPI and EEDIII
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to Licens
PYE AND GOLESTANEH ON EQUIVALENT ELECTRONIC CIRCUITS 7
COMPLEX PLANE
2000 I I
o l~.n SIMULATION
A IMP PROGRAM
.......
1600
f range=0,01 H~. - 10 kHz
R1=1000 ohms
R2=1000 ohms
R3=1000 ohms
CI=I uF
C2=1 uF
1200
r~
~, 8oo
400
| | i | i
1000 1400 1800 2200 2600 3000
Z(REAL), OHM
FIG 3--Nvqutst plot, of tmpedance-response data for the ctrcult of Ftg 2. obtained by CPI (IMP) and
EEDHI (EED)
lock-m amphfier) that measures the m-phase and out-of-phase components The lock-m amph-
tier compares two smusoldal signals The output can be used to obtain the phase angle between
the signals and the ratio of the peak heights All of this can be somewhat slmphfied with sophlst,-
cated electromc switches and operational amphfiers combined into a frequency-response ana-
lyzer (FRA) Details of the FRA system are discussed by Armstrong et al [ 6]
The real (Z') and imaginary (Z") components of the impedance (Z) are
Z'= Zcos0 Z v-- ZslnO
or
Z = Z'+jZ ~
wherej = ~ and 0 1S the phase angle

EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License A
COMPLEX PLANE
2000
|
frange=0.01 Hz - L0kHz
RI=1000 ohms
R2=1000 ohms
1600 R3=1000 ohms
CI=I uF
C2-150 uF
r
1200
<
~, 800
400
0
1000 400 800 2200 2600 LO00
Z(REAL), O H M
FIG 4-- Nyquzst plot, of tmpedance-responsedata for the ctrcutt of Fig 2, obtamed by EEDlll The capact-
tance values dtffer by a factor of 150
Data Plotting
Plots that take the format of imaginary versus real components (complex plane plots) are
referred to as "Nyqmst" plots or somet]mes as "Cole-Cole" plots Another plot format used
frequently ]s the "Bode" plot Th]s format plots Log Z a n d / o r phase shift, generally both, versus
Logarithm of the frequency
We chose to present our data m the Nyqmst format The Bode format could have been
selected as well with no comphcatlons
Equtvalent Czrcutts from Impedance Data

Th~s secUon outhnes how one can take an eqmvalent c~rcuit and, w~th e~ther known or
assumed component values, produce Nyqmst a n d / o r Bode plots Impedance spectroscopists can
become qmte adept at mtumvely vlsuahzmg an eqmvalent clrcmt from Impedance data and the
COMPLEX PLANE
2000
frJge=0 01 Hz - llkHz
RI= 1000 ohms
R2= 1000ohms
1600 R3= 1000ohms
CI= 0 001 uF
C2= 1 uF
1200 I
r~
800
400
I-hghf
0
1000 1400 1800 2200 2600 3000
Z(REAL), OHM
FIG 5--Nyqutst plot, of tmpedance-response data for the ctrcutt of Ftg 2, obtamed by EEDII! The magm-
tude of the capacttance values are smaller than m Ftg 4
corresponding Nyqmst and Bode plots If the data are simple and straightforward, a good match
can result However, as data become more comphcated such "mtumve" results become in turn
less and less reliable
The use of equivalent circuits to represent and explain ACIS data is widespread Cahan et al
[ 7] elucidated the nature of passive films on iron and also interpreted the kinetics of oxygen
evolution on oxide-covered metals with equivalent c~rcmts Shlh and Mansfeld [8] used com-
puter generated data and equwalent circuits to compare with experimental data
The question that we and others have posed is "Can we define the equivalent circuit analog of
an electrode/electrolyte system via computer modehng9" The following is a report of our at-
tempt to answer this question and the results of our efforts
Model Analysis
An eqmvalent clrcmt is viewed as two-dimensional The clrcmt elements of a real electrode

process are distributed over three-dimensional space, and the electrochemical behavior is af-
fected considerably as a result
The electrode can be described as having properties that are distributed over a surface that is
not smooth but rather has substantial surface defects, kinks, ledges, etc The charge distributions
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to
COMPLEX PLANE
2000
f ge 0 01 Hz - 5( , kHz
RI=1000 ohms
R2=1000 ohms
1600 R3=1000 ohms
C1--0.001 uF
C2=1 uF
O 1200
I,-,t
~, 800
400
High f
-V --..,.,
\
| , =
1000 1400 1800 2200 2600 3000
Z(REAL), O H M
FIG 6--Extending the upper lmut of the frequency range from 10 to 50 kHz changes the appearance of the
plot shown tn Ftg 5
over the surfaces are not uniform This conclusion can be summanzed by saying that the reac-
uon kinetics and the corresponding charge flow are dlstnbuted across the interface m such a
manner that our observations (l e , our measurements) are essentially averages over the effUre
electrode surface
On the one hand, the above analysis should be kept m mind so that we do not come to believe
that, simply because we generate an equivalent circuit, it is completely representative of the
electrode On the other hand, it does seem that these systems, even though complex, do lend
themselves to being approximated by equivalent circuits We might better think of the system as
being such that one or more equivalent c~rcmts elements can gwe a reasonable approximation of
the system If this IS the case, perhaps an equivalent ctrcmt that appears inadequate ~s simply
lacking an adequate number of elements a n d / o r appropriate values for the components
In view of this, an electrochemical cell which displays dlstnbuted impedance conduct should
be approximated by constant-phase elements (CPE) The CPE exhibits a more complicated
C1 C2
111~ 1 ~ ~ 1~~
R1 112
R3
-OUT 0 01 +OUT +IN -IN

FIG 7--Volgt equivalent ctrcult for N = 2 (t e, for two R C components)
frequency response than an undistributed, tdeal, c~rcmt element Th~s enhances the process of
fitting observed frequency data for a cell wRh dtstnbuted properties
There ~s another problem that is potentially a serious one In practice, an equivalent clrcmt
can be rearranged m various ways and still yield exactly the same impedance response at all
frequencies The experimental aspects of this paper deal with a number of these circuits and their
Identical impedance frequency response Consequently, the researcher is confronted with the
challenge of defimng the proper criteria for selecting the appropriate equivalent circuit for these
'hdentlcal" equivalent clrcmt posslbflmes
Procedure
We used two systems for computational techmques The first system consisted of a PC-based
Computer Assisted Engmeenng/Computer Assisted Design (CAE/CAD) system We chose the
EE Designer III / E (EEDIII) (Vlslomc Corporation, Santa Clara, Cahforma) although other
clrcmt simulation software systems can be used The CAE/CAD was used to prowde circuit
C1
In
100nF
R1
| I
110
C2
R2
0 825 uF 11 0
R3
-OUT 0 01 +OUT +IN -IN
FIG 8--Maxwell equivalent etreult for N = 2 Component values were calculated based on the
Votgt values o f
Ftg 7 to provide an equtvatent circuit
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Ag
+OUT R1 -OUT R2 R3
i t I ) t [-"'-I
0.01 100 [ 100
~t l u F == =mC1 luF =:=C2

i i
FIG 9 - - L a d d e r equivalent circuit for N = 2 RI was used as a " d u m m y " resistor in order to make
mTpedance calculanons possible on E E D I l l software
slmulaUon and, m turn, to obtain a-c frequency response s~mulat~on data and a Nyqmst plot
from defined equivalent circuits of interest A second system consisted of a series of computer
programs used to obtain imaginary versus real impedance data at different frequencies for some
equivalent ClrCUltSthat were also processed by the C A E / C A D system
It was then shown that the impedance results calculated from the results obtained from the
C A E / C A D software are consistent with the results obtamed from our computer programs This
consistency allowed us to use the powerful a-c simulation feature of the EEDIII software and
determine impedance responses ofequwalent circuits that are more complicated than the com-
puter program can handle Although computer programs can be written for the analysis of
circuits of any complexity, it becomes a tedious task The use of a C A E / C A D system greatly
slmphfies the chore
With these computational tools we investigated the following
1 The consistency of the impedance response data obtained from the C A E / C A D system and
the QmckBASIC programs
2 The effect of changing component values and frequency range on the shape of the complex
plane
C1
01
1.00 uF
R1
1 I
200
C2
R2
0 250 uF 200
R3
t t C)
-OUT 0 01 +OUT -IN +IN
FIG 1O--Component values calculated by the Ladder-to-Maxwell conversion techmque
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License
VOIGT CIRCUIT ANALYSIS
3200
f r~ge--0 01 ! z - 1 0 0 ~ z
2800 RI=1000 ohms E.
R2=1000 ohms
R3=1000 ohms
2400
J J
A []
2000 elL0 01 uF
C2=1 5 uF
Ci=l uF
C2=1 uF
C3= 225 uF C3=1 uF
1600
1200 /e"
800
/
400~ ~!hf
,v. .... .....
0 400 800 1200 1600 2000 2400 2800 3200
Z(REAL), OHM
FIG 1l - - Nyqutst plots obtainedfor the Votgt ctrcult wtth N = 3 and the capacitor values ( 1 ) equal D, and
(2) separated by a factor of 150 A Contrast these plots with those of Figs 12 and 13 obtamedfor the Maxwell
and Ladder circuits Data were generated by a computer program wrttten for this clrcult
3 The identical impedance response for a number of different equivalent clrcmts

4 Impedance analysis of the three eclulvalent circuits Vomit, Maxwell, and Ladder
Results
The results are shown in Figs 1 to 13 with explanations given by the captions
Discussion
Although a computer program can be written for a circuit of any complexity, doing so can
become very tedious for complex circuits The plot of Fig 3 indicates that CAE/CAD can be
used to satisfactorily simulate impedance data for complex circuits
Component values play an important role on the impedance response of various equivalent
M A X W E L L CIRCUIT ANALYSIS
1200
]f range=0 01 Hz - 100 kH
RI=1000 ohms
R2=1000 ohms
R3=1000 ohms
800
CI=0 01 uF CI=I uF
C2=1.5 uF C2=I uF
.< C3=I uF
C3= 225 uF
400
0 !
0 400 800 1200
Z(REAL), OHM
FIG 12--Nyqutst plots obtained for the Maxwell cwcutt with N = 3 and the capaotor values ( 1 ) equal f~,
and (2) separated by a factor of150 A Contrast these plots with those of Ftgs 11 and 13 obtained for the Votgt
and Ladder orcutts Data were generated by a computer program written for this ctrcutt
clrcmts Furthermore, the choice of a frequency range can further comphcate the mterpretatton
of the impedance spectrum by hiding some components from the equwalent clrcmt of mterest
For example, the capacitance of elements C 1 and C2 were changed m the c~rcmt of Fig 2 In
contrast to F~g 3, the same c~rcmt exhibits two separate semicircles, as shown m F~g 4, when the
capacitor values are separated by a factor of 150 In an electrochemical cell, the C 1 capacitor
may represent a "geometrical" capacitance, perhaps due to a paint coating for example, and the
C2 capacitor may represent a double-layer capacitance adjacent to the metal substrate
If we now consider a different magmtude of capacitances, the impedance data may reveal a
different picture, depending on the frequency range selected Figure 5 is the case of capacttor
values o f C l = 0 001 #F and C2 = 1 #F The complex plane of Fig 5, obtained at a frequency
range of 0 01 Hz to 10 kHz, reveals the presence of only one semicircle or time constant This is
ln&catwe of one capacitor element m the equwalent clrcmt However, if the frequency range is
expanded to 0 01 Hz to 50 kHz, the other semicircle starts to appear on the complex plane as
shown m Fig 6
L A D D E R CIRCUIT ANALYSIS
3200
f r~[ ge_-0 01 l z - 100 ~kHz

2800 : RI=1000 ohms 9
R2=1000 ohms
R3=1000 ohms
2400
I [
&
2000
I
O C l - ~ 01 uF CI=I uF
C2=1.5 uF C2=I uF
C3=225 uF C3=I uF
1600
1200
400 ( Fh!h f
0 .. [
v .... 3 (
0 400 800 1200 1600 2000 2400 2800 3200
Z(REAL), OHM
FIG 13-- Nyqutst plots obtained for the Ladder circuit wtth N = 3 and the capacitor values ( 1 ) equal [], and
(2) separated by a factor o f l SO A Contrast these plots with those of Figs 11 and 12 obtained for the Volgt and
Maxwell ctrcults Data were generated by a computer program wmtten for thts elrs
Three equwalent c]rcmts often encountered are Volgt, Maxwell, and Ladder [ 1 ] For the case
of two time constants or RC networks (N = 2), the clrcmts are shown m Figs 7 to 9, respec-
twely These clrcults can all yield the same impedance response for all frequencies when their
component values are properly related For the Ladder-to-Maxwell conversion, an arbitrary set
of component values were selected for the Ladder network as shown m Fig 9 Next, mathemati-
cal conversions were used to generate a set of component values for the Maxwell c]rcmt of Fig.
10 A C A E / C A D system frequency-response slmulaUon was performed on the clrcmts ofF~gs 9
and 10 The frequency response data were ~dent]cal m both cases A similar analysis was per-
formed on the Volgt-to-Maxwell conversion, and identical frequency response data were ob-
tained for the cases of Figs 7 and 8 The important conclusion lS that different eqmvalent
clrcmts may exhibit the same Impedance response at all frequencies
Interestingly, for three RC elements (1 e , N = 3), all of these circuits can yield three distract
arcs m the complex plane if the three ume constants are well separated A computer program was
written for each clrcmt of three Ume constants In each case, two s~tuaUons were analyzed First,
a value of 1 #F was assigned to each capacitor and 1000 fl to each resistor Next, keeping the
value of the resistors constant, the capacitances were separated by a factor of 150 by asslgmng
Ci, C2, and C3 as 0 01, l 5, and 225/zF, respectwely A wide frequency range of 0 01 Hz to 100
kHz was selected The ~mpedance response data are plotted m Figs 11 to 13
Conclusions
Equivalent orcmts are effectwe tools for characterizing electrochemical systems only if the
limitations of their use is reahzed within the scope of their apphcauon Although the eqmvalent
orcmt is capable of mimicking the behavior of the interface, the clrcmts that are often adopted
are too slmphsUc to be of much mterpretwe value However, the eqmvalent clrcmts can be
improved as representatwe tools One should change the experimental parameter and look for
important response changes For example, changes m temperature, polarization values, or the
addmon of inhibitor or adsorption speoes can be useful m order to select a parUcular eqmvalent
model The best equwalent orcmt model is one which better pre&cts the imposed changes The
researcher should be aware that more than one eqmvalent orcmt may fit a parUcular set of
expenmental data Furthermore, various electrochemical processes may occur in various, often
widely separated, frequency regmns Therefore as wide a frequency span as possible should be
covered by the expenmental measurements
Acknowledgments
We wmh to thank Reza Ehsam, Massoud Rostamkham, and Hung Ta for their assistance with
the CAD/CAE and computer programming
References
[1] Macdonald, J R, hnpedance Spectroscopy, Wiley, New York, 1987
[2] Mansfeld, F, Corrosion, Vol 36, 1981, pp 301-307
[3] Mansfeld, F, Ken&g, M W, and Tsal, S, Corrosion, Vol 38, 1982, pp 570-580
[4] Bockns, J O'M and Reddy, A K N, Modern Electrochemistry, Plenum Press, New York, 1970
[5] Macdonald, D D in Corrosion~87, National Assoctauon of Corrosion Engineers, Houston, Paper 479,
1987
[6 ] Armstrong, R D, Bell, M F, and Metcafe, A A, Journal of Electroanalytwal Chemistry and lnterfaclal
Electrochemistry, Vol 77, 1977, p 287
[ 7] Cahan, B D and Chen, C T, Journal of the ElectrochemicalSociety, Vol 129, 1982, pp 474-480 and
700-705
[8] Shlh, H and Mansfeld, F, Corrosion, Vol 45, 1989, pp 610-614
R. C. N e w m a n , 1 Q. Song, 1 R. A. CottlS, ~ and K. Sleradzkl 2
Atomistic Computer Simulation

of Alloy Corrosion
REFERENCE: Newman, R C, Song, Q, Cottls, R A , and Sleradzkl, K, "Atomistic Computer
Simulation of Alloy Corrosion," Computer Modehng in Corroston, ASTM STP 1154, R S Munn,
Ed, American Society for Testing and Matenals, Phdadelphm, 1992, pp 17-27
ABSTRACT: Atomlstlc computer s~mulatlon ~s concerned with the modehng of the behawor of
an alloy by modehng the dlssolutmn of individual atoms from a section of a simulated crystal
Monte Carlo techniques are used for the construction of a random array of atoms in the crystal
lattice and to decide on the behavior of mdwldual atoms The techmque has previously proved
valuable m understanding several aspects ofdealloymg, this paper is concerned with the extensmn
of this work to cover the actlve-passwe transmon m binary alloys such as Fe-Cr It IS found that a
very s~mple set of rules for est~matrag the dissolution probabdlty for an mdw~dual atom can give a
reahst~c representatmn of the acuve-passlve transmon These rules are based on the concept that
fully developed passwlty due to the chromtum content of the alloy depends on the existence of
continuous chains of-Cr-O-Cr- hnkages at the metal surface
KEY WORDS: passlwty, computer simulation, Monte Carlo method, lron-chrommm alloys
This paper ~s concerned w~th the use of a computer model to assist in the understanding of the
corrosion, and, m particular, the passlvatlon of homogenous alloys The classical example of a
binary alloy showing passwatlon is the ~ron-chrommm system, m which the chrommm gwes
passwatmn m a o d s m condmons whtch do not cause passlvatlon of ~ron There ~s a reasonably
sharp transmon m behawor at a c h r o m m m concentration of about 9 to 11%, when the alloy
starts to exhibit a pamal passwatlon at potentmls much lower than the passwauon potential of
pure iron However, the behavior is not fully " c h r o m m m - h k e , " and a secondary passwatlon
peak or shoulder Is observed, which may be assocmted with the formatmn o f a passwe film
incorporating iron As the chrommm concentration is mcreased, th~s secondary pass~vatmn
becomes smaller m magmtude (2 e , the peak current density falls) and d~sappears at chrommm
concentratmns of about 17% [ 1 ] Prevmus attempts to understand this behawor have covered a
range o f possibilities, but a c o m m o n feature has been their treatment o f the alloy as a uniform
continuum Th~s ~s clearly an overslmpllficatmn, as the random arrangement o f the atoms m the
crystal structure of the alloy wdl lead to local clusters which are rich m iron or c h r o m m m atoms,
and the corrosion behawor o f the alloy will be controlled by the dlstnbutmn of the atoms and
their response to the corrosive environment Slmdar factors are important in the related field o f
de-alloying, where a probabdlstlc model has been found to offer considerable insight into the
reasons underlying critical composmons and the effect of potentml on de-alloying [2] It is
notable that the compositmns at which passwatmn ~s first observed, and that at which the alloy
exhibits fully " c h r o m m m - h k e " behavmr, correspond to site percolation thresholds for interac-
tions up to the third and second nearest neighbors respectwely [3,4]
Umverslty of Manchester Institute of Scwnce and Technology, P O Box 88, Manchester, Umted
Kingdom
2 The Johns Hopkins Umverslty, Baltimore, MD 21218
17
The Model
In essence, the approach used In this work is to model the alloy by consldenng the corrosion of
a geometrically regular but compositlonally random array of atoms Individual atoms are as-
signed dissolution probabilities which are a function of their local environment, and in particular
the number and type of their nelghbonng atoms Thus an atom with only one nearest neighbor
will have a very high dissolution probability, whereas an atom with five nearest neighbors (as-
suming a simple cubic crystal structure) will have a very low dissolution probability (an atom
with six nearest neighbors will not be exposed to the solution and will therefore have zero
probability of dissolution) The corresponding rules for the two-dimensional case are similar
with atoms dissolving with increasing probability as the number of nearest neighbors falls from 3
to l
In the absence of film formation processes, if we knew the dissolution probabilities for each
type of atom in all possible combinations of neighbonng atoms, we should be able to estimate
the corrosion behavior of a small section of crystal simply by iteratlvely allowing all the surface
atoms to dissolve with the appropriate probablhty This principle forms the basis of the atomlstlc
model of de-alloying which has been described elsewhere [ 2 ] There are some hmltations to this
approach It is extremely computatlonally intensive, especially when trying to consider three-
dimensional crystals of a reasonable size, and it is difficult to use a large enough sample to have a
realistic dislocation density The presence of at least one screw dislocation emerging through the
metal-solution interface is essential in order to provide a continuing supply of ledge sites, at
which corrosion will be concentrated There is also very httle information on the relevant disso-
lution probabilities, and the selection of values to use is largely a matter of informed guesswork
While these limitations hinder the development of a fully quantitative approach, they do not
prevent the use of the model with very simple assumptions to give valuable insights into the
atomlstic processes underlying de-alloying
The extension of this model to cover passive systems IS largely a question of modifying the
dissolution probabilities to take into account the formation of passive oxide It must be appre-
ciated that this introduces some additional complications In particular, it is currently necessary
to assume that the corrosion of an individual atom is influenced only by the environment of the
atom in the metal, and not by any features in the solution Thus there are questions about the
ability of dissolution to occur through very narrow pores in the metal, and about the influence of
surface films on the dissolution In the case of a simulation ofpasslvatlon, the latter constraint is
clearly significant, but it is possible to accommodate the development of local regions of passlv-
ation by modification of the dissolution rules, as will be seen below
The first stage In the development of the model is the construction of a random two- or
three-dimensional gnd of atoms This is achieved by selecting atoms for each grid site with a
probability which is proportional to the concentration of each species
For the two-dimensional array the two "sides" of the grid are linked together as indicated in
Fig 1 This may be thought of as treating the array as a section of an indefinitely repeating
sequence of identical arrays, or as a hollow cylinder The primary advantage of this approach is
that it ehminates problems of edge effects A range of grid sizes has been used, up to 300 by 200
atoms
The three-dimensional array consists of a simple cubic grid with a screw dislocation running
through the center of the grid and lying normal to the surface of the grid exposed to the solution
(Fig 2) This ensures that there is always a ledge on the surface, which rotates around the screw
dislocation as the sample corrodes The block could be linked across opposing edges, effectively
"tiling" a plane with Indefinitely repeating blocks However, this would correspond to a very
high dislocatton density, there are also some problems of detail associated with the treatment of
the step associated with the screw dislocation For these reasons edges have been treated in the
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to L
NEWMAN ET AL. ON ATOMISTIC COMPUTER SIMULATION 19
FIG. l--Configuration of the two-dimensional grid, showing connection of the two sides.
three-dimensional case by applying an extra layer of "insoluble" atoms around the four sides of
the sample. This is not thought to have resulted in significant errors, as the corrosion invariably
propagates downwards and outwards from the center of the screw dislocation. The three-
dimensional analysis suffers severe problems of storage space and computation time, which
restrict the size of "block" which can readily be processed, and most work, including that
reported here, has used a 30 by 30 by 20 atom block.
Having constructed the grid of atoms, the dissolution rules are applied to each exposed atom.
~X
~C~?ssssS4. ~ s6-~
Y NN
NN
i V
Z
FIG. 2--Configuration of the two-dimensional grid.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No fu
The simplest algonthm examines each atom m turn, and decides whether or not it is going to
corrode on the basis of the number of neighbors it has and the relevant &ssolutlon probablhty
This Is very efficient in terms of storage space, since each grid position can be described In one
byte or less However, it is also very inefficient m terms of computation speed, and several
methods have been used to accelerate the computation The program is currently run on a
20-MHz 80386-based IBM PC compatible coAnputer and is written in Turbo Pascal The most
important method used to accelerate the program ~s to use integer arithmetic for all calculations
within the main loop Thus probabilities are represented as integers in the range 0 to 10 000,
corresponding to the range 0 0 to 1 0 Additional mo&ficatlons to the "dissolution" algorithm
are employed to minimize the number of atoms which have to be processed on each computa-
tion cycle The most important of these is the maintenance of lists of atoms of the two types
which are exposed to the solution, thereby eliminating the need to consider atoms within the
bulk of the metal For the three-&menslonal case this transforms the calculauon from order N 3
(where N is the hnear &menslon of the block being analyzed) to approximately N 2 An ad&-
tlonal advantage of this approach is that the order of the atoms in the lists may be randomized,
thereby avoiding any artefacts which might arise due to the testmg of the atoms in a regular
order A second means of accelerating the calculation is to maintain a record of the number of
nearest neighbors for each atom to avoid a rather complex counting operation This is best done
by using two bytes for each grid posmon, although the information can be encoded into one byte
at the expense of some computational complexity
A further acceleration can be achieved by mo&fymg the method of selection of the atoms
which are to corrode in each cycle In the simple algorithm a random number is generated for
each atom in turn, and this number is compared with the probability of dissolution appropriate
to the atom and its environment to determine whether or not it wdl dissolve However, an
alternative approach can be employed which will reqmre the generation of fewer random num-
bers in many circumstances If separate lists are maintained for ~ltoms with particular numbers of
nearest neighbors, the problem may be reduced, for each list, to the determination of the number
of atoms &ssolvmg (which will be a sample from the binomial &stnbutlon) and the selection of
random atoms from the list for corrosion, which is a straightforward problem While it offers the
prospect ofslgmficant speed advantages for larger arrays, this approach requires further increases
in storage for each grid point As atoms &ssolve, their neighbors will need to be transferred from
one hst to another This can only be done efficiently lfa pointer to the entry in the list is stored in
the main array, at the cost of doubling the size of each entry (assuming that 16-bit pointers are
adequate) For the relatwely small arrays used in this work the additional complexity of this
algorithm and the reduction in size of array which can be processed have outweighed the speed
advantages, and this approach has not been used for the work reported here
Dissolution Rules
The construction of the gnd of atoms and the processing of the dlssoluUon of the relevant
atoms are reasonably straightforward computational problems The real science of this study is
concerned with the development of the rules which describe the probability of &ssolutlon of an
atom m a given environment In this respect it is useful to consider the slmulat~on process as an
experiment, m which the feaslbdlty of the dissolution rules being used are tested by the compari-
son of the outcome of the experiment with actual behavior.
We can approach the selection of reasonable rules by consldenng tn a quahtatwe sense the
behavior we expect for the two types of atoms m the alloy We shall primarily refer to the
three-dimensional case, the rules for the two-dimensional case are similar For slmphclty, we
shall refer to these as iron and chromium, but it will be recognized that these are just examples of
the non-passivating and passwatmg components of the alloy
Dissolution Probability
1.0E§
1.0E-01
1.0E-02
1.0E-03
1.0E~ ~ i l i i t i
-4 -3 -2 -1 0 1 2 3 4
Potential (Nominal Units)
FIG. 3-- Variation of dissolution probability with nominal potential.
At negative potentials (around E0 for iron, but well above E0 for chromium), iron will have a
low dissolution probability, while that for chromium will be high. As the potential increases, so
the dissolution probability for iron will increase rapidly, probably being an exponential function
of potential. However, the chromium dissolution may become chemically limited [ 5,6 ], and the
dissolution probability will change relatively slowly with increasing potential. The resultant
variation in dissolution probability with potential (on an arbitrary scale) is shown in Fig. 3.
It will be noted in the discussion above that the chromium atom is considered to remain in the
metal surface when it has formed a passive oxide, only disappearing from the metal lattice when
it has dissolved into solution. While this may be a slight oversimplification, it provides an
effective model for the solid-state formation of passive oxide from the chromium atoms in the
metal. It will be appreciated that this will give quite different characteristics to alternative models
involving precipitated films of oxide.
So far we have been considering the behavior of individual chromium atoms. However, an
individual chromium atom cannot, by itself, form a very protective passive oxide, and it will tend
to dissolve at a reasonably high rate. Much more effective passivation can be achieved when
chains of chromium atoms are bridged by bonds to oxygen atoms (Fig. 4). This is expected to
occur optimally for chromium atom spacings corresponding to second-nearest neighbor posi-
tions. Atoms at the ends of the -Cr-O-Cr- chains (i.e., with only one exposed Cr first or second
nearest neighbor) will not be fully protected by the oxide and are expected to dissolve, but atoms
within the chain (i.e., with two or more exposed Cr neighbors) will have a very low dissolution
probability. It is also possible for -Cr-O-Cr- links to be formed between chromium atoms in third
22 COMPUTERMODEUNG IN CORROSION
FIG 4--Cr-O-Cr brtdges leading to passtvatlon
nearest neaghbor locauons, but these bonds are more stramed and therefore less protectwe
Passwatlon wath films including thard nearest neighbor linkages as thought to be responsable for
the first onset of primary passwataon at 9 to 11% Cr, whach as not being considered here, we
concentrate on the &sappearance of ~ron-lake behavior
The above consaderataons lead to the following samphfied rules for the calculataon of&ssolu-
tlon probabdaty
( a ) Exposed aron atoms wath four or less nearest neighbors wall dassolve wath a probabdlty
whach increases as the "potentml" mcreases (three or less nearest neighbors m the two-
&mensaonal case)
(b) Exposed Cr atoms wath zero or one exposed Cr first or second nearest neighbors wdl
&ssolve wath a probabdlty which as independent of"potentml "
(c) Exposed Cr atoms with two or more exposed Cr first or second nearest neaghbors wall not
&ssolve
It wall be recogmzed that the above rules contain several slmphfymg approxlmataons How-
ever, they provide a reasonable descnptaon of the expected behavaor m a form whach lends atself
to efficaent computauon They also have the advantage of extreme slmphcaty, such that there are
very few adjustable parameters m the model, whach maght be used to force the results to fit
expectataons Refinements m the model (such as the mcorporataon of more complex relation-
ships between &ssolutaon probabdaty and local envaronment) generally only affect the detailed
quanmatwe response
Results
Typtcal results of analyses wtth the above rules are shown m Figs 5 to 7 Figure 5 shows a
two-&mensional lattice which has been corroded until passwatlon has been achieved (note the
continuous chain of exposed Cr atoms, shown m grey) Figure 6 shows the correspondmg
three-dimensional result, presented as a series of atom planes parallel to the surface of the block
(note that there Is a dlscontmmty running down from the screw &slocatlon m the center of each
plane to its bottom edge, where the right-hand part of one plane joins the left-hand part of the
plane below)
The ano&c current density may be equated to the rate of &ssoluuon of atoms In order to
chromate transaent effects, the dissolution rate as estamated over the second half of the analysis
The resultant "polarization curves" for three-&mensaonal samulataons of alloys wath a range of
chrommm concentmuons are shown an Fag 7 A total often independent simulations have been
performed at each "potential", the mdwldual results are plotted m Fag 7 for the 26% Cr case (the
&amond markers) Only the average curves are shown for the other Cr concentraUons in order
to avoid cluttenng the dmgram Away from the actwe-passwe transmon ~t can be seen, for the
26% Cr case, that the response as reasonably repeatable, but there as a wide variation m the results
around the actwe passwe transmon as a combined result of the small sample saze coupled wath
z
m
z
m
-4
.i
-=
0
z
-4
0
0
"u
e"
-4
FIG. 5 - - Result of two-dimensional simulation, Fe-45% Cr, showing passivation at a dissolution probability of O.1 for Fe and 0.01 for Cr. m
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further reproductions authorized.
0
0
"13
c
-I
m
0
o
m
r-
0
0
z
FIG. 6--Result of three-dimensional simulation, Fe-26% Cr, showing passivation at a dissolution probability of O.I for Fe and 0.01 for Cr.
Dissolution Rate (atoms/cycle)

1000000
17%
100000
10000 ~ ,,.,'f 20%
1000
1 O0
10
0.1
0.01 0 0 00,~
I I L I I k
0.001
-4 -3 -2 -1 0 1 2 3 4
Notional Potential
FIG. 7--"Polarization curves"for alloys of Fe-I 7 to 32% Cr, showing dissolution rate as a function of log
(dissolution probabifty for Fe/dissolution probability for Cr).
the random variation in surface composition and arrangement of atoms. The fluctuations in the
average curves around the active-passive transition similarly result from the random nature of
the simulation and are not significant. Similar simulations in a body-centered-cubic (bcc) lattice
would give chromium-like behavior at around 17% Cr, as in real life.
Discussion
In examining the results of these simulations, it should be appreciated that no attempt has
been made to simulate the first onset of primary passivation at 9 to 11% Cr, which is thought to
be associated with third nearest neighbor interactions between chromium atoms. We are there-
fore concerned with the characteristics of the active-passive transition and the full disappearance
o f iron-like behavior at about 17% Cr.
The results obtained from the simulation show several features which are consistent with
experimental observation. These include:
( a ) The more rapid corrosion of higher-chromium alloys at more negative potentials in the
active region.
(b) The decreasing critical current density for passivation as the chromium concentration
increases.
(c) The more negative active-passive transition potential for the higher-chromium alloys.
( d ) A critical chrommm content for passwlty close to Pc(1,2) [site percolation threshold for
interactions up to second nearest neighbors]
Th~s match between expenment and slmulatton ~s not, of course, a conclusive argument for
the physical model used m the construction of the simulation However, the simulation has
proved to be a powerful technique for the testing of ideas about the physical model, and many of
these ideas are reflected in the physical model described here
It wdl be clear from the descnptmn of the rules defimng the &ssolutlon probabdmes that there
are many ways in which these could be refined to "improve" the match between simulation and
expenment However, to concentrate on these developments would be to miss the fundamental
point that simulation techniques such as those described here are at their most powerful and
effective when used to test stmple concepts, albeit apphed to a complex system
Conclusions
The use ofatom~st~c simulations has prowded valuable insights into the corrosion and passiv-
atmn of alloys In respect to the passwat~on of lron-chrommm alloys they have shown that the
passwatmn can be explained m terms of the formaUon of Cr-O-Cr bridges, which tend to protect
the chrommm atoms from dlssoluUon, with "full" passlvaUon occurnng when continuous
chains are formed
References
[1] Newman. R C, Foong, T M, and Sleradzkl, K, Corrosion Scwnce. Vol 28, 1988, pp 523-527
[2] Sleradzkl, K, Corderman. R R. Shukla. K, and Newman. R C, Phdosophtcal MagazmeA. Vol 59,
1989, pp 713-746
[3 ] SongQlan, Newman, R C. Cottls. R A. and Sleradzkl, K, Journal of the ElectrochermcalSocwty, Vol
137, 1990, pp 435-439
[4] Song Qlan, Newman. R C, Cotus, R A, and Sleradzkl. K, Corroston Scwnce. Vol 31. 1990, pp
621-626
[5] Keddam. M, Mattos, O R, and TakenoutL H, ElectrochtmwaActa, Vol 31, 1986, pp 1147-1158
[6] Keddam, M, Mattos, O R, and Takenoutl. H. ElectrochtmtcaActa. Vol 31, 1986, p 1159
DISCUSSION
U Bertoccl I (written dtscusston)--(1) I suggest putting some mlsonentatlon steps on the

surface The periodic boundary condmons will act as to maintain the step density Th,s might be
computatlonally simpler than a screw &slocatlon and possibly easier to interpret by visual
inspection
(2) Does the dislocation wind up onto ~tself when the potential is increased so that the
dissolution rate mcreases9
R C Newman et al (authors" closure)--( 1) Since prepanng this paper we have done this, and
it is simpler (and therefore faster) computatlonally It gwes similar results to that for the screw
&slocatton
(2) The rate of dissolution does not change the corrosion morphology, only the speed with
National Institute for Standards and Technology, Galthersburg, MD 20899

DISCUSSION ON ATOMISTIC COMPUTER SIMULATION 27
which it occurs Owing to the effect of the passlvating element, there is generally a rather small
tendency for etch pitting (which is essentially what we understand the questioner to mean by the
"dislocation winding up onto itself") to occur around the dislocation As a rule we should only
expect etch pitting when all components of the alloy are dissolving under activation control,
such that the corrosion morphology is dominated by the effect of the ledge associated with the
dislocation
N Srtdhar 2 (wrztten dtscusszon)--While this more or less geometrical model can explain
passlvatlon as a function of potential and Cr content m Cr-containlng alloys, it cannot explain
passivity in pure Cr unless a dissolution probability dependent on potential for Cr is assumed,
which is contrary to the ongmal assumptions of the model
R C Newman et al (authors' closure)--We agree, but the passlvatlon with which we are
concerned occurs at a potential that is significantlydifferent from that at which the passivatlon of
chromium Is expected
2 Southwest Research Institute, San Antomo, TX

M. H e l m l A t t l a 1
Thermal Modeling of Crevice Corrosion

and Its Interaction with Fretting
in Confined Geometries
REFERENCE: Attla, M H , "Thermal Modeling of Crevice Corrosion and Its Interaction with
Fretting in Confined Geometries," Computer Modehng m Corroston, ASTM STP 1154, R S
Munn, Ed, Amencan Society for Testrng and Materials, Phlladelphm, 1992, pp 28-43
ABSTRACT: Local nucleate boiling m the crewce region between non-conforming contacting
bo&es causes an increase m the chemical concentratmn of the solution flowing rn this region This
in turn may result m accelerated crevice corrosmn damage This paper is concerned w,th the
development of a computer model for accurate pre&cuon of the temperature field and the occur-
rence of nucleate boiling m the crevice regmn The model recogmzes the closed-loop interaction
between the boding process and the temperature field, through the changes in the condmons of
heat transfer at water-cooled surfaces It also accounts for the volumetric effect of the thermal
contact resistance (TCR) and allows evaluating the thermal bamer effect caused by the increase in
the TCR due to fretting corrosion Analysis of the results indicated the slgmficance ofmodehng the
nonhnear behavior of the system for accurate predictions The results also m&cated that the
increase in the TCR with fretting corrosion can cause the crevice corrosion process to be a self-
hmmng one
KEY WORDS: crewce corrosion, fretting corrosion, thermal modehng, computer slmulatmn
In boding a h q m d at a gwen pressure, several regimes o f b o l h n g can be observed, d e p e n d i n g

on the temperature rise (mlsat) o f the heat transfer surface above the saturation temperature o f
the liquid As Alsat IS increased, the heat flux at the heating surface increases slowly ( n a t u r a l
convectwe superheating regime) a n d t h e n increases rapidly as bubbles form at active nuclei
on the heat transfer surface ( n u c l e a t e boiling regime) It is also well-founded that chemical
concentration, which can be e n h a n c e d by local nucleate boiling in the crevice region o f n o n -
conforming contacting bodies, can lead to an accelerated crevice corrosion, w h e n th~s concentra-
tion reaches a certain cntlcal level C o n o u et al [ 1] reported that a change in the concentration
o f h t h t u m hydroxide solution from 2 to 10 g / L increases the corrosion rate of zirconium alloys
by 100 times at 3 6 0 ~ Th~s critical concentration vanes significantly with temperature, it
increases from 0 4 g / L at 3 6 0 ~ to 6 g / L at 3 3 0 ~ It has also been reported in the literature
that only a few degrees rise m the surface temperature above the saturation point is sufficient to
reach the critical concentration From the design point o f view, this illustrates the importance o f
accurate modeling o f the heat transfer process fissoclated with crewce corrosion J o h n s t o n et al
[2,3] stated that while the seventy o f localized corrosion in the P W R (pressurized-water-
reactor) steam generator tube-support plates can be minimized by water chemistry a n d im-
proved matenals, the formation a n d m a i n t e n a n c e o f dry regions, as an initiator o f corrosion
damage, is a problem o f heat transfer a n d fluid mechanics A similar approach was followed by
others [e g , 4] In heat transfer equipment, the sites susceptible to crevice corrosion are usually
can&dates for fretting corrosion as well, due to flow-induced vibration
A system approach to the thermal aspect o f the crewce corrosion process is presented in this
t Research Engineer, Mechamcal Research Department, Ontario Hydro Research Dwlston, Toronto,
Ontario, Canada M8Z 5S4
28
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agree
ATTIA ON CREVICE CORROSION 29
paper and used to develop a heat transfer model which recognizes the nonhnear nature of the
problem This nonhneanty is primarily due to the fact that local boiling is both controlling, and
being controlled by, the conditions of heat transfer at the contact and crevice regions In this
computer-simulation model, the coefficient of heat transfer, h, is neither assumed nor imposed
on the system, but is an integrated part of the sought-for solution The effect of the time variation
o f the thermal contact resistance ( T C R ) due to vibration-Induced fretting corrosion is also
included in this model The proposed approach is demonstrated through a case study using the
finite difference method, in which the effect of the thermal contact resistance is accounted for
Effect of Fretting on Thermal Contact Resistance (TCR)

In static contact, as the heat flow lines approach the interface they converge towards the least
resistance paths, gwmg nse to a "thermal constnctlon resistance" (Re) The temperature distri-
bution in a plane normal to the nominal interface seems to be discontinuous, exhlbmng a
"pseudo"-temperature drop (Atl) at the interface to overcome R c
Atl
Rr = ~ (1)
q
where q Is the heat flux When the contacting surfaces experience an oscillatory relative motion
of small amphtude < 100 to 130 tzm [5 ], due to flow-induced vibration or any other vibration
source, fretting corrosion will take place U n d e r such a condition, the thermal contact resistance
changes because of the following two effects
l The change in surface roughness and generation of fretting wear debris

2 The relative reclprocatory motion, resulting in the heat input to one o f the two contacting
solids being due to a moving (oscillating) heat source
A fundamental study o f the effect o f the reclprocatory mode o f motion on R c has been c a m e d
out by Attla et al [6] It was assumed that an asperity o f a umform square cross section oscillates
over a semi-infinite body The maximum temperature rise due to fretting is expressed in terms o f
the heat accumulauon factor ( H A )
cop 1 1
HA = 0 ~ - - - - (2)
4t.t p A
and the following dimensionless groups
the amphtude ratio (A) = a / L
at
the Fourier number ( Fo) = --~
where
0 = the temperature rise at the interface,
Cp,p = the specific heat and mass density of the material, respectively,
a = the amplitude of oscillation,
L = half the length o f the side o f an aspenty o f square cross section,
a = the thermal dlffUSlVlty of the matenal,
t = time,
# = the coefficient o f friction, and
p = the contact pressure
In terms o f the heat accumulation factor ( H A ) , the maximum quasi-steady temperature nse
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to Li
1.0
A=0.1
RECIPROCATING A=O.1
MOTION A= 1.0
lx10 -1
A=IO.O ~ I.~-A=10.0
/
=r
o
I-
U lxlO -2
.<
M.
<:
-r.
UN IDI RECTIONAL
SLIDING
lx10 ~
STATIONARY
CONTACT
lx10-q[ , , ~ , ,,L,I , ~ ...... I , , ,

lx10 -3 lx10-2 lx10-1
Pe/A
FIG I--Change tn the ma ~:tmum value of the heat accumulatton factor (HA) wtth frequency parameter
(Pe/A)for dtfferent amphtude ranos ( A ) and modes of morion [6]
obtained at t h e center of contact is presented m Fig i as a function of the frequency and

amphtude parameters Pe/A and A, respectwely, where
H A oc A" (3)
1..e 9
O OC A m+l (4)
where Pe is Peclet number, Pe = a f . L / a

Figure 1 indicates that for small amphtudes (l e , A < 1 0) the exponents n = 1 and m = 0
(1 e , O Is hnearly proportional to the amphtude a and the frequency f ) As A is increased to 10,
th~s hneanty is only vahd for Pe/A < 0 01.
A'I-FIA ON CREVICE CORROSION 31
~/" 8 80
tL
Zr-2.5 % w t N b / Z r - 4
O a= :~,5 l ~ n -- 70
E 7 E
E f=6Hz
t~
Pc = 0 . 8 5 M P a -- 60 I--
Z
LU t c = 150"C tU
o -- 50 tU
z 5 a
oo o
-- 40 O.
N 4 to
W o a
it.
-- 30 O
o 3
iii
a
- 20
-J
..J Q.
< - 10 <
n"
IJJ
~0 I
1
I
2 3
I
54
I
6
I
7
I
8
I
9
..,
10
I
11 12
I I I
TIME, days
FIG 2--Changes m the thermal contact reststance wtth the progress m fretting [ 7 ]
For the same model as presented m Ref6, the temperature rise at the center of contact under
unidirectional shdmg and stationary contact is also shown m Fig 1 From the figure, one can
conclude that, for the same average heat mput, the heat accumulation factor HAt, and conse-
quently the maximum temperature rise m reciprocating mouon, exceeds the heat accumulation
factor HA, m stationary contact To a first approxlmauon, the rauo
HA,
= (5)
HA,
can be conmdered as a correction factor to be apphed to the static TCR Since P e / A is propor-
tional to real area of contact L 2, ~t can be concluded that
~ = b p m, m>0, 4><1 (6)
where b and m depend on the frequency and amphtude of osclllauon and can be determined
from the results gwen m Fig 1
Although there is a large volume of expenmental data on the change m the electncal contact
remstance with fretting, no such reformation ~s avadable for the TCR, with the exception of the
results shown in Fig 2 [ 7] For the test condmons described m Fig 2, it is concluded that the
thermal contact resistance (Re) increases continuously with time as a result of the change m
surface roughness and debris formaUon The rate of change Rc was shown to decrease progres-
mvely, however, untd a steady value was reached In this figure, the value of Re is expressed m
terms of the eqmvalent addmonal length AI of a thermal remstor made of the parent matenal
(Zry-4)
Thermal Boundary Conditions in the Crevice Region Formed by Non-Conforming Bodies

For a proper mmulatlon of the heat transfer process associated with crevice corromon m
confined geometry, dzfferent regions should be conszdered to express the thermal boundary
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuan
condmons namely the contact regmn and the crevtce region formed by the radlused surfaces of
the solids In the general case. when the geometry of the bodies m contact causes a slgmficant or
sudden change m the gap between them, a third regmn, which is termed here the open regton,
should be added
To define the boundaries of various regions, as well as the distribution of the thermal contact
resistance, the mechamcal contact problem should first be solved For sohds m elastic contact.
the extent of the apparent contact area (Aa) as well as the dlstnbuuon of the contact pressure can
be predicted from Hertzlan theory Knowing the local contact pressure (pc), the standard dewa-
tlon of surface asperity heights (tr). and the mean surface facets slope (tan 0), the micro-contact
configuration can be defined in terms of the following parameters
9 The average radms of contact rc
re =f{Pc, Pm, tan 0, a} (7)
where Pm denotes the y~eld stress of the metal

9 The raUo of the actual to apparent contact areas
, =f{p~,pm} (8)
9 The equivalent gap thickness between surfaces asperities in contact A
A =f{pc, pm. a} (9)
These parameters can readdy be estimated using avadable relations [e g. 8-11]
Knowing the parameters of the m~cro- and macro-contact configurauon, the thermal bound-
ary condmons of vanous regions can be described
Contact Regton
A large number of theories and correlations are available for obtaining the TCR and its
distribution along the interface [e g, 11-13 ] In a slmphfied functional form, the local value of
Rc is related to the m~cro-contact configuration and the material properties as follows
Rc = f { ( A , ~,~),(kg, kf)} (10)
where ks and k r symbolize the thermal conductwmes of the sohd and the interstmal fired,
respectwely The change in Rc with fretting can be accounted for by the analysis gwen in the
section on Effect of Fretting on Thermal Contact Resistance ( T C R )
Crevwe Region
The flow of a fluid film in a narrow passage can well be described by Reynold's theory In its
reduced form. where the squeeze and stretch terms are omttted, the distribution of the flow
velooty v is related to the pressure gradient along the crevice dp/dy, by the followmg equaUon
which satisfies the equlllbnum of the pressure and viscous forces
d2v= 1 dp (11)
dx 2 v dy
where p = vlscostty of the fluid
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to Lic
For thin film layers, the ratio of the heat transferred by convecUon to that transmitted by
conducUon across the film can be estimated by calculating the weighted Peclet Number (Pe)
[14]
~. H 2
Pe - (12)
o~-L
where
= the average velocity at a gwen film thickness H, obtained by v~rtue of Eq 11,
a --- the fired thermal &ffuswity, and
L -- the length of contact
When Pe approaches zero, conducUon becomes the dominant mode of heat transfer across the
crevice, unless nucleate bolhng is taking place
Open Regton
Within this regmn, the coefficient of heat transfer (h 0) depends on whether the flow is single-
or two-phase The available correlations [e g, 15] for single-phase hqmd flow can be used to
esumate h0
h0 = f { R e , Pr} (13)
where Re and Pr are the Reynolds and Prandtl numbers, respecuvely

Subcooled nucleate boiling occurs when the surface temperature (tw) exceeds the saturatmn
point (tat) and the solution temperature (to) at a certain locaUon
l,~> t~t> tr (14)
The nucleate boiling is a local surface phenomenon and depends neither on the hquld velooty
nor on the surface geometry To pre&ct whether nucleate bolhng is taking place m the crevice
region, the local surface temperature and heat flux should be compared to the onset bolhng
(ONB) curves and fully developed boding (FDB) curves These curves are expressed m terms of
the amount of superheat of the surface [At.t ]ONBand [At~t ]FDa that are required to start and to
establish a fully developed nucleate boiling regime, respectwely Bergles and Rohsenow's corre-
lation [ 16] expresses [ At~t]oNa as a function of the surface heat flux (qor~B) and the pressure (p)
[At.t]o~. = f { qONB,P, ~'} (15)
where '~' Is a parameter contammg the physical properues and depends on the surface/fired
combination For a gwen design pressure (p), Thom's correlation [ 17] can be used to pre&ct
[~t~tlrm = f { qv o , p } (16)
A partially developed subcooled nucleate bolhng exists between the subsaturatlon- and the
fully developed subcoohng bolhng-reglmes The geometric mterpolauon method proposed by
Bergles and Rohsenow [ 16] can be followed The heat flux dunng partial bolhng (qva) is there-
fore determined m terms of the heat flux for single phase forced convection (qSPL), the heat flux
CO
THERMAL CONTACT RESISTANCE TCR c

FRETTING i
CORROSION m
CREVICE GEOMETRY 0
HEAT INPUT I o
m
P
~>
DISTRIBUTION OF I z
CHANGE IN THE
TEMPERATURE S HEAT FLUX 0
ALONG THE BOUNDARY 0
LO
0J TEMPERATURE
+IC.R O
LU
g z
tW THE SOLUTION CREVICE
J CONCENTRATION CORROSION
I-
,< IN THE CREV4CE
I,g .~ hi ,,
Q.
I- o,~..,.o.,o.o~
~~CO~FIC,ENT L~ ~w
H~AT TRANS~ERr
/ ALONeT.~ BOUNDARY I
1
FLUID FLOWt
CONDITIONS
FIG 3--System approach for computer stmulatton of the thermal process assoctated wtth crevtce corroston
I E.'?AAc
...
LOADING.GEOMETR*
CHARACTERISTICS [
1
DISTRIBUTIONOF THE THERMAL I r- . . . .
I CHANGES L
INTCR DUE TO I
CONTACT RESISTANCE TCR F" ,NGCO'RO N 2
THERMAL LOADING AND

FLUID FLOW CONDITIONS
I
l INITIAL CONDITIONS
,,
- SINGLE PHASE LIQUID
- TEMPERATURE FIELD
d
--+
I
DISTRIBUTION OF CHT ALONG
THE WETTED BOUNDARY
I
YES
I TEMPERATUREFIELD AND I
DISTRIBUTION OF HEAT FLUX
ALONG THE WETTED BOUNDARY
REGION OF NUCLEATE BOILING
J
(END)
FIG 4--Flow chart representmg the method of solutton to predtct nucleate boding m the crevwe region
for fully developed regime (qvo), and the surface heat flux for fully developed nucleate boding
at a surface temperature corresponding to the onset of boiling (qFo/Or~B)
qPB = f { qSPL, qro, qm/o~B } (17)
System Approach for Thermal Modeling and Simulation of Crevice Corrosion

A system approach for computer simulation of the thermal eqmhbnum process assooated
with crevice corrosion is shown m Fig 3 This approach recognizes the nonhnear nature of the
process, due to the fact that the distribution of the surface temperature (tw) and the surface heat
flux (q) along the boundary is both controlling and being controlled by the &stnbutlon of the
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreem
coefliclent of heat transfer (h) along the wetted surface, which ~s unknown m advance This
thermal couphng results m a closed-loop interaction (Fig 3) As the heat flows into the contact-
mg sohds, both the temperature field and the heat flux adjust themselves according to the
&stnbutlon ofh This may result m different regaons ofsmgle-phase hqmd and nucleate bolhng
Thus the &stnbutlon of h wdl be altered, being enhanced at some location by the bodmg
process Consequently, the temperature field and the heat flux wdl be re&stnbuted and a new
boding region is estabhshed This cycle is repeated as many times as reqmred untd the steady
state of thermal eqmhbnum ts reached As shown m Fig 3, the blockwhtch represents the region
of nucleate boding ts mterrelated to the other two basic elements of the loop by the boding
curves (q { tw } ) and the coefficient of heat transfer-surface temperature relationship (h { tw } )
Gwen the relationship between the concentration of the solutton in the crewce and the surface
temperature (C { t . }), the occurrence of nucleate bodtng may cause the concentrauon of solu-
uon to reach its critical value (CR) The interaction between the corrosion process and the
changes tn the crevice geometry as well as the saturation temperature of the solutton (as shown
m Fig 3) introduce other sources of nonhneanty
If vibration is mduced m this system by the flow of the solution, or any other source, then
fretting corrosion wall take place at the contact interface From the analysis gwen previously, it is
postulated that the thermal contact reststance at the interface wtll be increased, causmg re&stn-
button of the temperature field m the sohds as well as the heat flux along their boundaries
A slmphfied scheme of solution ~s presented m Ftg 4, with this nonhnear behawor taken into
account The route starts with defining the macro- and mtcro-contact configuration to determine
the mmal &stnbutlon of the thermal contact resistance Re (Eq 10) and to define the geometry of
the crevice Knowing the flu|d flow condmons, the single-phase forced convection h0 ts estt-
mated (Eq 13) As an mmal guess, the coefficient of heat transfer CHT is assumed to be
uniformly &stnbuted along the water-cooled surfaces and is equal to the single-phase value
Under these boundary con&t~ons, and for the heat flux input to the system, the temperature
field and the &stnbutlon of the heat flux along the boundary are calculated With the surface
temperature and the local heat flux given at each boundary nodal point, one can predtct whether
local nucleate bolhng ts takmg place and, ff so, whether it falls reside the partmlly or fully
developed regimes (Eqs 14 to 17) This, m turn, allows updating the values of the local coeffi-
cient of heat transfer (CHT) The iteration scheme proceeds untd a sufficiently small &fference
between two successwe CHT distribution profiles is reached The accuracy of the final solution,
which represents the state of eqmhbnum, depends on the preset convergence cntenon
Generally, the effect of fretting on the change m the thermal contact reststance represents
long-term charges m the system performance dunng operaUon It is therefore placed within a
dotted-hne box m Fig 4 This box is transparent and wdl be by-passed by the solution algonthm
when only short-term predlcUons are required
Computer-Simulation Case Study

Statement of the Problem
A hypothetical case is analyzed m this section to demonstrate the apphcatlon of the algorithm
shown m Fig 4 and to examine the effect of the change in the thermal contact resistance due to
fretting on the nucleate bolhng process m the crevice region In this hypotheUcal case, two
non-conforming cyhndncal bo&es are considered The outer surface of the tuner cyhnder is
fin-shaped to take advantage of the symmetry and thus to slmphfy the fimte &fference ldeahza-
tlon of the problem (Fig 5) The geometry, &menslons, flow, and boundary con&tlons are
arbitrarily chosen to present a general case m which an "open region" exists and a partmlly
developed nucleate boding takes place m the crewce region The contacting bo&es were as-
sumed to be made of Zry-4/Zr-2 5Nb to be able to use the data given m Fig 2 Under the
assumed mechamcal loading, the distributions of the contact pressure and the thermal contact
reststance
Copyright over half
by ASTM the(all
Int'l contact
rightslength L areTue
reserved); shown
Feb m
10Fig 6 TheEST
09:33:27 latter is expressed in terms of
2015
FIG. 5--Nodel representation of the contacting bodies-finite difference approximation of two-dimensional

heat conduction.
the equivalent additional length Al of a thermal resistor made of the same material as the parent
solid bodies. With the assumed curvatures, the crevice gap thickness varies from 0 to 65 #m.
To simulate the effect of fretting, three additional thermal contact resistances equivalent to Al
= 0.75, 1.5, and 3.75 mm were superimposed on those shown in Fig. 6. These levels can be
related to operational conditions and time, using data similar to that shown in Fig. 2. The change
in the crevice profile due to fretting and crevice corrosion is ignored.
A two-dimensional, steady-state temperature field within the domain of the contacting bodies
l and 2 is assumed. The finite difference method, whose nodal network representation is shown
in Fig. 5, was used. The analysis is also based on the following assumptions:
9 The fluid pressure and flow velocity in the open region are 9 MPa and 8 m/s, respectively.
9 The fluid temperature tf and saturation temperature ts are 293 and 303~ respectively.
9 The heat input to the system at the I.D. of the inner cylinder is 1100 k W / m 2.
Solution of the Problem

As shown in Fig. 5, the two-dimensional heat flow field is divided into a grid, the size of which
Copyright by ASTM
was varied Int'l (allto
in relation rights
the reserved);
expectedTue Feb 10of09:33:27
pattern EST 2015
temperature gradient. Apart from the contact
38 C O M P U T E R M O D E L I N G IN C O R R O S I O N
00 10 x
00- 00 ' ~ DISTANCE
I L
Od
01- ~ 01
o
02- o-~
E 0c
E ~ 02
J
9~ 03- tu
04- ~ 03
Z
8
05-
04
FIG 6--Dtsmbutton "the contact pressure and the thermal contact resistance along the interface
interface, two different types of elements are used to conform to the boundanes of the domain
and to accommodate elements of different sizes the triangular and the annual segment
elements.
The energy balance on the control volume surrounding each nodal point ( i , ] ) , shown m Fig
5, results In a set o f finite difference equations of the form [ 18]
Ct "t,-l,j + C2"t,+l.j + C3"l,.j-I + C4"t,.j+l + C.'t,.y + D = 0 (18)
where
1 r
Ar I + Ar 2
C3
2" r- Aq~1
Arl + Ar 2
G 2" r. Aq~2
4
c.=zc,
#=1
D = q.a,j
ks
i!
13C
u
~~
ll(J
n- 10C
t~/i~I '~"~4~ .,/- ~t = 0.375mm (ADDITIONAL TCR)
z
I--
.~..o,. S.~:/ REFERENCE CASE, At - 0
"i-
z
,w
U 5~ ~ h o (FOR SINGLE PHASE LIQUID, FORCED CONVECTION)
t "e.
i 9
U O
Z
3( I \ O
i "= 3O
I"rl
20 <
\ m
0
1 l t ~.- i | I I I I I
O
0.2 0.4 0'.6 0'.8 1.0 !.2 I 3.0
l'.q 116 i'.8 210 2.2 22q 2.6 2.8 I 31.2 31.q 3.6 3.8 q!O q!2 q.q q.6 q.8 5.0
LENGTH ALONG THE BOUNDARY, mm O
O
CONTACT CREVICE -I- SIDE OF OPEN REGION Z
INTERFACE REGION
FIG. 7--Calculated distribution of the coefficient of heat transfer (h ) along the water-cooled surface. CO
r
Q
"~ oo
O
O
E
"10
E
~t~ ~ SURFACE H E A T F L U X , kW,'m z .-I
~ SURFACE HEAT F L U X , kW/m z SURFACE HEAT F L U X . kW/m 2
m
~ ~ . . . . . . = . ~ . . . . . -~ g ~- . . . . . . . . . . . . . tf tl If I1 Ii il tl It 11 1t tl II ill il tl
~, " . . O r * . 0 il O i~r i ? " , ~ T J ' i i I , J J
L . . . . !I'' * L I ' " I- " I- I,~ I E
0
o
m
i-
~. ~1-/ ',:
,~
I~1
I~_1
IV
I i
::.~ 151
li~l
I-I - !~;..
<::, F i.,. I~1 I i~ 131 | ~E
lie I:~ 9 iX
_~ kI ' l l ,*
I
1=_311,
I~1 I ',
,
i
I~1
I Z"'J
r\
I- ' ~
,I o
0
IL \ i I -,%, i " ' ~ 0

~- ~ ill I . i l 31 I I : . . . . . ~L ~ I i= Go
~: I I B
. . . _. \ .. , _ _ ...................................................
, /<, \ - L .... _k_..... L_ ................... .;_ z
,.,t I i I ~ I
I I > J . . . . . I
"~ "7'' 7 7
ATRIA ON CREVICE CORROSION 41
where
q, a,j = the input heat flux and the elemental area surrounding the nodal point, respectwely,
and
k, = the thermal conductwlty of the sohd
As for the triangular element, the energy balance for each nodal point t (see inset of Fig 5 ),
results m the following relauon
n
Cvtj + C.t, + D = O (19)
J~l
w h e r e j represents all nelghbonng nodes with which the node t exchanges heat, and
Cot ~j + Cot 82
C,~= 2
D = q.a!
ks
where a, = the area of the polygon surrounding node
Results and Dtscusston

As mentioned earlier, the cornerstone of the present approach is the recognmon of the effect
of the distribution of the coefficient of heat transfer h on the thermal behavior of contacting
solids, and the need for its determmauon as a necessary and integral part of the solution The
distributions ofh obtained m the present analysis are shown m Fig 7 F~gure 7 indicates that the
distribution of h is highly nonuniform and differs slgmficantly from the lnmal value h0 assumed
m the solution routine for a single-phase liquid, forced convection This indicates the erroneous
predictions of the onset of nucleate boding and the surface temperatures in the crevice region,
had the coefficient of heat transfer h been assumed The change in the TCR at the contact
interface, due to fretting, has a s~gnlficant effect on the distribution of h m the crevice region
This effect is, nevertheless, of a local nature and ts mslgmficant m the open region
Superimposed on the boding curves, the results shown m Fig 8 are presented m terms of the
heat flux-surface temperature relationship of the boundary nodal points ofsohd 1 along the line
ABCDE This format of presentation will allow us to predict whether or not nucleate boding wdl
occur The analysis has been repeated for different levels ofaddmonal thermal contact resistance
AI = 0, 0 75, 1 5, and 3 75 mm of Zr The case ofAl = 0 is constdered as the reference case and is
presented as a fine dotted hne m Fig 8 From the figure, it can be concluded that, in the absence
of fretting, nucleate boding is confined within a crevice gap of approximately up to 45 tzm Parts
of the crewce and the sides of sohd 1 fall within the single phase regime, but as one moves
towards point D (Fig 8a), the bolhng process changes from a partmlly to a fully developed
nucleate boding regime The analysis of the results shows also that with the increase m the
thermal contact resistance due to fretting by addmonal AI = 0 750 m m of Zr, the extent of the
nucleate boding region w~thm the crevice ~s reduced to gaps up to 25 m thickness mstead of 45 m
(not shown m Fig 8) A further increase to AI = 1 5 and 3 75 mm of Zr causes the surface
flux-temperature curve to be shifted outside the boiling zone, suggestmg an arrest of the crevice
corrosion process Therefore one can reach the conclusion that while the thermal barrier induced
by the fretting corrosion process (through the increase in T C R ) is of a local nature, It can cause
the crevice process to be a self-limiting one
Conclusions
From the analysis presented m this paper, the following conclusions can be drawn
1 A computer-simulation model for the heat transfer process in the crevice region is devel-
oped This model, which predicts the onset o f nucleate boiling and the surface tempera-
ture, accounts for the system nonhneanty
2 Information pertaining to the distribution of the coefficient o f heat transfer h {x} along the
wetted surfaces is generated by this model This dlstnbutlon could be highly nonuniform
Without including h {x) as a part o f the sought-for solution, serious errors m surface
temperature and onset o f nucleate boiling predictions would result
3 The effect of the thermal b a m e r induced by the fretting corrosion process, through the
increase in the thermal contact resistance, can cause the crevice corrosion process to be a
self-hmitlng one
References
[1] Conou, M, Grail, L, Meumer, J , Perlas, M, and Wdlermoz. H, "Corrosion du Zlrcoloy Dams Dwers
Mlleux alcahns a Haute Temperature," Journal of Nuclear Mater:als. Vol 7, 1962, p 320
[2] Johnston, B S, Sharon. A , Kozawa, Y, and Bankoff, S G , "Boding Heat Transfer m a Narrow
Eccentnc Annulus," ASME Winter Annual Meeting, Paper No 82-JPGC-NE-7, 1982
[3] Johnston, B S and Bankoff, S G , "Boding Heat Transfer m a Narrow Eccentnc Annulus Part III--A
Model of Dry Patch Extent and Temperature Dlstnbuuon," Transactions of ASME. Journal of Heat
Transfer. Vol 108, 1986, p 433
[4] Tlezen, S. Merte, Jr, H , Arpao, V S. and Selamoglu. S, "Crevtce Boding m Steam Generators,"
Transact:ons of ASME, Journal of Heat Transfer. Vol 109, 1987, p 761
[5] Waterhouse, R B, Fretting Corrosion. Pergamon Press, New York, 1972
[6 ] Attla, M H and D'Sdva, N S, "Effect of Mode of Motion and Process Parameters on the Prediction of
Temperature Rise in Fretting Wear," Journal of Wear. Vol 106, 1985, pp 203-224
[7] Attla, M H, "Thermally Controlled Fretting Wear Tnbometer-A Step Towards Standardization of
Test Equipment and Methods," Journal of Wear. Vol 135, 1990, pp 423-440
[8] Yovanovxch, M M, "Thermal Contact Correlauons," Progress tn Astronauttcs and Aeronauttcs. Vol
83, 1982. p 83
[9] Duklewlcz, R K. "Interfaclal Gas Gap for Heat Transfer Between Randomly Rough Surfaces," in
Proceedings. 3rd Int Heat Transfer Conference, 1966
[10] Tsuklzoe. T and Htsakado, T , "On the Mechamsm of Heat Transfer Between Metal Surfaces m
Contact-Part 1 Theoreucal Analysis and Experimental JusUficatlon of Theory," Heat Transfer-
Japanese Research. Vol 1, No 1, Jan 1972
[11] Sanokawa, K, "Heat Transfer Between Metalhc Surfaces m Contact-lst Report The Condmons of
Both Metals m Contact Being the Same," Bullenn ofJSME. Vol I I. No 44, 1968
[12] Vez~roglu, T N, "Correlation of Thermal Contact Conductance Expenmental Results," in Proceed-
rags. 7th AIAA Thermophyslcs Specmhst Conference. New Orleans. La, Apnl 1967, pp 879-907
[13] Yovanovlch, M M, "Thermal Contact Resistance Theory and Apphcatlon," Lecture Notes, Mechan-
ical Engraeenng Department, Umverslty of Waterloo. Canada, 1976
[14] Aggarwal, B B and Wdson, W R D, "Improved Thermal Reynolds's Equations," m Proceedmgs.
Leeds-Lyon Symposmm on Tnbology. Mechamcal Engmeenng Publlcaaons Ltd, 1979, pp 152-161
[15] Rohsenow, W M and Hartnett, J P. Eds, Handbook of Heat Transfer. McGraw-Hill, New York,
1973
[16] Bergles, A E and Rohsenow, W M, "The Determmauon of Forced Convection Surface Bolhng Heat
Transfer," ASME Paper 63-HT-22, 1963
[17] Thom, J R S, Walker, W M, Fallon, T A , and Relsmg, G F S, "Bolhng m Subcooled Water
Dunng Flow Up Heated Tubes or Annuh," Proceedingsof the Instttute of Mechamcal Engineers, Man-
chester, 1965
[18] Schneider, G E and Yovanovlch, M M, "Finite Difference Modelhng of Heat Conduction m Gen-
eral Orthogonal Curvlhnear Coordinates Using Taylor Senes Expansion," m Proceedings. AICA Int
Symposmm on Comp Methods for Partial Dlff Equauons, Pennsylvama, June 1975
Tetsuo Shojt, 1 Shm-lchl Mortya, 1 and Ken-tchz Yoshida
Computer Simulation of Stress Corrosion

Cracking Behavior of Reactor Pressure
Vessel (RPV) Steels in Light Water Reactor
(LWR) Environments in Slow Strain
Rate Tests (SSRT)
REFERENCE" Shojl, T , Monya, S, and Yoshlda, K , "Computer Simulation of Stress Corro-
sion Cracking Behavior of Reactor Pressure Vessel (RPV) Steels in Light Water Reactor
( L W R ) Environments in Slow Strain Rate Tests ( S S R T ) , " Computer Modehng In Corrosion.
ASTM STP 1154, R S Munn, Ed, Amencan Society for Testing and Materials, Phdadelphla,
1992, pp 44-66
ABSTRACT: Based upon a slip dissolution model, crack imtlatlon and growth behavior of stress
corrosion cracking of reactor pressure vessel steels, in pressurized high temperature water, was
simulated by FEM (fimte element method), with a combination of nodal force release techmques,
simulating the crack growth by dissolution
Results obtained from the computer simulation for this materials/environment combination
agree well with experiments m overall load/&splacement curves of the tests and also can simulate
crack inltmtmn and propagation behavior This computer simulation of slow strata rate (SSR) tests
also focused on the significance of the multiple crack problems in SSR tests, particularly for smooth
specimens, in relation to an evaluation of an actual crack t~p strain rate It was also found that crack
growth rates, under such a multiple crack situation, can be umquely plotted as a function of crack
t~p strain rates when evaluated correctly
KEY WORDS: slow strain rate (SSR) test, stress corrosion cracking, shp dlssolunon mechanism,
finite element method, computer simulation, PWR water, RPV steels, multiple crack initiation,
crack tip strain rate
A n extensive effort has been put forth to m a i n t a i n the structural safety a n d integrity o f nuclear
power plants In order to ensure the structural safety, reliability, a n d lntegnty, effects o f environ-
m e n t s specific to a nuclear power system, upon stress corrosion crack initiation a n d subsequent
subcntlcal crack growth, have been taken into consideration as one o f the key issues which have
crucial influences u p o n mechanical behavior o f materials u n d e r operational c o n d m o n s
For example, corrosion fatigue crack growth behavior has been extensively investigated De-
tails on stress corrosion cracking a n d mechanistic u n d e r s t a n d i n g o f crack growth e n h a n c e m e n t
o f reactor pressure vessel ( R P V ) steels in light water reactor ( L W R ) coolant can be s u m m a n z e d
as shown m Fig 1 T h e significance o f sulfur c o n t e n t m steels, flow rate, strain rate, a n d electro-
chemical potentml ( E C P ) was d e m o n s t r a t e d Similar behavior has also been observed in the
cracking o f slow strata rate test ( S S R T ) plato specimens where a critical cracking potential,
above which cracking can take place, was obtained as a function o f sulfur c o n t e n t in steel a n d
also o f the c o n t e n t o f SO~- added m solution [ 1 ] Higher c o n t e n t o f sulfur b o t h in steels a n d in
Research Institute for Fracture Technology, Tohoku University, Aramakl Aoba, Sendal/980, Japan
44
SURFACE EFFECT I
(Thlcknessand Sizeeffect)
Go
ir
adogVar,ab,es 0
iI
#s
0
z
i"
0
.i t
z
~D
Ii
m
--I
m
Oo
--I
Oo
FIG l--Summarized mteraenon o f various parameters influencing EAC of R P V steels m htgh temperature water
i '"",
Ftlm rapture
)
Film rapture Film rapture
t
Aa~ Aan
Crack tip -a 9 -=
M M
Aal-- ~-~Q1 &an = p--~Qn
FIG 2--Schemattc representatton offilm rupture process and repeated dtssolutton
solutton shifted a cracking potential lower Shp dissolution model can explain most of these
phenomena observed m experiments Numerous SSRT experiments have been conducted for a
wide variety of material/environment systems However, most of these data have been used only
for quahtatwe and relatwe evaluaUon for cracking susceptlbdlty The reasons are
1 Lack of detaded and quantltatwe exammauon of statable parameters obtainable from

SSRT and justification of the parameters for quanUtatlve evaluation of stress corrosion
cracking suscepubdlty
2 The need for full understanding of crack ruination and propagaUon in SSRT tests includ-
ing more quant~tatwe analys~s of stress and strata d~stnbut~on after crack ruination
3 The need for analysis of a relationship between apphed stram rate and local strata rate
4 The need for analysis of mulUple crack ruination and propagation and its effects upon
stress/stram d~stnbuUon
5 The lack of relevant SSRT data to actual situations m terms of the aforementioned needs
Because of numerous combinations of mechamcal and environmental parameters, the intro-

duction of numerical experiments, namely, computer s~mulat~on of environmentally assisted
cracking (EAC) is urgently required for improvement of predlctwe capabdlty of environmen-
tally assisted cracking In this paper, a numerical simulation procedure of environmentally
SHOJI ET AL. ON SLOW STRAIN RATE TESTS 47
3 into
I
FIG. 3 - - FEM meshes for plain SSRT specimen.
assisted cracking was developed for smooth specimens under monotonic slow loading (slow
strain rate tests) by paying special attention to the evaluation of strain rates. Finite element
analyses for the evaluation of overall strain distribution and of crack tip strain rate for crack
initiation and for subsequent growing cracks were performed. Based upon a model of slip disso-
lution, crack initiation and growth processes were simulated by means of a nodal force release
A 5 0 8 C L. 2 Observedareaby O M
15 = 6 0 9. i (cm~)
10
I I
~ Q I
-O-
I
0 50 100 150 200
Surface area of M n S at Surface (pro2)

FIG. 4 - - M n S distribution for a high sulfur steel.
technique. In connection with the theoretical crack growth model, the significance of multiple
crack initiation, strain rate, and crack opening on crack growth rate was demonstrated.
Modeling and ComputerSimulation Procedure

In this paper, the environmentally assisted crack initiation and growth process was reproduced
numerically based upon a slip dissolution model. The slip dissolution model consists of the
following three processes:
1. Rupture of oxide or protective film.

2. Enhanced anodic dissolution of bare metal.
3. Covering of bare surface by oxide or protective film.
Mechanical straining breaks the oxide or protective film and a new surface, which is quite
reactive, is formed at the crack tip, followed by dissolution current flow at the bare surface and
repassivation. Hence the crack growth rata is equivalent to the dissolution rate of the metal at the
crack tip, according to Faraday's Law:
v=M_____~__.Q~ (l)
p .F.n tf
where M = atomic weight,
p= density,
n = change in charge due to dissolution process,
F = Faraday's constant (96 500~
tf = period of film rupture, and
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreeme
~ , START
I Elastic-Plastic I
Solution
Yes
No
I Node Release Start (
SCC Solution
by .~ Fig. 5 (b)
Slip Dissolution Model
, ~Yes
Crack Propagation
and
Next Node Release Start
F|G.
I
5a--Flow chart of compuwr simulation of crack initiation and growth.
Calculation of crack volume

(crack length, crack opening dmplacement, thickness)
Calculation of average S042- coneentratlon m crack
dissolved S from MnS--~total amount of S04S--~SO42"concentratlon
Total S042" m crack

SO42" Cone. =
Crack Volume
Determlnatxon of I and n to characterize i(t)curve in Eq.(8)
Calculation of the amount of charge transfer

by dissolution for I film rupture
Total amount of charge
Crack growth simula~on
I
FIG 5b--Equivalence of dtssolutton chargeand crack advancement
Qf = dissolution charge density dunng a period of film rupture, tf

The amount of crack growth Lf, dunng each cycle, tf, is
M
Lf - - Qf (2)
p.F.n
Figure 2 shows the sequence of a cycle of film rupture, dlssoluuon, and repasswatlon as a
function of time and the corresponding repeated crack advances Qf can be obtained from a
dissolution current decay curve as
Qf = flfl(t)dt (3)
where t ( t ) is a function of a material/environment combination Crack tip solution chemistry

and electrochemical potential are the most important parameters determining t ( t ) for a given
material / environment combination
Computer simulation becomes possible by fo.owmg the procedure described above, provided
that required data can be obtained experimentally and numerically In this paper, numencal
SHOJI ET AL ON SLOW STRAIN RATE TESTS 51
12OO
1OOO
800
600
Ib 400
Young's Modulus E=205.8 GPa
Yield Stress CTv= 4 4 5 . 6 MPa
200 V=0.3
Poisson's Ratio
0 I I I I I I I i
0 .2 .4 .6 .8 1.0 1.2 1.4 1.6 1.8
FIG 6--Stress-stram curve used for FEM analysts
analysis was performed by finite element analysis Stress and strain analysis and crack initiation
will be explained m more detail later Crack growth analysis was performed by the finite element
method ( F E M ) The FEM analysis (taking into account crack growth by dissolution) was
performed on plain smooth specimens loaded monotonically at slow strain rates Finite deforma-
tion elastic-plastic incremental theory and homogeneous work hardening property are repre-
sented by the Prandtl-Reuss equation In the case of a large geometry assumption, Jaumann's
stress increment ~s used instead of true stress increment to keep the stress unchanged by rigid
rotation
Stmulatton o f SSR Test on a Smooth Spectmen
Environmentally assisted cracking in SSR tests, conducted on a plain smooth specimen, were
simulated by use of FEM assuming large geometry changes of two-dimensional elastic-plastic
under plane stress conditions, based upon slip dissolution model Simulation analysis was per-
formed on a 3 mm w~de by 40 mm long by 1 mm thick plate specimen that was divided into 800
elements of eight-point lsoparametric elements of 0 5 by 0 3 mm size (Fig 3) In order to take a
microstructural vanatlon upon yield strength, yield stress was distributed over each element by
use of a normal dlstnbution MnS inclusions were also dlstnbuted over 800 elements based upon
experimental data shown in Fig 4 which is for high sulfur matenals (0 015 wt%) For low sulfur
matenal (0.003 wt%), sizes of MnS were reduced by a factor proportional to sulfur content in
steels, namely a factor of 1] 50 Distribution over the 800 elements was the same as in the case of
high sulfur steel Crack initiation and growth were s~mulated in accordance with the procedure
shown In Fig 5 This flow chart shows a sequence of simulation including elastic-
plastic stress/strain analysis, evaluation of crack volume from crack opening displacement and
crack length, calculation of dissolved sulfur content from Mn-S at the crack tip and crack
r-%
v T
(a) Before crack inltlat2on
t-%
! v
(b) At crack lnltlatlon
Input ei new nodal polnt

Start of release o• nodal polnt
(c) Crack propagat aon
Input of new nodal polnt

FIG 7--~hematw dlustratton ~crack mtttatton p r ~ s ~ no~ release techmque
surface, evaluation of crock tip solution chemistry in terms ofconcentratton of SOl-, dissolution
process, and also strain redistnbutton at crack tip regaon induced by dmsolutlon Figure 6 shows a
stress-strain curve of the material used in this analysts The crack inmatlon process was stmulated
by the separation of one node into two nodes, giving a new nodal number as shown m Fig 7
when the condmon for crack Initiation was achieved
A specimen was loaded at an extension rate [?g (Vg = load-hne dmplacement) to satisfy the
crack lmtiation condition Once the condition for crack initiation was satisfied, the crack growth
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to Lice
~j.k r"
p.po-,,~.~-z~,o
FIG. 8--Schematic illustration of crack growth process by node release technique.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No furt
101
10 0
10 -1
-1520 [] 1000
-'-" - 100 rnV ~ 3000
9 5000
10 .2 , , i)l I , , ,I , , , ,I I I 1 I
10-3 10-2 10-1 10 o 10 ~

Time (sec)
FIG 9--Current decay curves used for SSRTslmulatlon
process was simulated Although incremental increase in Vs, at a time interval At, should be
chosen to give a At that IS equal t o / f , this process is very time consuming because the number of
film ruptures is so large The authors attempted to minimize the computational time by main-
taining a reasonable accuracy of analysis Therefore it is necessary to determine the number o f
film ruptures dunng At Strain distribution e(r, O, Vg) can be calculated by FEM where no strata
slngulanty was observed at a crack tip because o f rather short crack length in smooth specimens
For a given V8 or At, a crack can grow to an amount, At, and the number of film ruptures, N, can
be evaluated as
~" cdr
N = - - (4)
r Ar
Associated with these repeated film ruptures, crack advance by dissolution can be evaluated
by Eq 1 Crack growth by dissolution was simulated by correlating the oxtdatlon charge density
to the crack growth of one mesh size denoted by Aa, as
p.F.n
Qc- M Aa, (5)
If mesh sizes at a crack tip are known, then Qc can be calculated easily as shown above
Oxidation charge density, AQ, for a time interval, At, can be obtained by
10 2
288"C BWR
Pulse -1520mV(SHE) --'- -100mV(SHE)
I01
<
....o 10 ~
! 0 "i ' J I II I I I II I ~ ~ II t , t )
101 10 2 10 a lO ~ 05
[S042"] (ppm)
FIG l O--Trend ofdtssolutton rate as afunctwn of SO~- concentration
~AtlN
AQ = N [ t(t)dt (6)
,10
where N is the number of film ruptures for z~t Hence crack growth was simulated by a nodal
force release techmque cons]denng Qc, AQ and P,o (P,o is the traction force before node release
as P )
P=-~cc P,o (7)
where P is load on the node in the opposite direction ofP, o and the crack advance by the amount
of Aa, is completed when Qc = ZAQ or P,o = ZPIs satisfied Further crack growth is simulated by
repeating these processes with increasing displacement Figure 8 shows schematically this slmula-
uon process of crack growth. In this case, current decay curves are expenmentally obtained as a
TABLE la--Chemtcal composmon (wt%) of SA508 CI II steel

C Si Mn P S Nl Cr Mo Cu
0 20 0 28 0 92 0 10 0 015 0 88 042 0 59 002

i
TABLE I b---Mechamcal propertws of SA508 Cl H steel

0 2% Offset Tensde Reduction
Temp Strength Strength Elonganon of Area
(~ (MPa) (MPa) (%) (%)
20 476 620 23 0 66 9
300 405 588 20 8 64 7
function of water chemistry in terms of SO24- concentration by a potential pulse techmque as

shown in Fig 9 Figure l0 shows a plot of the inmal value of l,i(O) as a function of SO 2-
concentration and the transition in t ( 0 ) at the concentration of 500 to 1000 ppm is clear above
which t ( 0 ) shows a saturation tendency In this case, current decay curves can be approximated
by the equation
t(t)= I.t-" (8)
where I and n change on the way from the early stages of the decay curve to the later stages of the
current decay curves These current decay curves are measured in simulated boiling water reac-
tor ( B W R ) condition with S O l - at a potential o f - 100 mV versus SHE (standard hydrogen
electrode) This potential was chosen as the highest of possible potentials during normal opera-
tlonal conditions with &ssolved oxygen ( D O ) of n 0 1 ppm Strain distnbuuon m SSRT speci-
mens IS rather uniform, and this trend is kept even after a small amount of crack extension
FIG 11--Schematw dlustratton of two-dimensional crack under plane stress condition

FIG. 12--Cracks observed on a specimen surface.
Hence it is not necessary to estimate a crack tip singular strain as has been done in analysis of
compact tension (CT) specimens [2]. Strain values in SSRT simulation were adopted as the
average strain of each four Gauss integration points for two elements ahead of the crack tip in the
case of post-initiation. With increasing load or displacement, cracks can initiate at several nodal
points where the condition of crack initiation is satisfied. The condition of crack initiation is that
Simulation N~
---.. \
0.8 Experiment -'f" x
x
X
a
E 0.6
o. 0.4
0.2
0 I I
0 2 4 6
Disp. (ram)
FIG • 3_C•mparts•n between numertca• slmu•atl•n and expertments •f ••ad•e••ngatt•n curves •f S S R T m
inert enwronment
2000
-~.Expedmet 500p~
150C / / / / 3000ppm
/
//
/
~ 1000
500 ~app= 4=lO'esec '
0 I !
0 2 4 6
Disp (mm)
FIG 14--Compartson between numerwal stmulatton and expertment o f load-elongatton curves o f S S R T m
htgh temperature water
~app=4-10-~ sec -'

0.7 Simulabon
0.6
0.5
E
E
v 0.4
o~
_O0~_A
9 ~ .,,,,""
0.3
/ // / e
02 /,," _..M.~,~
o,
I/// 24.6
. ,
I
0 "~ - 5 10 15 20 25 30
Time ~103 sec)
FIG 15--Crack growth charactertstws as a function of testmg time
2000
1500
Number of Cracks
.... 9 1
V
----' 10
,< 1000
0. J ~ : 50
500
00 I I I ]
1 2 3 4 5
DISP. (mm)
FIG 16--Calculated load-elongation curves for S S R T tests w~th a fixed number of crack lmttatton sites
~,app= 4 ~ 1 0 "6 s e c -' Number of Cracks

9 1
110
I 0 -4
1150
C.)
(D
r.o
\
E
E
1 0 -s
i 0 -e I I I I illl[ I I I I I Ill[ I I I I ill

0-8 1 0 -B I 0-4
eCT (S e C-i)
FIG 17--Plot of calculated crack growth rate as afuncnon of crack np strmn rate
the average strain of the elements, shanng the nodes being released, reaches the critical strain for
film rupture of 0 003 as suggested by Ford et al [3] for a similar material/environment
condition
Experiments
Slow strata rate tests were performed on smooth specimens of SA508 C1 II RPV steel with low
and high sulfur content The chemical composmon and mechanical properties of high sulfur
steel are hsted m Tables I a and 1b The reference load-displacement curves were measured in a
288~ water environment tested at a faster extension rate where no environmental effects affect
the results The SSRT experiments on smooth specimens were carried out m simulated BWR
water with and without addmon of sulfate ion simulating a crack tip solution chemistry m a
range of 500 to 5000 ppm Plato plate specimens, fabricated from 240-mm-thlck A508 C1 II
steel with a tensde axis parallel to the transverse direction, were machined The speomens had
threaded ends and a 3 00 by 3 00 mm cross section by 40 0 mm long gage length One set of
facing surfaces was pohshed very smoothly by a diamond paste of 0 6 #m and another set was
pohshed roughly by -#500 sandpaper to promote crack initiation only on a set of surfaces which
can assume two-dimensional cracking and are close to numerical simulation (Fig 11 ) Slow
strain rate tests were performed on 99-mm-long speomens and m a small 316L stainless steel
refreshed autoclave using a screw-driven SSRT machine with a loading capacity of 2 tons The
electrochemical potential was monitored dunng the tests by Ag/AgC1 external reference elec-
10 6
A508CL.2
A
10 s
E
t-~
t).
High S
dr-- 10'
o
t.)
I
10 a
Lo S
102 ,, I I
0 0.5 1.0 1.5
Displacement ( mm )
FIG 1 8 - - E s t i m a t e d average S024 - concentration tn crack as a function o f elongatton
trode All potentials quoted hereafter are with respect to the normal hydrogen electrode as
standard A ZrO2 disk was inserted between speomen and gnps as an electncal insulator
In simulated BWR condmon, water conductivity IS very low and it is difficult to keep that
potential by using an electrochemical potentlostat Hence the quantity of air bubbhng at the
make-up tank was controlled to obtain a reasonable potential In cases of SO ]- addmon, the
potential can be easdy controlled by a potentlostat because of htgh conductwity
Figure 12 shows distribution of cracks under Eapp= 4 2 X 10-6 s-I Cracks are dlstnbuted over
the whole specimen, but long cracks are distributed around the rupture surface, where a trace of
Mn-S inclusion can be seen at the mmaUon point of cracking
Mn-S distributed at the speomen surface can dissolve qmckly even under a low stress condi-
tion and pits are formed These pits have high potential to grow into cracks under hsgher stress
condmons Also MnS at the crack tip and crack surfaces can dissolve at a certain rate, but here
the rate was assumed to be proportional to the rate of crack extension of the elements which
contain MnS Tests were conducted at a potentml o f - 1 0 0 mV versus SHE and nominal strata
rates of 2 • l0 -6, 4 X l0 -6 and 2 • l0 -5 s -1 were chosen Most of the experiments on smooth
specimens were completed until broken Fracture surfaces and side surfaces of specimens were
examined m detail by SEM and binocular microscope to study cracking characteristics and the
number of cracks initiated from surfaces
Results and Discussion

Compartson of Stmulatlon and Experiments on Htgh Sulfur Matertals
Stmulatlon Results m an Inert Envtronment--In order to take into account the m~crostructural
vanatlon upon yield strength, yield stress was dlsmbuted over each element by use of normal
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant
3
A508CL.2 /
A
E
E 2
e-
e-
_1
Low-S
o
0 I
0 2.0 4.0 6.0

Dsi pa
l cemen(tmm)
FIG 19--Stmulated crack growth as a functton of elongatton for htgh and low sulfur steels
&stnbutlon as mentioned before Figure 13 shows load-displacement curves ofexpenment and

s~mulatmn resulting from inert enwronment S~mulat~on results were s~mdar to the experiment
untd maximum load, but after that the simulation showed a longer plateau regmn at the max~-
mum load than &d the experimentally observed result Th~s result shows that an ~mprovement
of the FEM code for plasUc mstabdlty might be necessary
Stmulatton Results in Water Envtronments--The condmon for crack ruination m the slmula-
uons was that an equwalent plasUc strata reached film rupture strata (~f = 0 003) Figure 14
shows load-displacement curves obtained by the simulation under an apphed extension rate of
~avp = 4 • 10 -6 s -1 and using current decay curves for SO~- concentraUons of 500, 1000, and
3000 ppm, respectwely The number of cracks mmated from nodes was 158, a value greater than
the 70 observed m an experiment The curve obtained by simulation using 1000 ppm of SO~-
concentration was very s~mdar to the experimental result F~gure 15 shows the crack growth of
the longest crack as a function of time The curve by slmulauon, using 3000 ppm of SO~-, was
stmdar to the experimental result
As menUoned before, the number of cracks was 158 but m the experiment the number of
cracks was 70 under ~app = 4 • 10 -6 s - ' In order to evaluate the crack growth behavior under a
multiple crack sttuatlon, the number of cracks was assumed to be 1, 10, and 50 m simulation
Figure 16 shows load-displacement curves under ~app = 4 X 10 -6 s -t for each number of cracks
In load-&splacement curves, elongation become smaller and maximum loads tend to become
lower for larger numbers of cracks. Thus it ts clear that the curves for each number of cracks are
qmte &fferent from each other However, the maximum crack growth rate for these s~mulat~ons,
w~th different numbers of crack mltmuon, can be umquely plotted as a function of crack t~p
strain rate by the equauon (Fig 17)
a = m~ ~ (9)
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) p
lo-2 "~t app) s e c -1

S:0.015 wt.%
2 X 10 -s
O 4 X 10 -s
A 2 x l o -6
4 X 1 0 -7
[] 4 X 1 0 -s [SO42-]lOpprr
A 2 X 1 0 -s L.S{,S : O . 0 0 4 ,
Mechanical wt%)
8, SCC
1 0 -3
f l l
rO
(D
0g
T II I
E 1 A ~
V
E SCC/c
y High--S
A Oi.-...................-.....-......;-;.;,
iii::iiiiii~i~iiiii~i~iiiii~i!ii!ii!i~i~:
numerical
E 0_4
I
V
Low-S
iii!!i!!i::iii::iiiiii!!!!!!i numerical
<3 (S:O.OO015wt%)
10-5 _
10-6 v
-700 -600 -500 -400 -300 -200 -100 0

Es.t (m V )
FIG. 20--Comparison of crack growth rate obtained by simulation and those by experiments,
10-3
A508CL,2
o
E
E I
O
T
~ 10_4
2
Q.
v, O I ' Experimental
o
0 O' Numerxeal
10-w I I I I
O 0.005 0.O 10 0.O 15
$ Conc. (wt%)
FIG 21--Stgmficant effects of sulfur content m steels upon average crack growth rate m SSR T at a strata rate
of 4 • 10-6 s - l a n d at ECP of 100 m V (versus SHE)
where a is crack growth rate m m m / s and Ecr ~s m s -~ Th~s result confirms that the Ume base
crack growth rate can be umquely descnbed as a funcuon of crack Up strata rate even where
multlcracks inmate along a gage length m SSRT expenments
Effects o f Sulfur Content m Steels on Cracking Charactenstws
Effects o f sulfur content m steels were examined by computer simulation on high sulfur
(0 015 wt%) steels MnS &stnbutton was assumed to be the same, but the size of MnS was
&fferent Low sulfur steel contains much finer MnS inclusion Figure 18 shows the vanaUon of
SO 2- concentration in a crack as a funcUon of s p e o m e n &splacement
The trend o f decreasing SO 2- concentration with increasing deformation is clear both for high
and low sulfur steels and, as a natural consequence, high sulfur steel shows much higher SO42-
concentration within a crack This decreasing tendency o f SO~- concentration in a crack can be
attnbuted as follows With increasing deformation after crack Initiation, the crack opening be-
comes larger, which is a function ofcrack length (proportional to a) Hence crack volume can be
propomonal to a 2 On the other hand, the amount o f M n S dlssoluuon depends upon the surface
area Hence the amount o f SO~- can be proporttonal to a Hence the concentrauon o f S O ~ - m a
crack is proportional to a / a 2 = 1 / a Therefore, with increasing deformation, a becomes larger
and consequently the concentration of SO 2- becomes lower (proportional to l / a ) This is a
very rough approximation, but the general trend can be understood m this manner
SHOJI El" AL ON SLOW STRAIN RATE TESTS 65
Reflecting this trend of SO 2- concentration is a crack Crack growth rate 1s retarded after crack
extension of about 0 7 mm for low sulfur matenals (Fig 19) because of the decrease in SO42-
concentration to less than the threshold value However, as can be seen clearly, for high sulfur
materials crack growth rate can be regarded as almost constant This suggests that the SO 2-
concentration was kept h~gher even after some amount of crack extension
Taking the averaged crack-growth rate in Fig 19, crack-growth rate obtained m this simula-
tion can be compared with experimental data reported as a function of potentml Figure 20
shows the comparison of these data, and a reasonable agreement can be seen between the two
growth rates The summanzed plateau crack growth rate, as a function of sulfur content in steel
obtained in simulation and experiments, is shown in Fig 21 The increase of crack growth rate is
about one order of magnitude and can be seen in Fig 21 with increasing sulfur content in steels
Hence this computer simulation code can quantitatively predict the crack growth rate in SSRT
and can be applied to other geometries
Conclusion
Based upon the mechanistic understanding of EAC of RPV steels in LWR environment, a
computer code for numerical simulation of SSRT was developed based upon a shp-dlssolution
model coupled with FEM analysis where multiple crack ruination processes is also simulated as
well as following short crack growth The significance of the crack tip strain rate and sulfur
content m steels is also demonstrated The validity of the computer code was confirmed by
making a comparison of numencaUy simulated data with that of experimental data
References
[1] Shojl, T, Takahashl, H, Alzawa, S, and Salto, M in Proceedmgs, Third International Symposium on
Environmental Degradation of Materials in Nuclear Power Systems-Water Reactors, G J Theus and
J R Weeks, Eds, The Metallurgical Society, 1988, p 251
[2] Shojl, T, Morlya, S, and Tada, S In Proceedings, Fourth International Symposmmon Environmental
Degradation of Matenals m Nuclear Power Systems-Water Reactors, Jekyll Island, Ga, 6-10 Aug
1989, forthcoming
[3] Ford, F P, EPRI NP-2589, EPRI Final Report, Menlo Park, Cahf, Vol 25, No 8/9, 1982, pp
673-682
DISCUSSION
R S Munn I (written discussion)--(1) In the analysis flowchart (Fig 5a), why is crack
mmaUon checked after crack propagation9
(2) How is elastic energy considered in rules for crack initiation and propagations9
T Shojt et al (authors'closure)--( 1 ) In order to handle easily both crack initiation and crack
propagation of different elements in FEM analysis, propagation is evaluated first
(2) Crack initiation and propagation is evaluated in terms of strain because the model of SCC
in this analysis is based upon the film rupture process where film rupture is controlled by strain
It is not necessary to consider elastic strain energy in this model
U S Naval Underwater Systems Center, New London, CT 06320

G Cragnohno2 (wrttten dlscusslon)--Could you simulate with your model the existence o f a
cnUcal potential for SCC which appears m your experimental data9 How is the dependence on
strata rate simulated m terms of the role of sulfur compounds released at the crack tip 9
T Shojl et al (authors'closure)--Thank you for your questions They are both very good ones
deserving o f answers m depth and &scuss~on m exphc~t detail
2 Southwest Research Institute, San Antonio, TX 78228

S. Turgoose, 1 R. A. Cottis, 1 a n d K. L a w s o n i
Modeling of Electrode Processes and

Surface Chemistry in Carbon Dioxide
Containing Solutions
REFERENCE: Turgoose, S, Cottls, R A , and Lawson, K , "Modeling of Electrode Processes

and Surface Chemistry in Carbon Dioxide Containing Solutions," Computer Modehng m Corro-
ston, ASTM STP 1154, R S Munn, Ed, American Society for Testing and Matenals, Philadelphia,
1992, pp 67-81
ABSTRACT: Corrosion processes and the rates of the individual electrode reactions in carbon
dioxide containing solutions are well known to be affected by solution composition and hydrody-
namics There are many different mechanistic explanations for the observed, from rotating-disk
studies, cathodic current-potential-rotation speed relationships, most of which obtain the ob-
served currents by the simple addition of two or more currents due to processes (for example,
chemical reactions and diffusion) that are considered to act independently The vahdtty of this is
not clear, since many of the species conmbuting interact m the boundary layer
A model is described that derives cathodic current densities and surface solution chemlstnes for
the rotating-disk electrode over the range of conditions of practical relevance The model allows for
the slow homogeneous chemical step of carbon dioxide hydrauon, diffusion, convection, charge
transfer processes, and the rapid acid-base equdtbna It is shown that the expenmental data are
adequately modeled without the need to consider a heterogeneous surface hydration of carbon
dioxide, and that the electrochemical response under conditions not previously studied is pre-
dicted Further, the increase m cathodic hmitlng current at pH > 6 is shown to be a consequence of
the solution chemical equlhbna and the direct reductmn of bicarbonate is not necessary to explain
the expenmental data None of the mechanisms previously proposed is valid over the entire pH
range of interest
The concentration profiles in the near surface region throw light on the rate determining steps m
the cathodic process and can be used to predict the possibility of surface film formation
KEY WORDS: carbon dioxide, corrosion processes, surface chemistry
T h e r e have been several studies o f the kinetics a n d m e c h a n i s m o f the cathodic reaction m

slightly acidic oxygen-free CO2-containing solutions o f the type e n c o u n t e r e d in oll a n d gas
production [l-.5] T h e m a j o n t y o f studies have been in the pH range 4 - 4 5, with the pH
controlled by the partial pressure o f carbon dioxide, a n d whilst there are still disagreements
a b o u t the precise mechanism, the i n v o l v e m e n t o f potentially complex preceding or subsequent
chemical reactions is k n o w n to modify the electrochemical responses T h e l n m a l aim o f the
model reported here was to calculate the local solution chemistry at the metal surface, especially
since some experimental data were most readily explicable if c a r b o n a t e film formation could
occur u n d e r conditions where the bulk chemistry was n o t favorable, a n d also because the interfa-
Corroston and Protectton Centre, UMIST, P O Box 88, Manchester, M60 IQD, Umted Kingdom
67
cial pH may have an influence on the action of corrosion lnhIbItors However, the model also
predicts the cathodic current as a function of bulk pH and pCO2 for a rotating disk electrode, and
this also helps understand the mechanism of the cathodic process The emphasis of this paper is
on the latter
Mechanism of the Cathodic Reaction in CO2 Corrosion
There have been many studies of the cathodic reaction mechanism, and several different
processes and rate determining steps have been proposed These include rate determining reduc-
tion of carbonic acid with subsequent reformation from the bicarbonate and protons [ 1 ] and rate
hmiting diffusion of bicarbonate [ 2 ]
The first, whilst consistent with the experimental data at the time, does not explain data
obtained subsequently (e g , in R e f 3 ) , and the second covered only a small pH range and does
not explain the results obtained using rotating disk electrodes It has been shown [3.4.6] that
there is a cathodic limiting current, but this current is not purely a diffusion limited current This
limiting current depends on the rotation speed of the disk, w, according to the equation
lhm = IR -~- a'wl/2 (1)
This experimental observation has been widely confirmed, but there are different interpretations
of mechanism
The rotation speed dependent component, avr~, where a is an experimental constant, has
been associated with the diffusion of protons to the surface and the intercept, and the flow
independent current, tg, with the reduction of carbonic acid, the rate of production of which is
controlled by the slow hydration reaction of dissolved carbon dioxide with water The onglnal
observations of this relationship (Eq 1 ) were from Schmitt and Rothmann [3] and based partly
on the non-hneanty of a plot oftR versus pCO 2 and partly on the effect of metal composition on
the intercept, they suggested that this hydration was of adsorbed carbon dioxide However, the
intercept with platinum and iron is similar
Enksud and Sontvedt [ 5 ] stated that the calculated diffusion independent current for the CE
process (an electrochemical step preceded by a chemical reaction) shown in Eq 2, with the
chemical process being the homogeneous CO2 hydration reaction, was close to that observed
ks
CO2 + H20 # H2CO 3
kb
H2CO 3 + e ---*H + HCO~ (2)
Wieckowskl et al [ 4] also did not consider it necessary to assume a heterogeneous reaction to

explain the observed currents and found little evidence of adsorbed CO2 from electrochemical
and radio-tracer studies [ 7] However, they concluded that the electrochemical response was
consistent with a catalytic EC' mechanism where the reduction of carbonic acid or bicarbonate
yields bicarbonate or carbonate, respectively, which subsequently reacts with water to regenerate
the starting material plus hydroxide
TURGOOSE ET AL ON CARBON DIOXIDE CONTAINING SOLUTIONS 69
H2CO 3 + e --* HCO~ + H
or
H C O ~ + e --~ C O l - + H
H C O 3 + H 2 0 --~ H2CO 3 + O H -
or
CO 2- + H 2 0 --~ HCO~ + O H - (3)
The CO2-Water System

Solution Chemistry
T h e chemistry o f the CO2-water system discussed below is from Kern [8] unless otherwise
stated, a n d all data are for 25~ C a r b o n dioxide dissolves m water according to
CO2(g ) = CO2(aq ) (4)

with Ke = 10 -~ 5 mol d m -3 a t m -~ T h e dissolved c a r b o n &oxide reacts with water to give
c a r b o m c a o d according to the slow e q u t h b n u m
k:
CO2(aq) ~- H2CO3 (5)
kb
with k / = 0 0375 s -l a n d kb = 13 7 s -l , gwmg K = 0 0027 In a l k a h n e solutions c a r b o n dioxide

h y d r a u o n can also occur by
kf2
CO2(,q) + O H - ~ HCO~ (6)
kb_,
with kf2 = 8500 m o l - ' d m 3 s -l a n d kb2 = 1 9 X 10 -4 s -1

C a r b o m c acid undergoes dissociation, first to bicarbonate ( E q 7 ), t h e n to c a r b o n a t e ( E q 8)
H2CO3 = H + + HCO~ , pK~l = 3 77 (7)
HCO 3 = H + + COl-, pKa2 --- 10 3 (8)

As a result o f these e q u d i b n a , the c o n c e n t r a t i o n o f each species in solution, at pCO2 = 1 atm,
is as shown m F~g 1 It is i m p o r t a n t that the actual p K ~ is m u c h lower t h a n that normally
reported (pKal = 6 3 ) , since this latter value is based o n carbonic acid plus &ssolved CO2 a n d
not just o n carbonic acid A result o f this is that the solutions are less well buffered, over short
time scales, than would otherwise be expected
Analytical Soluuon for CE Mechamsm

T h e chemical hydration controlled reaction scheme proposed by Schm~tt a n d R o t h m a n n a n d
by Erlksud a n d Sontvedt for the flow i n d e p e n d e n t current can be d e s c n b e d as o f the C E type,
70 COMPUTERMODELINGIN CORROSION
O.11 C02 ._~ ~ ' ~ ' ~
~176
o ~176176 -,
g
0
- i J i i i
3.5 4 4.5 5 5.5 6 6.5 7 7.5

pH
FIG. 1--Concentration of carbonate species in bulk solution for pCO_, = 1 aim at 25~
with a chemical reaction preceding the electrochemical process. The current expected can be
calculated, assuming that the hydration is a homogeneous solution reaction, using the rate
constants above.
The variation of current with angular velocity of a rotating disk, for the CE reaction scheme in
Eq 2, is given by
nFDC*
i- - - (9)
6N + # / K
where n is the number of electrons in the electrochemical step ( = l here); F i s the Faraday; ~ is
the kinematic viscosity, cm 2 s-~; and D, cm 2 s -~, is the diffusion coefficient of CO2(,q) and
H~CO 3, assuming them to be equal. The other terms are defined by
C* = [CO2]b~k + [H2CO3]b.,k
6N = 1.61Dl/SUl/%o 1/2
k = k s + k~
K = kf/kt, (10)
Equation 9 is valid for the conditions given by
,0~k
(_;)"3 (ll)
At higher rotation rates the current approaches the hmltlng diffusion current for carbonic acid
reduction
In the low ~oregaon the current ,s proportional to ~01/2, due to control by CO2 diffusion, with
this applying at 0J < 1 tad s -l and not being experimentally determinable The transition from
the chemically controlled current to carbonic acid diffusion control occurs around 140 rad s -I
The flow Independent current calculated according to the data Dven prewously is 101 t~A cm -2 ,
which IS close to the diffusion independent current observed as pointed out by Enksud and
Sontvedt [ 5 ]
Thus the flow-independent current found by Schmltt and Rothmann (and many others) can
be explained as being due to this reaction sequence with the hydration reaction occurring in
solution, and, for this reason, the model here only allows for the homogeneous reaction The
overall current is then gwen by addition of a diffusion controlled proton reduction
However, it is not clear that this approach is valid under all conditions for the CO2-water
system, since the solution chemistry is more comphcated than suggested by Eq 2 or 3 In particu-
lar, the carbomc acid is in equilibrium with bicarbonate and protons and it is not obvious that the
chemical process and proton diffusion can be considered separately and simply added
Finite Element Model
The basic approach to the development of this model follows, where appropriate, that given
by Bard and Faulkner [9] The approach m this work is, essentially, to calculate the current
decay, on a rotating disk electrode, for the cathodic process on application of a potential step
from a potential where no reaction occurs to one in the limiting current region, although it is the
steady-state current that is of interest The model yields both the steady-state currents and the
concentration profiles of all speoes in the near-surface region The model considers the electron
transfer reactions, diffusion, convection, the slow chemical hydration reactions, and the rapid
solution equilibria An outline is given in Fig 2 The model was written in Turbo Pascal (Bor-
land) and run on either a 286 based or, later, on a 386sx based computer, both with math
coprocessors As an indication, the model takes about 40 rain per data point to run on the former
and about 8 mln on the latter
An important consideration is that the model here makes no assumptions about the mecha-
nism of any effect of solution chemical reactions on the cathodic current The model, as de-
scribed here, simply assumes that the current IS generated by reduction of protons and carbonic
acid
The component parts of the model are described briefly below
Inmal Conditions
The concentrations of all species are set according to the equihbna in Eqs 4, 5, 7, and 8 The
pH was either entered into the model (In the range 4 to 6 5 to cover those encountered in ollfield
formation waters) or could be calculated as being controlled by the CO2 pressure, reflecting the
two posslblhtles in the system The latter case reflects much of the published work, whereas the
former is probably more relevant in practice If the pH was calculated as being controlled by the
CO2 pressure, this was done using the equilibria in Eqs 4, 5, and 7 (Eq 8 being negligible in the
input (pH), pCO2, omega I

I
Iset initial condations I
1
set box size and time )nterval
I
Icurrent I
I
I I
I
slow chemical kinetics I
I
convect I
I
[equilibrate I
I
I finished ? I
FIG 2--Finite element model
pH range considered) with the &ssooatlon constant of water, Kw = 10 -14, and with the charge
balance cntenon
[n +] = [rico;] + [on-] (12)
Box Stze and Ttme Interval

By experience, it was found that dlv|slon of the Nernst &ffuslon layer, t5N, as defined m Eq 10,
mto 30 boxes was suffioent, and the calculation was camed out over 60 boxes (2"6N from the
surface) The time interval was calculated by using Eq 13 with the largest diffusion coefficient m
the model (that for H +)
D6t
= 045 (13)
6x 2
The total time for each calculauon was about twice the time, gwen by Eq 14, reqmred to reach
w~thm 1% of the steady-state current, and involved about 5000 t~me steps
l = --
2(;),,,
ca)
(14)
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further reproductions auth
TURGOOSE ET AL ON CARBON DIOXIDE C,ONTAINING SOLUTIONS 73
An increase in the number of boxes or a decrease m the Ume interval &d not have a noticeable
effect m the more acidic solutions, although some of the calculations at higher pH were depen-
dent on the time interval, as discussed later, probably because the overall mechamsm of the
process changes It should be noted that the number o f calculations is proportional to the cube of
the number of boxes
Current Calculation
The results reported here make the assumptmn that in each time interval all the protons and
carbomc acid m the innermost box are consumed according to the reactions in Eq l 5 The
current is calculated according to Faraday's law
H2CO3 + e ~ H + HCO~
H + + e ---} H (3)
and the concentrations of protons, carbomc acid, and bicarbonate adjusted accordingly Other
calculations were run allowing for the reduction of bicarbonate, but these are omitted here since
this was not found necessary to explain measured currents or trends in behavior By inserting
values for the exchange current densities for the two electrode processes, the current m the
actlvatmn controlled region can also be calculated and a polarization curve developed, but these
data are not presented here
Diffusion
Diffusion is allowed for usmg Flck's law
dC
flux = - D - - (16)
dx
From this. the change in concentration of a species m box n in a given time mterval is gwen by
DSt (17)
AC. = ~ x 2 (C.+, + C._, - 2C.)
Convection
The transport of solution by convection is dealt with according to Eq 18, which defines the
new x-coordinate (distance from electrode surface), x2, after ume ~t, for an element originally
at x~
1 1 _ 0.51o~3/2u_1/28t (18)
X2 XI
Slow Homogeneous Chemical Reacnons

The carbon dioxide concentration changes in a ume interval according to
A[CO2] = &(-k:[CO2] + kb[H2CO3] - k:[CO2][OH-]k~2[HCO~]) (19)

2.6-
2.4"
[] model analytical I
2.2-
2-
"~ 1.8-
1.6-
1.4-
1.2.
1- [][] ES]Rrq rmmarmr~rm~,
0.8
0 ~ ~ ~ ~ 6
dimensionless time
FIG. 3--Current decay from model compared with Eq 20 for a simple 0 + e = R reaction. X-axis is
cot(D/p) 113
The concentrations of the other species involved change according to the relevant terms of this
expression.
Equilibration
The final step allows for the rapid protonation-deprotonation equilibria to be achieved. The
equilibrated state is calculated by using the equilibrium constants for Eqs 7 and 8, Kw, a charge
balance, and a constancy of total concentration of carbonate species.
Results
Cathodic Currents
The initial test of the model was to calculate the current decay and steady-state current for a
simple reduction process with no complicating chemical processes. The decay was compared to
that calculated on the basis of the approximate analytical solution given by Eq 20 [ 10], and this
comparison is shown in Fig. 3.
i( t) _ ( -m2_~2Dt I
i(ss) 1 + m=
~l exp r )
(20)
The steady-state current is identical to that given by the Levich equation (Eq 9 as # tends to 0),
as shown in Fig. 4; thus the diffusion-convection part of the model is considered valid.
For the CO2 the current as a function of rotation speed was first calculated for solutions where
0 0003
I Levlch [] model
0 00025-
~" 0 0002-
'<~ 0 00015-
o 0 0001-
5E-05-
0~
sqrt(omega)
FIG 4--Current denstcy-w j/2 plot for model data compared with Lewch equatton for a simple 0 + e = R
reaction, w t n tad s -/
the pH was controlled only by the carbon dioxide pressure (1 e , condmons equivalent to those
stu&ed experimentally by Schmltt and Rothmann [ 3 ]) The results are shown m Fig 5 for pCOz
between 0 1 and 1 atm and for w between 1 and 100 rad s -t For w > about 10, the plots are
approximately linear, although they deviate to higher current at lower rotauon speeds, especially
with the h~gher carbon &oxide pressures The results of the model are very slmdar to those
obtained experimentally [ 3]
The calculated pH for these systems are between 3 85 and 4 45 The slopes of the "hnear"
regions can be compared to that calculated for proton d~ffUSlOnat the various bulk proton
concentrations, and the model values are found to be within a few percent of those calculated
The intercepts of the curves m Fig 5, calculated by a regression analysis for w 1/2 > 4 are
plotted against pCO2 in Fig 6 Due to the curvature of the plots the intercept of this regression
hne depends on the range of to used, and here that chosen is both the most hnear pomon and that
easdy experimentally accessible It can be seen that the &ffuslon independent current is not a
hnear funcuon of pCO2, and also that the model values agree well with the experimental ones
from Ref 3 This curvature is obtained consldenng only the homogeneous hydration process,
showing that the assumption of a heterogeneous hydration reaction ~s not necessary to explain
these results
In practice, especmlly m odfield formation waters, the pH is not solely controlled by the CO2,
and the pH as often higher than those relevant to the above calculations Figure 7 shows the
variation of current with rotation speed for various bulk pH at pCO2 = 1 atm The vanataon of
slope and intercept with pH are shown in Fag 8, although the non-hneanty apparent from Fag 7
introduces considerable uncertainty, especially an the latter In the higher pH solutions, the
results of the model are shghtly dependent on the tame interval for the lteraUon However, the
effect of decreasing the tame anterval is to increase the calculated current and so the trends seen
here are considered correct although the absolute numbers may need modification It seems
0.0005
[]
0.2
0.00045-
[] []
[] .-I- 0.4
0.0004-
X
--I-
[] 0.6
0.00035- +
[] + X
+ X 0.8
0.0003- [] []
-t- X
1
E 0.00025-
[] 4" X []
x []
[] -I- []
X
[]
0.0002- [] E~ 4- X []
.-I- + X [] 9
0.00015- [] 9
x 9
x [] 9
0.0001-
[] 9
5E-05-
0
0 ~, ~ ~ 1'o 12
sqrt (omega)
FIG. 5--Current density-o~i/2 plot of model data for various COe pressures with bulk pH controlled by COe, co
in rad s -I.
possible that the origin of this time interval dependence, which is not seen at pH 4-5 where most
of the testing of the model was carried out, is in the much greater influence of the equilibration
stage on the solution compositions at the higher pH.
In general, the slope of the curves decreases as the pH is raised from 4 to 5 but increases again
above pH 6. The curves in Fig. 7 also show increasing currents at low rotation speeds. The
suggestion that the slope of these curves represents the contribution of proton diffusion should,
from the Levich equation, result in a linear relationship between slope and [H+], or a constant
value o f s l o p e / [ H + ] . This is plotted against pH in Fig. 9, from which it can be seen that this is
true in the pH range 4-5, but not at higher pH. In the region 5.5-6.5 the value of slope *[H § is
approximately constant. This implies a diffusing species whose concentration is inversely pro-
portional to the proton concentration.
Concentration Profiles
The origin of some of the effects above can be deduced for the concentration profiles in the
boundary layers. Figure 10 shows these for a pH 4 solution, pCO2 = 1 atm. The profiles are
plotted as differences between the local concentrations and the bulk concentrations (given in
Fig. 1) to enable the different species to be shown on the same plot without using logarithmic
axes. The horizontal axis in all the plots is the dimensionless distance x/~r~, where the Nernst
diffusion layer thickness is that for protons. Figure 10 shows expected behavior. The concentra-
tions of both carbonic acid and protons decrease approaching the surface, and the depleted layer
is thicker for protons reflecting the higher diffusion coefficient. There is some depletion of
carbon dioxide at the surface, although this is only a small change from the bulk concentration,
0 00014
0 00012-
0 0001-
E
Q. 8E-05-
E
v
B. 6E-05-
2
4E-05-
2E-05-
01
0 0'1 0'2 0'3 0'4 0'5 0*6 0'7 0'8 0'9
p C02
FIG 6--Dtffuston independent currentfrom Fig 5 compared with experimental data from Ref 3
and bicarbonate concentration increases towards the surface The changes in the concentrations
of hydroxide and carbonate are small, as are the actual concentrations
Figure 11 shows equivalent data for a bulk pH of 6 5 The most noticeable feature of this is the
unusual bicarbonate concentration profile with the concentration increasing in the boundary
layer and the decreasing again as the metal surface is approached In this case significant m-
creases In carbonate and hydroxide occur near the metal surface
Discussion
The results of the model at pH 4-4 5 agree well with pubhshed data At pH 6 5 the current
rotation speed plot is similar to that obtained by AI-Sayed [6], who also showed that m static
condmons the cathodic limiting current decreased slightly in the range pH 4-6 and Increased
greatly at higher pH Again the model pre&cts this effect of pH Further expenmental work is
required to test the model at intermediate pH
The data at the lower pHs can be explained in terms of the CE mechanism, which is due to the
fact that chemical equlhbration reactions following the electrochemical step have little influence
on the local concentrations At the higher pHs this approach does not predict the currents, since
under these circumstances the following reactions dominate the local concentrations The con-
centratlon profiles in Fig 11 show that the proton flux near the surface is largely earned by
bicarbonate It IS interesting that the depletion of bicarbonate can occur without any direct
electrochemical reduction of bicarbonate In physical terms it is not clear that this process should
be considered a catalytic one but rather a process where the high bicarbonate concentration
enables production of carbonic acid via a dlsproporhonatlon reaction (Eq 21 )
600"
550"
500"
9 x
450"
OJ s
E 400"
r
cL
35O"
s
._u 3OO" +
E
+
250"
+ X
200" + x 9
+ x A []
150"
[] []
10(} m ~
0 2 4 6 8 10 12 lr4 lr6 118 20
sqrt(omega)
FIG. 7--Current density-co I/2 plot of model data for various p H at pCO: = 1 attn. co in rad s -I.
Chemically this is equivalent to the second stage of the EC' mechanism (where
2HCO~ = H2CO 3 + CO 2- (21)
a chemical reaction after the electrochemical step regenerates the reactant), Eq 3, but with
further reaction of the hydroxide with more bicarbonate. The conceptual difference is that here
the source of the bicarbonate is not considered to be the initial electrochemical step, but to be,
predominantly, the large bulk solution concentration. The concentration profiles in Fig. 9 may
also explain the pH dependence of the slope of the current-rotation speed plots, since the
bicarbonate concentration, in the bulk at least, is inversely proportional to the bulk hydrogen
ion concentration.
A further feature of interest is the higher than expected currents in the low rotation speed
range. It is possible that this is an artifact of the model, since it has not been exhaustively tested
under these conditions, but such behavior has been reported in practice [4], where the currents
in static conditions were greater than expected from extrapolation of Eq I.
On the assumption that the corrosion rate'is equal to the limiting cathodic current, by ignoring
the effect of any precipitation reactions, the possible surface ferrous ion concentration can also
be calculated in the model. When this is combined with consideration of the surface carbonate
concentration, the possibility of exceeding the solubility product of ferrous carbonate can be
calculated. (The possibility of formation of a ferrous carbonate film also depends on the poten-
tial being high enough for it to be stable with respect to iron metal.) When this was done, it was
found that pH 4 solutions with pCO 2 = 1 atm gave surface conditions just saturated with ferrous
carbonate (with a surface pH around 5.8); therefore at bulk pH > 4 the formation of carbonate
films is possible.
TURGOOSE
ETAL.ONCARBONDIOXIDECONTAINING
SOLUTIONS 79
3 0 ~ 200
-180
25 160 A
I
1140 oE
-120 ~"
O
-lOO _,-3
E
-80
60 2
t--
"40
"20
04 4'5 ~ 5'5 6 6~
pH
FIG. 8--Variation of slope and intercept of plots in Fig. 7 with pH.
100000000: :0.01
0.001
10000000
4-
"1-
0.0001
0
1000000:
1 E-05
100000i
4 4.5 5 5'.5 6 6.5
1 E-06
pH
FIG. 9 - - Variation of slope * [ H +] and slope/[ H +] (slope = slope of plots in Fig. 7) with pH.
'1 I~
"
~"
o
:i0 0:2 Or4 0:6 0:8 i 1:2
distance (x/~,,}
1:4 1:6 1:8
I-~~
2
-1 o
I --I- H i H2C ~" HCO3- L7 CO2 I
FIG. l O--Concentration profiles, expressed as C(x)-C(bulk), tool cm-~, in boundary layer for pH 4, pCO 2
= 1 arm. ~ = 160 rad s - i . 6N"for H +. from Eq I0.
4 1.6
]
3 oF
-~ - 1.2 ~" x
~, ~ 002
=~ ~ -o.8 ~, .2co3
hc
7 \%-'-'--. _~ oo~
~- 0.2 ~
~ -1
d
.21
0 0'.1 0'.2 0'.3 0'.4 o'.s o'.6 0'.~ o'.a o'.9 1
distance x/g,,
FIG. I I--Concentration profiles, expressed as C(x)-C(bulk). tool cm -J, in boundary layer for pH 6.5.
pCO_, = I acre, *o = 250 tad s - i . ~ , for H +. from Eq 10.
Conclusions
The model describes the current rotatton speed behavtor for the cathodic process m CO2-
containing solutions and demonstrates that the various proposed mechantsms are simply specml
cases of the effects of the complex solution chemistry, with the nature of the tmportant chemtcal
steps dependent on the bulk solution chemistry Consideration of both the calculated currents
and the concentration profiles mdtcates that the CE mechantsm ts a good approxtmatlon in the
pH range 4-5, but that above pH 6 the rate ts controlled by the production ofcarbontc acid from
the htgh concentration of btcarbonate
Other features demonstrated by the model mclude
1. The assumption of a heterogeneous hydration process for carbon dioxide is not necessary
to explam present experimental data
2 The increase m current at pH > 6 ts exphcable w~thout needmg to consider bicarbonate
reduction
3 The model also calculates the local solutton chemistry, which is important in understand-
lng the nature of rate controlling steps, and can also be used to predict the possibthty of
surface film formation
References
[1] De Waard, C and Mdhams, D E, Corrosion, Vol 31, 1975. p 131
[2] Ogundele. G I and White, W E, Corrosion, Vol 42, 1986, p 71
[3] Schmm, G and Rothmann, B, Werkstoffe und Korroston, Vol 28, 1977, p 816
[4] Wmckowskl,A, Ghah, E, Szklarczyk, M, and Sobkowskl, J, ElectrochtmlcaActa, Vol 28, 1983, p
1619
[5] Enksud, E and Sontvedt, T, m Advances m CO2 Corrosion, R H Hausler and H P Godard, Eds,
NACE, 1984, p 20
[6] AI-Sayed,M, Ph D thesis, UMIST, Manchester, U K, 1988
[7] Wmckowskl,A, Ghah, E, Szklarczyk, M, and Sobkowskl, J, ElectrochtmlcaActa, Vol 28, 1983, p
1627
[8] Kern, D M, Journal of Chemtstry Education, Vol 37, 1960, p 14
[9] Bard, A J and Faulkner, L R,ElectrochemwalMethods, Wdey, New York, 1980
[10] Swer, Yu G, Russian Journal of Physical Chemistry, Vol 33, 1959, p 533
DISCUSSION
Earl Pye I (written dlscusswn)--CO2/H20 systems do have buffenng You suggested, how-
ever, that there was little buffenng Why is there little or no buffenng m the system9
S Turgoose et al (authors'closure)raThe CO2-water system does have buffenng ability under
the conditions considered here, but the reactions causmg the buffenng reaction are slow With
contmuous addition of hydroxide, as from a cathodic reaction, it is possible to raise the local pH
more than would be expected from thermodynamic considerations This is because when CO2
dissolves m water the major species present is dissolved carbon &oxide, with only small amounts
of carbonic acid, and the hydration of carbonic acid is slow This means that It is possible to
deplete the carbonic acid, and so raise the pH, dunng hydroxide addmon, even though the
system might be well buffered over longer time scales
t Cahfomla State Polytechnic Umverslty, Pomona, CA 91766

A n d r e w F. Palus ~ a n d Cynthia A. Nienart I
The Use of Computer Modeling in the

Interpretation of Filming Inhibitor Mechanisms
REFERENCE: Palus, A F, and Nmnart, C A , "The Use of Computer Modeling in the Inter-
pretation of Filming Inhibitor Mechanisms," Computer Modehng m Corrosmn, ASTM STP 1154,
R S Munn, Ed, Amencan Society for Testing and Matenals, Phdadelphm, 1992, pp 82-91
ABSTRACT: The computer has made the collecnon and interpretation of data easmr The advent
of computer controlled mstrumentatmn made ~t possible to easily acqmre electrochemical ~mped-
ance data, unfortunately the complex nature of the data made tt dtfficult to interpret One classacal
approach to mterpretatmn ~s to hypothesize an equivalent c~rcmt to model the electrochemical
system Since the equatmns and algorithms of electrical clrcmts are well defined, a computer
program can do an excellent job ofmodehng these eqmvalent ctrcmts We will discuss how the use
ofa commercmlly available ~mpedance modehng program can be used m the interpretation of real
impedance data
Cmnamaldehyde is known to act as an inhibitor to steel corrosion in hydrochloric acid The
mechanism for protecnon is assumed to be twofold The chemlsorptmn of trans-cmnamaldehyde
(TCA) Is usually proposed as the major contributor to Inhibition A secondary, but slgmficant,
contribution is caused by the polymenzanon of the TCA to form a film Growcock and Lopp [ 1 ]
have studmd the nature of these two mechanisms They showed through corrosion rate studies,
orgamc analysis, NMR, FT-IR and GC/MS the nature and functmn of the orgamc film formed by
TCA
We have studied the film formanon of TCA on 1018 steel m HCL solunons using electrochemt-
cal impedance spectroscopy Experiments were run to try to d~stmgulsh the difference between the
two major mhlbmon mechamsms The impedance spectrum of an adsorbed TCA dlffuston barrier
should differ from the spectrum of either a polymer film or a combmanon polymer film and
diffusion bamer The Eqmvalent Circmt modehng program of Boukamp [ 15] was used to assist m
interpretation
KEY WORDS: cmnamaldehyde, mhlbltors, mechamsms, modehng, steel, hydrochloric acid, im-
pedance, corrosion
Electrochemical corrosion m e a s u r e m e n t instruments have b e e n used in the m e a s u r e m e n t o f

corrosion inhibition [ 2] In general, the methods used have b e e n direct current in nature a n d
provide only information on the corrosion rate While useful for inhibitor studies a n d the rank-
lng o f effectivity o f lnhibltors, these techniques do n o t provide information o n inhibitor
mechanisms
Electrochemical i m p e d a n c e spectroscopy ( a n ac electrochemical t e c h n i q u e ) can be used to
investigate surface p h e n o m e n o n at electrochemically active surfaces [ 3 - 6 ] Some workers have
a p p h e d this t e c h n i q u e to the investigation ofcorroslon inhibitors [ 7-9] T h e a d v e n t o f c o m p u t e r
controlled instruments a n d c o m p u t e r modeling programs for the t e c h m q u e make its applicatton
to practical corrosion m e a s u r e m e n t s available to the large majority o f workers This t e c h n i q u e
has the capabdlty to distinguish between m a n y different m e c h a m s m s at the electrode surface
t EG&G Pnnceton Apphed Research, P O Box 2565, Pnnceton, NJ 08543
82
PALUS AND NIENART ON FILMING INHIBITOR MECHANISMS 83
Ci
Ri I( ce
FIG l--Eqmvalent circuit modelfor polymer film where RI = soluuon reszstance, R2 =film resistance, R3
= charge transfer resistance, C 1 = film capacitance, and C2 = double-layer capacttance
Unfortunately, the complexity and interactions at an electrochemical surface makes direct de-
duction o f mechanisms from the data nearly impossible
One approach to determining a mechanism at the surface of a metal of interest is to propose
equivalent clrcmt models o f the pathways o f interest Since the equations that predict electronic
circuit elements are well known, simulated data can be generated for proposed equivalent cir-
cuits These theoretical models can then be compared to the real data obtmned for the corroding
system We have chosen a well investigated system of inhibition to study using this approach
The corrosion inhibition effect o f trans-clnnamaldehyde ( T C A ) on mild steels has been well
documented [ 10] The mechanism o f that inhibition has been the subject of some debate Some
researchers assume that the primary mechanism is chemlsorption [11 ] Recent papers have
suggested that the main mechanism for inhibition at elevated temperatures is the formation of a
polymer-like film [ 1] In this paper the results o f electrochemical impedance experiments at
room temperature will be presented
Procedure
Measurements were made in 15% HC1 at room temperature (20 ~ The metal used was 1018
steel which was polished to a 600-grit finish pnor to use The trans..cmnamaldehyde ( T C A ) was
obtained from Aldnch and was used with no further punfication Fresh HC1 solution was pre-
pared for each expenment T C A was added after immersion o f the metal and measurement o f
the corrosion characteristics without the inhibitor
Corrosion experiments were conducted in a cell as descnbed in A S T M G 5-82 The exposed
specimen area was 1 cm 2 m a planar configuration Impedance measurements were made with
an E G & G Pnnceton Applied Research Model 273 potentiostat, Model 5210 lockln analyzer,
and Model 388 electrochemical impedance software Data were collected in the frequency
Ci
Ri I(
R2
FIG 2--Equivalent circuit model for chemtsorptton where R1 = solution resistance, R2 = charge transfer
resistance, C I = double-layer capacitance, and Zo = diffusion layer impedance
CINY5E
0 Simulation
E
J=
2
E_
N
0 I
I
0 5 10 15
Z real, [ohm] -->
FIG 3--Fit of chemtsorptlon model to no-tnhtbztor data
regime of 0 01 to 100 000 Hz Modeling was done using the Equwalent C~rcuit program of
Boukamp [ 15]
Results
The two different mechamsms for mhlbmon can be modeled by two different equwalent
c]rcmts A polymeric film could be modeled as shown in Fig 1 Here we have the typical
capacitor and resistor used to model the electrochemical reaction, but then we have a second
+ 210 Mm
40
V 180 Mm.
* 91 Mm.
I
l
1~ 36 Mm. +
+ +
.X No Inhib
& +
1-" + ~ &
O
20 m & +
+
-k & 4"
gl &
[] ++
U a -k %
rJ aa ~
!
I , , I I I ' J I .I
O~ ' ' ~"
0 20 40 60 80
Z . t e a 1. [ohm] ~>
FIG 4--Nyqulst plots of 250 ppm TCA added after various ttmes
x No Inhib.
Q 20 M)n
* 90 Min.
V 160 Mm.
+ 310 Mm
+ + +
50
+ zx t~ A +
t-
o + ~r *
.
IV
| !
0 50 iO0
Z.real, [ohm] -->
FIG 5--Nyqutst plots of lO00 ppm TCA added after various times
resistor and capacitor combination that represents a coating on the metal This representation
can be thought of as a polymer film that must be penetrated before the actual corrosion reaction
can happen Th~s model for a coated electrode has been proposed by many workers [ 12-14]
The chemlsorpUon mechanism can be modeled as shown m Fig 2 Here we have our well
accepted Randles-type circuit but with a constant phase element added m series with the charge
transfer resistance The Z0 symbol IS used to represent an impedance element whose frequency
behavior is predicted using the hyperbohc cotangent function This represents a fimte length
diffusion layer that is permeable to the diffusing species
The Z0 c i r c u i t element behavior is generally found m corrosion related diffusion [ 15] This
can be seen ffwe model the data for the 1010 steel m HC1 with no inhibitor present Figure 3
compares the fit of simulated data for the chemlsorptlon model (F~g 2) to the real data obtained
for the corroding system This Nyqmst plot is typical of a corroding system The semi-circle is
depressed probably due to multiple corrosion sites and uneven current distribution
The Bp value of approximately 8 fl was obtained from the calculated values used for the fit of
the chemtsorptton model as shown in Fig 3 Th~s Rp value would correspond to a corrosion rate
of approximately 1250 mpy based on the equation
C R (mpy) = [130Ir W )]/d
where lr lS expressed in mA and can be calculated from the equation
I~o~ = (B, Bc)/[2 3(B, + Be)Re]

40
A CY7E
O Simulation
z~
A
1
20 /x A
E
=o
E_
N
I
0~
0 20 40 60 80
Z real, [ohm] -->
FIG 6--Fit of chemtsorptton model to 1000 ppm TCA data
where B a a n d B c were b o t h assumed to be 100 m Y / d e c a d e , E W ( e q u w a l e n t weight) is 27 5, d

( d e n s i t y ) is 7 8, a n d the area was 1 cm 2 T h e corrosion rate o f the system mcreased with time b u t
with httle change in the i m p e d a n c e behavior o f the system
T h e a d d m o n o f the T C A at levels o f 250 a n d 1000 p p m resulted m a slow decrease m the
corrosion rate with u m e T h e impedance data are shown as Nyqulst plots m Figs 4 a n d 5 If the
40
A C9
O S=mulatlon
20
Z
o.
_E
N
I I
0 20 40 60 80
Z real, [ohm] -->
FIG 7--Fit of polymer model to 250 ppm TCA data

Z~CY12E
O Simulation
50
o~
_E
N
0 I I I I I I I I I
0 50 I O0 150
Z real, [ohm] -->
FIG 8--Fit ofpolymermodelto 1000ppmTCAdata
same chemlsorptlon model used above Is apphed to the data for 1000 ppm TCA after a 20 mm
exposure, the model fits faLrly poorly (Fig 6) Close examination of the data using the modehng
program led to the behef that a second t]me constant (RC clrcmt) mtght be observed m the data
A better model for this behavior ~s the eqmvalent c~rcult suggested m F~g 1 A s~mulat~on ofth~s
clrcmt, which includes two time constants, for both the 250 ppm data and the 1000 ppm data
compared to the real corroding system data, is shown m Ftgs 7 and 8
Addmon of higher levels of TCA (5000 ppm) showed almost lmme&ate improvement in the
corrosion rate (an mcrease m the R v value, see Fig 9) However, there ts no apparent change m
the mhlbmon mechamsm, the data do not fit the chemlsorptmn model of Fig 1 The polymeric
400
+ 160 Mm
? 90 Mm.
* 40 Min
[3 10 MJn
r" X No Inhlb
0
200 + + + +
+
~
E rlqr A
I
~ , I J I I I I~1 I I ,4- ,4-

0 200 400 600 B00
Z.real, [ohm] -->
FIG 9--Nyqulst plots of 5000 ppm TCA data after vartous tones
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further reproductions auth
05 --
A CINX21
O S=mulatlon
I
oo
00 05 10
Z real, [ohm] (x10"3) -->
FIG lO--Ftt of polymer model to 5000 ppm TCA data
film model again gives a very reasonable fit to real i m p e d a n c e data for the corroding system (Fig
10) T h e fit parameters for the p o l y m e n c film model to the data for Figs 7, 8, a n d 10 are shown
m Table 1
Discussion
T h e chemlsorptgon m e c h a n i s m can be t h o u g h t o f as a competing reaction to the corrosion In
this case, the T C A could occupy distinct sites o n the surface that might otherwise serve as
corrosion sites (Fig 11 ) This leads to a decrease in corrosion rate, since there are fewer corro-
sion reaction sites W e see n o evidence that th~s m e c h a m s m is ever in effect for the T C A system
This Is m contrast to the previous findings in the literature [ 11 ] b u t corroborates the more recent
findings [ 1 ]
T h e polymeric film m e c h a n i s m o f m h l b m o n is the same as coating the metal with a n orgamc
polymer film m u c h hke paint only at a slgmficantly smaller film thickness In this case the
inhibitor forms a b a m e r that the corrodant must penetrate before the oxldaUon o f the metal can
occur (F~g 12) At room temperature, the polymer does not form a thick film A n estimate o f
the film thickness based o n the c a p a o t a n c e o f the coating a n d a n assumed &electric c o n s t a n t o f
10 for the 5000 p p m data ~s approximately 8 rma This was calculated from the equation
d = EEoA/C
TABLE 1--Calculated values for circuit elements used m numencal fit Note that Q's representing CPE's
were used m place o f C's (see text)
Rl (ft) Ql (F) nl R2 (f0 R3 (ft) Q2 (F) n2
F~g 7 0 41 8 65 • 10-5 0 87 33 8 21 7 1 52 • 10-3 0 64

F~g 8 0 66 2 62 • 10-5 0 89 18 4 122 1 1 19 • 10-4 0 68
Fig 10 020 1 1 7 • 10-6 080 1865 6136 1 9 8 X 10-5 063
FIG 1l--Simple modelfor the chemlsorptton of TCA
where E is the dtelectnc constant of the coating, Eo Is the permlttlVlty of a vacuum (8 9 • 10-14
f/cm), A Is the area, and C ts the capacitance As Table 2 illustrates, the calculated thickness
increased with increasing inhibitor concentratmn Even at the h~ghest inhibitor concentratmn
studied, the thickness does not approach some reported thicknesses at higher temperatures [ 1 ]
No electrochemical system can behave hke an ideal capacitor The proposed model (chemlsorp-
tlon and polymeric film) was fitted to the real data using constant phase elements (CPE) m place
of the drawn capaotors The frequency dispersion relation for a CPE is [ 15]
R
O0
F1G 12--Simple modelfor a polymer film ofrCA

TABLE 2--Comparison of thickness of polymerw fihn at various inhibitor concentrations
lnh,bltOr Concentration Capacitance Thickness

Data From (ppm) (F) (nm)
Fig 7 250 8 65 • 10-5 0 10
Fig 8 1000 2 62 • 10-5 0 34
Fig 10 5000 1 18 • 10 -6 75
(jw)-"/Yo
where j is the square root o f - 1 , w ts the angular frequency, and Y0 is a parameter of the
electrochemical system This Is a generahzed dispersion relationship that will fit different known
components based on the value of the exponent, n When n is equal to 1, the CPE is a capacitor
When n is equal to 0, the CPE is a resistor An n o f 0 5 is a Warburg impedance For the
1018 [ T C A system studies (Table 1 ) the CPE o f the film has an average n o f 0 85 This indicates
that the film is behaving like a "leaky" or "lossy" capacitor This helps validate the assumption
of the polymenc film model A film of nonconducting material with charge on either side should
resemble a capacitor
The CPE of the charge transfer double layer of the metal surface has an average n of 0 6 This
is consistent with a pseudo-capacitance that has been observed for corroding systems This xs
equivalent to a surface that has many corrosion sites This dispersion of corrosion sites tends to
give a depressed semi-circle in the Nyqulst plot. as is observed in these data [3]
Conclusion
The results of the electrochemical impedance study on the T C A / 1 0 1 8 steel system agree m
pnnctple with previous work There ~s ewdence that the formation of a polymer film is the main
corrosion inhibition mechanism o f T C A on mild steel The use o f m o d e h n g software made the
comparison of proposed mechantsuc models to the real data simple and relatively rapid
References
[1] Growcock, F B and Lopp, V R , Corroszon. Vol 44, 1988, p 248
[2] Rlggs, O L m Corrosion Inhtbttors, C C Nathan, Ed, NACE. Houston, Tex. 1977, pp 7-27
[3] Sdverman, D C m Electrochemwal Techmques for Corrosion Engineers, R Babolan, Ed, NACE,
Houston, Tex, 1985, pp 73-79
[4] MacDonald, J R , hnpedance Spectroscopy Emphasmng Sohd Materials and Systems. Wiley, New
York, 1987
[5] Mansfeld, F. Corrosion. Vol 37, 1981, pp 301-307
[6] Mansfeld, F, Corrosion. Vol 44, 1988, pp 856-868
[7] Mansfeld, F and Kendlg, M W in Proceedings. 6th European Symposmm on Corrosion lnhlbltors,
1985, pp 817-829
[8] Kendtg. M W et al, m Electrochemwal Techmquesfor Corrosion Engineers. R Babotan, Ed, NACE,
Houston, Tex. 1985, pp 151-160
[9] Sflverman, D C and Cameo, J E, Corrosion. Vol 44, 1988, pp 280-287
[10] Hugel, G , m Proceedings. 1st European Symposium on Corrosion Inhlbltors, Ferrara, Italy, 1960
[I 1] Growcock, F B and Fremer, W W, "Inh.bluon of Steel Corrosion m Hydrochloric Acid by trans-
Clnnamaldehyde," 170th Meeting of the Electrochemical Society, San Diego, Cahf, Oct 1986
[12] Mansfeld, F et al, Corrosion Scwnce, Vol 23, 1983. pp 317-329
[13] Scully, J , "'Electrochemical Impedance Spectroscopy for Evaluauon of Orgamc Coating Detenorauon
and Underfilm Corrosion A State of the Art Technical Review." David W Taylor Research Center
Report SME-86/006, 1986
[ 14] Granata, R, "'EvaluaUonof Orgamc Coatingsby ElectrochemicalImpedance Measurements," Apph-

cation Note AC-2, EG&G PARC, Prmceton, N J, 1985
[15] Boukamp, B A in ComputerAtdedAcqutsmon of Corroswn Data, M W Kendlg, Ed, The Electro-
chemical Society, Pennmgton, N J, 1985, p 146
DISCUSSION
J C Fan I (wrlttendlscusston)--TheNyqutstplotofTCAshowsastrongtlmedependenceof
the film resistance m your experimental umeframe Consldenng the number of data points on
the plot and the frequency range employed, each scan reqmres about 15 mm to fimsh Conse-
quently, the continuous film growth dunng the expertment could result m a serious d~stort~on m
the Nyqmst plot, especially m the low frequency regime As a result, it is mcorrect to reject the
chemlsorptton mechamsm based upon the misfit between the experimental data and the fitted
data
A F Palus and C A Ntenart (authors' closure)--Although you are correct that the time
dependence of the reaction may seriously distort the Nyqmst plot, we still believe that one can
reject the chemlsorptlon mechamsm If the changing nature of the film under study strongly
influenced the data, we would expect to see e~ther noisy or scattered data We would not expect
that the d~stort~on of the data would give a two time constant response It is the observation of
two ume constants that leads us to reject the chemtsorpt~on model One can see these two t~me
constants qmte clearly m the data for the experiments with 5000 ppm TCA added
0 F Devereux 2 (wrttten dlscusston)--In my expenence Fig 12 can also be modeled by a
Randles clrcmt with a fimte length Warburg element This would imply, not a polymenzed film,
but a soft, possibly adsorbed film that serves to impede dtffuslon of a reactant to, or product
from, the surface Did you try such a model9
A F Palus and C A Ntenart (authors" closure)--Whde we did not try a spectfic model with a
Warburg element, the use of a CPE should cover this quesuon If a Warburg element were a
better fit to the data, we would expect that the n value for the CPE would be closer to 0 5 rather
than its value of 0 85
) W R Grace & Co, Dearborn Dwlslon, Lake Zurich, IL 60047

2 Department of Metallurgy, University of Connecticut, Storrs, CT 06268
Corrosion Data Fitting and Modeling of
Electrode Kinetics and Impedance
S. C. Kranc 1 and A. A. Sagues t
Computation of Corrosion Macrocell Current

Distribution and Electrochemical Impedance
of Reinforcing Steel in Concrete
REFERENCE: Kranc, S C and Sagues, A A . "Computation of Corrosion MacroceU Current
Distribution and Electrochemical Impedance of Reinforcing Steel in Concrete," ComputerMod-
ehngin Corroston. A S T M S T P 1154. R S Munn, Ed, American Socmty for Testing and Matenals,
Philadelphia, 1992, pp 95-112
ABSTRACT: The case of a reinforcing steel bar experiencing locahzed corrosion in a concrete
cylinder has been modeled numerically to obtam the d-c macrocell current dtstnbutton and the
assocmted electrochemical impedance response The bar contains a small anodlc and a large
cathodic region Cyhndncal symmetry has been assumed The d-c polarization problem was solved
using finite-difference equations apphed to a two-dimensional grid The boundary condiuons
included polanzation at the cathode, accounting for both acttvation and dlffuslonal effects The a-c
~mpedance calculation was made for cyhndncal counter electrodes The computation used a two-
dimensional eqmvalent circuit resistive grid representing the electrolyte and calculated for cyhndn-
cal geometry The a-c polarization conditions at the bar surface were represented by discrete
impedance elements, computed from the current densmes obtained m the d-c calculaUon Both
activation and dlffuslonal impedance components were considered as well as mterfacml capaci-
tance The model was used to investigate macrocell current distribution and the apphcabfllty of
electrochemical impedance to the measurement of corrosion currents m reinforced concrete struc-
tures with large cathode-to-anode area ratios Predicted impedance spectra for concrete resistivity
of l0 000 fl-cm, with an effectwe oxygen diffusion coeflioent of l0 -s cm2/s, and for vanous
cathode/anode area ratios are presented The results show that the dtstnbuUon of the alternating
current exotation emphasizes the ~mpedance contribution of the cathodm reacaon to the overall
impedance spectrum
KEY WORDS: corrosion, concrete, steel, rebar, reinforcing, macrocell, polarization, d~ffuston,
Warburg, impedance, oxygen, reslstwlty computauon
The corroston of reinforcing steel bars (rebars) in concrete is a growing problem affecting the
mtegmy of a vast number of structures [ 1] The reinforcing steel is embedded m the concrete,
whtcb mmally provides an alkaline environment conducive to surface passwation U n d e r these
conditions, metal dissolution takes place at an extremely low rate However, depasswatlon of the
steel surface can take place if chlorides (from highway deicing salts or from seawater) penetrate
through the concrete cover and reach tile rebar Depasswation can also result from penetration
of a carbonation front (and consequent pH reduction) through the concrete as a result of
exposure to atmospheric carbon dioxide The locally active steel surface behaves predominantly
as an anode while the entire bar may serve as a cathode The main cathodic reaction is thought to
be the reduction o f oxygen [ 2,3 ], whlch is transported to the metal surface through the concrete
cover, Metal ions dissolved at the anodlc region form corrosion products which are expected to
occupy a volume significantly larger than that of the initial metal Crocking and spalhng o f the
1 Department of Civil Engmeenng and Mechamcs, University of South Honda, Tampa, FL 33620
95
FIG. l--Simplified representation of the reinforced concrete cylinder used in the calculations. A half-space
grid with rotational symmetry was usedfor the d-c calculations. The a-c calculations used afull length equivalent
circuit, also with rotational symmetry. The grid equations and component values included the radial dependence
needed for cylindrical scaling.
concrete cover eventually follow, requiring expensive repairs or replacement of the structure.
While this corrosion problem is widespread, the slow rate of development and hidden nature of
the damage make its characterization difficult. There are few quantitative studies aimed to
predicting the distribution of corrosion in concrete macrocells [4-9]. Moreover, these predic-
tions cannot be confirmed easily by non-destructive electrochemical corrosion measurements.
This is because the polarization conditions at the steel surface are complicated by slow transport
of oxygen and corrosion products, interfacial capacitance, and current distribution inhomogen-
city due to the high concrete resistivity [ 10]. There is a need for detailed quantitative prediction
of corrosion in steel in concrete accounting for complex polarization conditions, and for develop-
ing reliable criteria for evaluating the predictions. This need was addressed in the present paper
by matching calculations of the distribution of corrosion and the response to Electrochemical
Impedance Spectroscopy (EIS) measurement excitation in the same reinforced concrete system.
Procedure
Reinforced Concrete Configuration
The system chosen consisted of a reinforced concrete cylinder (Fig. 1) with a single axial
rebar. The system is cylindrically symmetric. All concrete and rebar dimensions are finite. The
bar surface contains a central, purely anodic region of finite length. The rest of the bar surface is
KRANC AND SAGUES ON MACROCELL CURRENT DISTRIBUTION 97
purely cathodic The length of the cylinder is L, b and a are the concrete cylinder and rebar radii
respectively, and la is the width of the anodlc region The physical configuration chosen is
frequently encountered in laboratory test specimens used in EIS investigations of reinforcing
steel in concrete [5]
Direct Current Polarization Conditions

The concrete is treated as a homogenous medmm which has uniform resistivity, and where
dissolved oxygen is transported by diffusion The cathodic polarization is assumed to follow the
same potential-current relationship over the entire cathodic region The relationship includes
mixed activation and diffusion control, obeying simple Butler-Volmer kinetics for the case where
the polarized potential E is greatly removed from the equillbnum potential
tc = t o ( Q / C o ) exp[(2 3 / b r E - Eo) ] (l)
where
lc = cathodic current density,
Io exchange current density for the cathodic reaction,
C s = effective oxygen concentration of concrete at the rebar surface,
Co x effective oxygen concentration of concrete in direct contact with air,
b r = activation Tafel constant for oxygen reduction on passive steel in concrete,
Eo = equilibrium potential for the cathodic reaction, and

E = polarized potential The sign convention used in this paper IS such that all potentials are
with respect to the metal Thus the more positive E is, the faster the rate of the cathodic
reaction tends to be
The value of Cs along the rebar surface is determined by the transport conditions for oxygen
over the entire cyhndncal concrete region, coupled with the polanzatlon pattern along the rebar
Solution of that complicated problem IS beyond the scope of the present paper As an approxi-
mation, oxygen diffusion along the axial direction will be neglected Solution of the steady-state
radial-only diffusion problem is straightforward By application of Flck's first law
Co - Cs = JDa l n ( b / a ) (2)
where
J = flux of oxygen at the rebar surface (mol per unit area per unit time), and
D = effective diffusion coefficient of oxygen in the concrete
By Faradalc conversion, and assigning four electrons to the reduction of each oxygen mole-
cule (OE + 2H20 + 4e ~ 4 O H - ) , the cathodic current density becomes
tr = 4F(Co - C s ) D / a In ( b / a ) (3)
At the diffusion-limited extreme (C, = 0) the limiting current density t~ is reached
tl = 4 F C o D / a In ( b / a ) (4)
Apphcatlon to Eq 1 yields
1r = l l / [ ( l l / l o ) exp(--(2 3 / b c ) ( E - Eo)) + 1] (5)
The value of be can be gleaned from polanzatIon measurements performed with steel in
concrete at very slow potential scan rates [ 11 ], which yielded values in the 100 to 200 mV range
This agrees with Tafel slopes of about 160 mV commonly observed for oxygen reduction of steel
in alkaline solutions [ 12], and with recent observation of long-term static polarization behavior
of partially exposed steel in concrete [ 13] A value of 160 mV will be used in the calculations
presented here
For a given choice of be, the actwation-hmIted cathodic polanzation behavior requires a
suitable combination of E o and to values to define the operating point The combination need
not be umque, as long as the adequate value Ofto/exp(2 3 Eo/bc) is obtained (see Eq 1) Based
on typmal steel in concrete behavior [5,8,11], the combination Eo = 0 V (SCE) and to = 2
• l0 -8 A / c m 2 will be used as a representative value in the subsequent calculations
There is limited quantitative informatmn on the diffusivity of oxygen in concrete [2,3] The
value of D is expected to vary strongly with the moisture content of the concrete [2] An
effective value o f D = 10 -5 cm2/s is representative of those in the range observed for concrete
exposed to humid environments [2,3] and will be chosen for the following calculations Consis-
tent with that choice and the treatment used in Ref3, the oxygen concentration will be expressed
also as an effective value, equal to that of water in local equihbnum with the concrete Thus the
value of Co will be 2 5 • 10-7 mol/cm 3 (typical of fully aerated conditions) For the cylinder
dimensions used here, these choices correspond to tl = 8 05 • 10 -7 A / c m 2
The polarlzauon charactenstics of the anodlc reaction of steel in concrete are not well known
However, by analogy with iron dissolution in aqueous media, it may be expected that the
reaction be predommantly activation-limited, with a relatively small Tafel constant (on the
order of 0 060 V [ 14]) On account of this relatively small value and the assumed absence of
diffusional effects, the d-c anodic behavior will be simplified by treating it as that of an unpolar-
izable electrode (as was done in Ref8) This choice results in a zero anodic Tafel slope, which
permitted defining the polarization condition of the anodic region by assigning a suitable con-
stant potential A representative value of 600 mV (SCE) was chosen for the calculations
The concrete will be considered as a homogeneous electrolyte joining the cathodic and anodic
regions, with a constant resistivity of l0 000 ~-cm As in the choice of the diffusion coefficient,
this value is representative of concrete in a relatively humid environment [ 15 ]
Alternating Current Polarization Conditions

Computation of the d-c state of the system yields, as will be shown below, values of the direct
current density at every position in both the concrete and on the metal surface (which were
divided into suitable elements) The direct current densities at the metal surface were used to
calculate the small-signal admittance per unit area at each element of the bar surface The
calculation was based on established relationships derived from the low-amplitude hmlt of the
Butler-Volmer electrode kinetics equations (for the Faradalc admittance) [ 16-18], and on the
assumption of a uniform interfaclal capacitance per unit surface (as a non-Faradaic admittance
element) As in the d-c treatment, both activation and diffusion phenomena were considered in
calculating the distributed admittance of the cathodic portion of the bar
From the treatment of Haruyama and others [ 16-18] the Faradaic impedance of a discrete
cathodic surface element in a one-dimensional diffusion case can be descnbed by
Zfr = br 3I~ + [br 3(I1 - Ir tanh ( J ~ ) / J V ~ (6)

or simply
Zfc = Rc + W
where
Ic = cathodic current at the surface element,

Ii = hmmng cathodic current density for that surface element,
u = 2~rfd2/D, where f l s the a-c test frequency and d is the effective diffusion distance,
j = ~'S~, and
Re, W = actlvaUon and &ffUSlOnal(Warburg) components, respectively, of Zfr
The relationship between a-c response of mdw~dual surface elements and their respectwe
direct currents is expected to be more complicated m the system considered here, because of the
presence of adjacent elements and three-dimensional dlffuslonal flow As a first approach in
deahng with this intricate problem, Eq 6 will be assumed to be locally valid at each surface
element The dtffuslon distance, d, m a one-dimensional sltuatton is related to the hmmng
current density by 4 = 4FCsD/d By analogy with Eq 4, the diffusion distance, d, in Eq 6 will be
then approximated by
d = a In ( b / a ) (7)
In the d-c calculauons, the anode was treated, for slmphclty, as an unpolanzable electrode
While that approxlmatton has a limited effect on the overall direct current dlstnbuuon, a singu-
larity wdl result lfapphed to calculating small-signal a-c impedance This was avoided by assum-
ing that the anodlc portions of the bar behaved as if corrosion were subject to simple activation
polanzaUon This yields for a discrete anodlc surface element the following Faradalc impedance
[16-181
zr. = b d 2 3/~ (8)

where
ba = acUvaUon Tafel constant for anodlc dissolution of iron, and
la = anod~c current at the surface element
Zf. Is a real impedance and as such it can be visualized as a simple reslsuve component Ra As in
the case of the cathodic impedance, it will be assumed that Eq 8 represents the behavior of
individual anodlc surface elements in the actual bar surface
For both cathodic and anodlc surface elements, the respective admittances Yc and Ya will
include the admittance provided by the interracial capaotance C,.~ of the element'
Yr = l/Zfc +127rfC.. (9)
Y. = 1/Zr, +j27rfC.. (10)
The customary arrangement in EIS measurements uses a counter electrode to dehver the
alternating current to the working electrode (the rebar) through the concrete The a-c potenUal
is measured by a reference electrode at a chosen test point The calculations presented here
include explonng the effect of counter and reference electrode placements The base case con-
slders a counter electrode covenng one third of the cyhnder surface, starting at one of the ends
This configuraUon approaches EIS tests where the lower portion of an upright specimen is
submerged m a conductwe hqmd through which the exotauon current is applied
For the purposes of the calculations the a-c potential will be considered constant and equal to
a preset exc~tauon signal over the entire concrete surface m contact with the counter electrode
In addmon, it will be assumed that the counter electrode creates no disturbance on the previ-
ously calculated d~rect current distribution pattern These assumptions are introduced for simpli-
fication, since in reality the counter electrode will have some degree of small-signal a-c polanza-
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant t
tlon (creating non-umformlty of a-c potential at the underlying concrete surface) while not
experiencing complete polarization at &rect current (thus altenng somewhat the previous d-c
macrocell current pattern)
Reference electrodes wdl be considered pomt-hke and are normally placed at three &fferent
possible locations on the concrete surface at the outer radius at either end of the cyhnder, and at
the mid-point The electrochemical ~mpedance is computed by calculating the complex poten-
tml at each of the reference electrode positions and dividing by the total complex current of the
bar
Computer Model Direct Current PolarJzauon

Because the concrete reslstlvlty m the problem statement is constant, the electrical potential U
m the electrolyte sausfies Laplace's equation
V2U = 0 (ll)
The current density J m the electrolyte ~s related to the potential distribution by Ohm's law
S.grad U = J (12)
where S = 1/concrete reslstwlty

At the metal surface, the component of J normal to the surface will be considered as the d-c
polanzatlon current Thus, tr or ta will be given by
/c,a = S,grad UI. (13)
where n Is the normal to the surface

The solution to the d-c problem therefore consists m obtaining U at every point in the con-
crete such that Eq 11 is satisfied, with the following boundary con&tlons
At the anode (non-polarizable as mdlcated earher)
U = constant (in this case U = 600 mV) (14)
At the cathode (combme Eqs 13 and 5)
S.grad U]. = l[l[(ll/lo ) e x p ( - ( 2 3/bc)(E - Eo)) + 1] (15)
At the free concrete surfaces (no current)
S.grad UJ. = 0 (16)
To solve Eq 1 l with con&tlons ( 14-16 ) a standard fimte &fference technique was employed
The region of interest was dwlded by a regular grid employing circular and axial symmetry as
shown m Fig 1 For the half-space analyzed, 26 nodes in the radial direction and 76 nodes m the
axial &rectlon were taken The &fference equations for each node were written to reflect the
two-&menslonal grid arrangement, with a radially dependent term accounting for the cyhndncal
symmetry The method of solution was a Gauss-Seldel lteratwe technique, chosen because of the
comphcated boundary condlUOn in Eq 15 This condmon demands that the gradient of the
potential and consequently the current at the boundary depend m a nonhnear fashion on the
potential along the wall In order to successfully accommodate this condition, it was necessary to
perform
Copyright a fixedInt'l
by ASTM point
(all iteration dunng Tue
rights reserved); eachFeb
relaxation step
10 09:33:27 EST 2015
As the relaxation process converged, the current along the bar was computed and the change
from the previous step was analyzed As a satisfactory convergence ~s reached, the net current
(anode plus cathode) should approach zero, per Gauss' Law The process was quite slow and
typically 105 steps were required to reach a point where the total cathodic and anodic currents
differed by less than 5% from each other The calculation was terminated when that condition
was reached or exceeded The calculated potentials at every point of the grid and currents at the
bar surface were stored for further processing
Computer Model Alternating Current Polartzatton

For this calculation the corroding system was modeled by a passive discrete component net-
work as shown In Fig 1 The electrolyte was modeled by a two-dimensional equivalent circuit
resistive gnd (typically 6 nodes in the radial direction by 151 nodes in the longatudlnal direc-
tion) The value of the resistors was calculated by scaling for the physical dimensions, cylindri-
cal symmetry, and the concrete resistivity The a-c polanzatlon conditions at the bar surface were
represented by discrete impedance elements At each test frequency, the impedance of each
element was computed from the current density obtained at the same point in the d-c calcula-
tion, applying Eqs 6 and 8 to 10 The appropriate scaling was used to account for the system
dimensions, symmetry, and number of divisions used Unlike the d-c calculation, the a-c model
uses a full cylinder-length simulation because the counter electrode was placed usually at one
end
The counter electrode was joined to the nodes at the outer surface of the concrete, over the
appropriate length, by small ( 1 ~2) resistors placed there to facilitate computation of the amount
of alternating current delivered The excitation signal was applied between the counter electrode
and the bar by the a-c voltage source, V, The complex a-c potential at points 1, 2, and 3 (Fig 1)
was divided by the total complex current delivered by the voltage source to obtain the complex
impedance at the test frequency used
Node equations were formulated for each point of the network This was done by estabhshmg
zero balance of current reaching the node from the surrounding nodes, as determined by their
potentials and the Intervening impedance values This involved typically a system of 906 equa-
tions, which were then developed to produce a 906 by 906 complex admittance matrix Y, which
is banded and sparse The external connections result in the lnhomogeneous part of the system
of equations, set as a 1 by 906 matnx
Once the equation set was generated, a packaged program (MATLAB) was invoked to solve
the matrix equation The result is a 1 by 906 matrix, gwing the complex potential at each node
Knowledge of the potential yields the complex current between any two nodes in the system In
particular, the current dlstnbutlon along the bar can be calculated and the current sum can be
used to compute the impedance at statable reference points as descnbed above In addition, the
current sum at the counter electrode nodes can be compared with the sum at the bar (which
should be the same), providing a secondary check of the accuracy of the result
Results
Dwect Current Polartzatton Calculattons
Calculations of the polarization state of the system were performed for the base case and
variants shown in Table 1 Figure 2 shows the current density along the metal surface for the
base case (2A), as well as the potential distribution along the bar surface and at the external
concrete surface (2B) As expected, the cathodic current density is greatest close to the anode
(where it approaches the hmltmg current density) and decays as the distance from the anode
Copyright by ASTM
increases Int'l (all
Likewise, the rights
anodlcreserved); Tue
current is Feb 10 09:33:27
maximum EST 2015
at the edges of the anode and somewhat
TABLE l--Calculatton parameters

Base C a s e Variants
Cyhnder length, L (mm) 300

Cyhnder diameter, 2b (mm) 110
Rebar dmmeter, 2a (rnrn) 10
Anode width, /a (mm) 6 2,10
Counter electrode length (mm) 100 300
Oxygen concentraUon at the external concrete surface, Co
(mol/cm3 (X [0-7)) 25
Oxygen &ffusion coefficient,D (cm2/s (Xl0-S)) I
Corresponding catho&c hmltlng current density, 6 (A/cm2
(X 10-7)) 8 049
Concrete reslstwlty,0 (f2-cm(X104)) 1
Anode potentml, Ea (mV vs SCE) 600
Unpolanzed cathode potential, Eo (mV vs SCE) 0
Catho&c exchange current density, to (A/cm2 (Xl0-S)) 2
Activation cathodic slope, bc (mV) 160
AcUvatton ano&c slope, b~ (mV) 60
lnterfacml capacitance, C,.t (t~F/cm2) 100
smaller at the center The potentml at the concrete ~mmedmtely next to the bar vanes sharply
with &stance to the anode At the concrete surface, however, the potentml variation (as ~t would
be seen by a survey reference electrode) is smoother The highest surface potential is signifi-
cantly lower than the actual anode potentml
The absolute value of the total catho&c or anodlc current (the total macrocell current) has
been &splayed m Fig 3 as a function of the anode size for the base case and the two variants
investigated The potential at the external concrete surface above the anode is shown m the same
figure As expected, the smaller-size anodes result m less macrocell activity, which m turn gives
less conspicuous potentml shifts at the concrete surface
Alternatmg Current Polartzatton Calculattons

Figure 2C shows the result of computing the impedance magmtude-unlt area at various test
frequencies along the bar surface using the &rect current density of the base case and Eqs 6, 8, 9,
and 10 The impedance at the anode is small and vanes httle with frequency, because of the large
current densxty which produces a dominant, real Faradmc admittance component The center of
the anode shows a somewhat higher impedance than the edges, reflecting the &fferences m
&rect current density described earher The cathode impedance ~s high and shows slgmficant
frequency dependence, because the admittance of the lnterfacml capacitance becomes compara-
ble to the Faradmc admittance at the h~gher frequencies At the lower frequencies the catho&c
Farada~c admittance is dominant It should be noted that even though the catho&c current
density ~s h~ghest next to the anode, the catho&c impedance magmtude at low frequencies is also
h~ghest there That effect results from the emergence of the &ffus~onal term at low frequency m
Eq 6 This term is proportional to 0, - It) -l, which is greatest near the anode because tc
approaches h there
As the excitation signal ~s apphed to the counter electrode, current flows through the concrete
and is &stnbuted along the bar according to the intervening electrolyte resistance and the local
impedance at the bar surface Figure 2C shows the results of calculating the distribution of the
alternating current density magmtude for the base case at various test frequencies
At any gwen test frequency, the magnitude of the current density tends to be greater near the
55o
i~ 450
400 i i i i i
40
ANODE
~" 30
0.85
,'1 ih
0.80
~ 0 . 7 5 _
0,70
10e
104Hz
I I0s ........................................ 7
o
IO'2Hz
104
1Hz
i 10s
102 L i i
~.~ 10"6
D
~ 104
o 10~Hz " .-.......,
~ 10n
~''t t""~.- . . . . . . . . . . . . . . . . ~-~':....... "-::::-~-"--

~ 10"~
lO-e L i i L i
50 100 150 200 250

DISTANCEALONG CYLINDER(ram)
FIG. 2 - - Results of application of the d-c and a-c models (base case, Table 1). ( A ) Concrete d-c potential (see
text for sign convention) along the cylinder, next to the rebar and at the external concrete surface. (B) Absolute
value of the direct-current density along the bar surface. ( C ) Modulus of the complex impedance-unit area along
the bar surface, at various frequencies. (D) Modulus of the alternating-current density along the bar surface, at
various frequencies. The counter electrode covers the first 100 mm starting at the left end. The modulus of the
excitation a-c voltage is 10 m V.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further reprod
104 COMPUTER MODELING IN C O R R O S I O N
80 200
60
..-/f f
300
ILl ,/
re" // A
n"
l 0
l
,,--I >
,..I 40 400
LIJ g
8re
0<
l[ 20 500
I.--
od 6'8 '
10
' 600
ANODE SIZE (ram)

FIG. 3 - - Macrocell current and potential at the external concrete surface (over anode) as a function of anode
size.
counter electrode, reflecting the shorter electrolytic path. Deviations from that trend develop at
the anode, with its low interfacial impedance, and on the cathode at either side of the anode.
This latter effect is due in part to the current demand of the adjacent anode, which reduces the
overall magnitude of the a-c potential in the surrounding region. At low frequencies the effect is
enhanced by the increase in diffusional impedance mentioned earlier. The difference in current
density between anode and cathode regions becomes less at the higher frequencies, when the
admittance at the bar surface is determined primarily by the interracial capacitance.
E I S Calculations
The results of EIS calculations are shown as impedance diagrams in the Nyquist form in Fig. 4
for the base case and variants. Calculations were performed for each of the three reference
electrode positions and for frequencies ranging from 10 -4 to 1 Hz. All diagrams show some
degree of distortion compared with the semicircular shape that would result in a system modeled
by a simple parallel resistor-capacitor combination. Most of the distortion is present at the low
frequency end of the diagrams. The shape, size, and position of the diagrams changed depending
on the position of the reference electrode; impedance magnitudes tended to become smaller as
the reference electrode was placed further away from the counter electrode. For the electrode
position farthest away, the real part of the impedance shows an interval of negative values at
moderately high frequencies.
Discussion
Direct Current Behavior

The calculations provided self-consistent results that converged within expected limits. The
anode potential value selected provided external surface potential readings in keeping with those
commonly observed in reinforced concrete systems that experience active corrosion [1 ]. The
500
1 I== 2mm
T E S T ~
500
il!
1 I=ffi 6mm
Et- 2
v
O
0 I I
500
la= 10mm
1
.0001Hz
0 ' I ' I '
0 500 1,000 1,500

Z' (ohms)
FIG 4 - - Results of the EIS calculattons, dtsplayed as Nyqulst dtagrams, for the three anode stzes mvestlgated
and calculated for each of the reJerence electrode test pomts (see Fig 1) The lowest test frequency used was
0 0001 Hz The potntsfor increasing frequency decades (up to 1 Hz) are marked wtth sohd symbols
calculated macrocell currents levels are also consistent with experimental observalons in compa-
rable systems [5,6] and with model calculaUons using a fimte element techmque m a system
with similar geometry [8]
The slmphfymg assumption of zero Tafel slope for the anodlc reaction was done m the
manner of Ref8 This s~mphficat~on ~s not expected to introduce unrepresentative results, since
cathodic control should be predominant because of the large cathodic activation slope combined
with the approach to dlffUSlOnal control near the anode The fimte difference model is neverthe-
less able to handle a polarizable anode and implementation of that feature is planned in future
work. The dlffUston problem treatment as a radial problem is a considerable slmphficatlon
subject to future ~mprovement However, increased modehng soph~stlcatlon at th~s ume may not
be advantageous until better measurements of diffusion coefficients of oxygen are available

[2,3,19]
The calculations showed that cathodic current densmes approached the limiting current den-
sity (typically within 90%) over the entire bar surface in all the cases tested That explains the
relatively small change in macrocell current when the anode size was vaned from 2 to 10 mm
(Fig 3 ) while keeping the diffusion coefficient the same The external potential reading over the
anode shows greater sensitivity to the anode size, possibly responding to the presence of a larger
effective dipole size as the anode becomes larger
Alternatmg Current Calculaoons

The model used in the a-c calculations is only an approximation to the complicated conditions
encountered in actual systems Computation of dlffUsional impedance behavior, which was
adapted from a one-dimensional case, could be further refined The results, nevertheless, pro-
vide insight on the accuracy ofpolanzat~on methods currently used to evaluate corrosion rates of
reinforcing steel in concrete In a discrete system where both cathode and anode are equally
exposed to the excitation signal, the overall impedance is given by the parallel combination of a
cathodic impedance (Eq 6) with an anodic impedance (Eq 8 ) and an interfacial capacitance
The effective resistance of the electrolyte acts in series with that combination Under those
condmons, the high frequency impedance response of the system dehneates a semicircle m the
Nyquist dmgram, with a dmmeter (which will be designated Raw ) given by [ 16-18]
R.pp = babel2 3 Ir b~ + be) (17)
where Icon is the value of the corrosion current [10].

The low-frequency response deviates from an ideal semicircle because of the presence of the
dlffUslonal term in Eq 6 Instead, a low frequency tail develops on the right side of the semicircle
At very low frequencies this tall converges toward the real axis at a value Rff given by [ 10,20]
Rp'= bJ 2 3Ir (18)
Equation 17 or 18 has been used in attempts to evaluate corrosion currents using the results of
polanzation measurements of reinforced concrete systems where a-c signal dlstnbution to cath-
ode and anode is markedly uneven (such as the cases studied here) Values ofba and bc are either
known from previous tests or estimated empirically [ 21 ] The validity of using equations based
on even excitation dlstnbution assumptions will be examined based on the result of the present
calculations The following discussion concerns estimation of the total corrosion current and not
current denslues
As shown in the diagrams in Fig 4, there is no low-frequency convergence to the real axis in
any of the cases calculated, even with frequencies down to 10 -4 Hz This is also a common
experimental observation [10,22,23] As a result, Eq 17 is the equation frequently used for
corrosion current determination, and its application was examined here The calculated imped-
ance response was treated as if it were the result of an experiment As is commonly done, Rapp
was equated to the approximate diameter of the roughly semicircular feature of each diagram A
value of I~o,~was then calculated using Eq 17, and the validity of the result was evaluated by
companng with the value obtained in the d-c model Table 2 lists the results of those calcula-
tions, showing that the corrosion current was consistently underestimated by a s~gnificant
amount Some of the factors responsible for these results are discussed below
A striking feature of the calculated diagrams (and many experimental observations in compa-
rable reinforced concrete system geometries) is the presence of a conspicuous diffusional tail
TABLE 2 ~ N o m m a l corroston current estimates
Anode Size
Magmtude 2 mm 6 mm 10 mm
R=pppos 1 (fl) 910 820 800
Rapppos 2 (fl) 700 600 600
R=pppos 3 (fl) 560 500 500
I~o,~esumated (~.A)
pos 1 21 23 24
pos 2 27 32 32
pos 3 34 38 38
leo,, actual (#A) (from mmal d-c values) 57 68 70
This is not expected from analysis of a discrete electrode, since at low frequencies the anodlc
admittance should become dominant, especially consldenng the relative values of the Tafel
constants used here (ba = 60 mV versus bc = 160 mV) Figure 5 dlustrates this concept Curve A
is the same shown m Fig 2 (center), corresponding to the calculations for a reference electrode
posmoned near the anode, on the outer surface of the cyhnder Curve B m Fig 5 is the ~mped-
ance response of the bar under the same d-c polarization condmons as for Curve A, but assuming
that all points of the bar are exposed to a uniform a-c polarization potential (in other words, as if
the alternating current distribution were not hmlted by the electrolyte and the bar would behave
as a discrete electrode) The impedance for Curve B is, m that case, given simply by the reverse
of the integrated admittance of the bar surface, calculated by directly summing the same mdwld-
ual element admittances used for calculating Curve A (the high frequency impedance limit for
Curve B is zero, for comparison purposes the curve was shifted to the right and superimposed on
Curve A) Curve C was calculated m the same manner as Curve A, but equating to zero the
second term on the right-hand side of Eq 6, that is, assuming that the dlffUSlOnalcontribution to
the impedance of the cathodic reaction is negligible
The difference between Curves C and A m Fig 5 confirms that the tad to the right of Curve A
500 ' f I
A
Ia = 6 m m
E
t-
O
0 I ' I ' I ~ '
0 500 1,000 1,500
Z' (ohms)
FIG 5--Curve A hnpedance dtagram for lest point 1, 6 mm anode case Curve B Impedance diagram for the
6 mm anode case but without mcludmg the effect o f electrolyte reststtwty tn the a-c calculatton (This curve has
been moved to the right to facdztate comparison wtth A and C ) Curve C Impedance dtagram for test potnt 1, 6
mm anode case but wtthout mcludmg the dlffustonal tmpedance term tn Eq 6
is due to the dlffUSlOnal component of the impedance and not to a transmlsslon-hne effect
[24-28] Companson between Curves A and B shows that while Curve B shows a small dlffU-
slonal tall, that feature is much more conspicuous m Curve A Curve B shows also a much
smaller value ofRapp ( ~ 2 9 0 fl) than for Curve A The corresponding value of I~o~ for Curve B
(66 #A) is m excellent agreement with the d-c corrosion current value for the case considered
(see Table 2)
The exaggerated Rapp values and dlffUSlOnal impedance presence exemphfied in Curve A
result from the uneven character of the a-c current &stnbut~on These uneven distribution
effects are due partly to the asymmetnc placement of the counter electrode, but more impor-
tantly to the difference in size between the cathodic and anodlc regions As indicated by Oltra
and Keddam [29] the constricted current flow to a small ano&c region results m an effectwe
electrolyte resistance that is significantly higher than that encountered by a larger electrode
(such as the cathode) As a result, the anode expenences a lesser level ofa-c excitation, com-
pared with what would be received if the electrolyte paths were the same, as m the case of a
discrete electrode An indication of the current dlstnbutlon between anode and cathode can be
obtained by defining a partmon function, Pf, such as
Pf= i./i, (19)

where I~ is the magnitude (length of the complex vector) of the total alternating current flowing
to the anode, and I t is the magnitude of the alternating current flowing to the entire bar surface
If both cathode and anode were exposed to the same excitation potential as in Curve B, (Fig 5),
then at the intermediate frequency limit (the condition used to determine Rapp) the partition
function would have a value close to bc/(br + ba) = 0 727 Because of the current constriction
effect mentioned earlier, the partition function has smaller values when the actual specimen
configuration is used This is demonstrated in Fig 6, where Pfhas been calculated as a function
of frequency for the different anode sizes investigated The results show that Pf at the frequen-
cies of interest to determine Rapp (around l0 -3 Hz) is slgmficantly less than 0 727, and becomes
smaller as the anode size decreases This indicates as expected that the cathode contribution to
the overall impedance response of the cathode becomes emphasized The effect is stronger when
the anode is smaller As a result, the overall impedance magnitude becomes greater and the
dlffUSlOnal component (which is contributed only by the cathode) becomes more conspicuous
Errors from these sources in the estimated value of I~o~by the unqualified use ofEq 6 can then be
expected when the anode size is significantly smaller than that of the cathode This is confirmed
by the results shown in Table 2 Note, however, that since the smallest anode sizes resulted in
smaller corrosion currents, the corresponding cathodic current densities were not very close to
the limiting value As a result, decreasing the anode size did not make the dlffUSlOnalcomponent
of the Impedance more noticeable within the series of examples chosen here
Figure 6 also shows the partition function for a case similar to the base case but with a counter
electrode extending over the entire cylinder length There is relatively little difference with the
low-frequency value of Pf in the base case This is to be expected since at low frequenoes the
lnterfaclal impedance of the cathode is large compared with the characteristic resistance of the
cylinder Under those conditions the main factor determining current distribution to the anode
is the current constriction around the anode, which is similar in both cases It should be noted
that at very low frequencies the catho&c impedance may become so great (see Eq 6) that the
anode behavior could become dominant again This is manifested by the upturn in Pf at the low
frequency end in Fig 6 However, that upturn is not conspicuous at the test frequencies of
interest
At the high frequency hmlt the partition function should become simply the area ratio of
anode to cathode, if the counter electrode covers the entire cylinder [29] This is confirmed in
1 I t I I I t
.b-7-2-7-- r:-L.................................................................................
........
It"- "..~
g
.... 10ram
00,0 ,
0.01 "'...
"'...
2mm
0.001 I I I I I I
0.0001 0.001 0.01 0.1 1 10
FREQUENCY (Hz)
FIG. 6--Par/i/ion function (P r) as a function offrequency for anode sizes o f 2, 6, and 10 ram, using the 100
mm counter electrode placed at one end o f the cylinder. A n additional curve ( * ) shows the case o f the 6 mm anode
but using a full-length counter electrode.
Fig. 6 (full counter electrode curve 1-6 mm anode) showing that ef converges to 0.02 at high
frequencies. For the partial counter electrode the limit value is less but consistently follows the
expected trend.
The reference electrode placement affected to some extent both the magnitude of the evalu-
ated corrosion current and the appearance of the impedance diagram. These variations may be
used to obtain information useful in deconvoluting the impedance response and eventually
achieving a better estimate of the corrosion current. Application of this concept to simplified
system configurations (such as slender beams or fiat slabs) has been presented in the literature
[ 2 2 , 2 4 - 2 8 ] . The calculations presented here are a prerequisite for implementation of similar
schemes in a system with less idealized dimensions.
The relatively squat geometry of the system examined here prevented the development of
appreciable dispersion of the high frequency EIS response by transmission-line effects [22]. In
addition, the capacitive component of the impedance was modeled by a simple frequency inde-
pendent capacitance. As a result, the calculated diagrams tend to have a high frequency intercept
with the real axis at an angle close to 90 ~ The use of a larger interfacial capacity value in the
model could have resulted in more noticeable transmission-line effects [22,24].
The region of negatwe real impedance m the dmgrams obtained for the reference posmon
furthest away from the counter electrode Is noteworthy This effect is a consequence of the a-c
phase shift between the overall current through the bar and the potential at a point remote from
the exotatlon posmon Slmdar behavior has been predicted and observed m studies of the EIS
response of a crevice configuratton [30] Observation ofthts effect m actual concrete beams may
be difficult, since there is evidence of considerable dispersion of the capacmve component of the
impedance, possibly as a result of steel surface roughness or electrolyte mhomogenelty [31]
Conclusions
A fimte difference model can be used to successfully calculate the d-c polarization problem m
a reinforced concrete cyhnder with fimte dimensions, incorporating highly non-hnear boundary
condlttons The system incorporated a small anode and a large cathode
The d-c polanzatlon condmons were used to estabhsh a-c elemental impedances along the
reinforcement surface An eqmvalent orcmt grid was then used to calculate the overall imped-
ance response of the system The d-c polanzatlon behavior was such that the hmmng current
density for oxygen reduction was approached m the porUon of the reinforcement closest to the
central anodlc region This resulted m the presence of a slgmficant dlffuslonal term m the
cathodic impedance
Because of the small size of the anode relaUve to the cathode, the amount ofexotatlon current
flowing through the anode was less than m the case of a discrete, uniform electrode As a result,
the anodlC contribution to the overall ~mpedance response was reduced, whde the effect of the
cathode was magmfied
The calculations showed that due to the uneven a-c signal distribution, tmpedance measure-
ments of the system could lead to underestimating the extent of the corrosion current ff com-
monly used conversion formulas were uncnucally apphed The alternating current distribution
effects also lead to emphas~s of d~ffUSlOnalimpedance features m the measured response of the
system
The impedance response was dependent on the posmon of the reference electrode The calcu-
lations suggested the posslbdlty of a small region of negattve real tmpedance component when
the reference electrode is placed far away from the exotaUon point
Acknowledgments
This work was partially supported by the Honda Department of Transportation (FDOT) and
the Engmeenng Computing Services of the Umverslty of South Honda (USF) The opinions,
findings, and conclusions expressed herela are those of the authors and not necessanly those of
FDOT or USF
References
[1] Slater, 3 , Corrosion of Metals m Associanon with Concrete, ASTM STP 8t8, Amencan Society for
Testing and Materials, Phdadelphla, 1983
[2 ] Tuuttl. K, Corrosion of Steel in Concrete, Swedish Cement and Concrete Research Institute, 1982
[3] Gjorv, O, Vennesland, O, and EI-Busaldy,A, Materials Performance, Vol 25, No 12, 1986, p 39
[4] Maklta, M, Morl, Y, and Katawakl, K, "Manne Corrosion Behaviorof ReinforcedConcrete Exposed
at Tokyo Bay," in ACI Pubhcatton SP-65, Performance of Concrete in Marine Envtronments, V Malho-
tra, Ed, American Concrete lnstttute, Detroit, 1980, p 271
[5] Agudar, A, Sagues, A, and Powers, R, "Corrosion Measurements of Reinforcing Steel m ParUally
Submerged Concrete Slabs," m Corroswn Rates of Steel in Concrete. ASTM STP 1065, N Berke, Ed,
American Society for Testing and Materials, Phdadelphta, 1990
[6] Sagues, A , Electrochemical Impedance of Corrosion Macrocells on Reinforcing Steel m Concrete,

Paper No 132. Corrosion/90, NaUonal AssoclaUon of Corrosion Engineers, Houston, Tex, 1990
[7] Rendell, F and Miller, W, "Macrocell Corrosion of Reinforcement m Manne Structures," m Corro-
sion of Reinforcement m Concrete, C Page, K Treadway, and P Bamforth. Eds, Elsevier Apphed
Science, London-New York, 1990, pp 167-177
[8] Nalsh, C, Harker, A , and Carney, R , "Concrete Inspection Interpretation of Potential and Reslstw-
lty Measurements." in Corroswn of Reinforcement m Concrete. C Page, K Treadway, and P Bamforth,
Eds. Elsevier Apphed Science, London-New York, 1990. p 314
[9] Elsener. B and Bohm, H, "Potential Mappmg and Corrosion of Steel In Concrete". m Corrosion Rates
of Steel m Concrete, ASTMSTP 1065, N Berke. V Chaker, and D Whiting, Eds, American Society for
Testing and Materials, Phdadelphla, 1990, p 143
[10] Sagues, A , "Critical Issues in Electrochemical Corrosion Measurement Techmques for Steel m Con-
crete," Paper No 141. Corrosion/91, National Assocmtlon of Corrosion Engineers, NACE, Houston,
Tex, 1991
[11] Sagues, A . to be pubhshed
[12] Fabian, C , Kazemt, M, and Neckel, A , Bet Bunsenges Phys Chem. Vol 84. 1980, p 1026
[13] Sagues, A . Perez-Duran, H. and Powers, R, Update Corroswn. Vol 47, 1991, p 884
[14] Kaesche, H, Metalhc Corrosion, NACE, Houston. Tex. 1985
[15] Mdlard, S G , GhassemL M, Bungey, J . and Jafar, M. "Assessing the Electrical Reslstwlty of Con-
crete Structures for Corrosion Durability Stu&es," m Corrosion of Reinforcement m Concrete. C Page,
K Treadway, and P Bamforth, Eds, Elsevier Applied Science. London-New York, 1990. p 303
[ 16 ] Haruyama, S, "Faradlc Impedance of Mixed Potentml Electrode," m Proceedings. Fifth International
Congress on Metalhc Corrosion, National Association of Corrosion Engmeers, Houston, 1974, p 82
[ 17] Tsuru, T . "Treatment of Diffusion Impedance in AC Impedance Method," 61 st Japan Soc Corr Eng
Symposium Report, 1985, pp 97-106
[18] Sagues, A A , Corrosion. Vol 44, 1988, p 555
[19] Morehead, W , "Diffusion of Dissolved Oxygen through Concrete (Discussion)," Materials Perfor-
mance. Vol 26, No 5. 1987, p 34
[20] Epelboln, 1, Gabnelly, C, Keddam. M, and Takenoutl. H , "AC Impedance Apphed to Corrosion
Studies," in Electrochemwal Corrosion Testmg, ASTM STP 727. F Mansfeld and U BertoccL Eds,
Amencan Society for Testing and Materials, Phdadelphla, 198 I, p 150
[21] Andrade, C and Gonzalez, J , Werkstoffe und Korroswn. Vol 29, 1978. p 515
[22] Macdonald, D, Urqm&-Macdonald, M, Rocha-Fdho, R . and EI-Tantawy, Y, Update Corrosion.
Vol 47, 1991, p 330
[23] Thompson. N, Lawson, K. and Beavers, J , Corrosion. Vol 44, 1988, p 581
[24] Macdonald, D . McKubre, M, and Urqm&-Macdonald, M, Corroswn, Vol 44. 1988, p 2
[25] Fehu, S, Gonzalez. J , Andrade, C, and Fehu, V, Materials and Structures. Vol 22, 1989, p 199
[26] Fehu, S, Gonzalez, J , Andrade, C . and Fehu, V, Corroswn Soence, Vol 29, 1989, p 105
[27] Fehu, S, Gonzalez, J . Andrade, C, and Fehu, V, Corroswn, Vol 44, 1988, p 761
[28] Fehu, S, Gonzalez, J , Andrade, C, and Rz-Manbona, I, "Errors Introduced by the Guard Ring
Device m the On-Site Measurement of Rebar Corrosion Rates," tn Corrosion of Reinforcement m
Concrete, C Page. K Treadway and P Bamforth, Eds. Elsewer Apphed Science, London-New York,
1990, p 293
[29] Oltra. R and Keddam, M, Corrosion Science. Vol 28, 1988, p 1
[30] Fraud, C, Keddam. M, Kadn, A , and Takenoutl, H, Electroehtrmca Acta. Vol 32, 1987, p 445
[31] DeLevle, R , ElectrochtmwaActa. Vol 9, 1964, p 1231
DISCUSSION
B Borgard I ( written dlscusston)--How do you see the application o f your techmque working
on real structures with real concrete w~th multiple rebars and unusual geometnes9
S C Kranc andA A Sagues (authors'closure)--At present the d-c techmques are being used
ChemLmk Industrial, Houston, TX 77084

to solve the coupled diffusion-potential problem in slmphfied reinforced concrete cyhndncal

columns with an embedded rebar cage, allowing for vanable resistivity and oxygen dlffuslvlty
The a-c solution is less restricted, since equivalent circuit equations for complex shapes can m
pnnc~ple always be formulated and solved using matnx methods
E Pye 2 (wruten dlscussmn)--Assume that the system you descnbed is extrapolated to pro-
wde many more anode/cathode sites--each smaller m size but larger m number--over the same
dimensions you described Would you expect the same results as you have outhned9
S C Kranc andA A Sagues (authors" elosure)--Ifthe anodlc and cathodic sites were many
more m number (but keeping constant the total anodlc ] cathodic area ratio), one would expect
the partition function to approach more closely the value bc](bc + b,) in the intermediate
frequency regime, since macroscopic current constnct~on would be less pronounced
U Bertoeet 3 (wrttten dlscusslon)--The data presented were obtained for an arbltranly chosen
ratio between anodlc and cathodic areas Since it is not obvious how to select this input quantity,
it would be interesting to know If the results depend sensitively on this ratio
S C Kranc and A A Sagues (authors" closure)--See our response to E Pye above
R A Coltm 4 (wrttten dlscusslon)--Would you expect your model to be able to indicate the
apphcabdlty of guard-nng techmques to the momtonng of corrosion in concrete~
S C Kranc and A A Sagues (authors" closure)--The model is well suited to calculate the
fraction of excitation current prowded by d~fferent portions of a split counter electrode, thus
evaluating the performance of possible guard-rang configurations Work is currently in progress
along those lines
2 Cahfornla State Polytechmc University, Pomona, CA 91768

3 Nauonal Institute for Standards and Technology, Galthersburg, MD 20899
4 UMIST, Corrosion & Protecuon Centre, P O Box 88, Manchester, England M60 IQD
K. R. Trethewey I a n d J. S. Keenan 1
Microcomputer-Based Corrosion Modeling

Applied to Polarization Curves
REFERENCE: Trethewey, K R and Keenan, J S, "Microcomputer-Based Corrosion Model-
ing Applied to Polarization Curves," Computer Modehng zn Corrosion, ASTM STP t t54. R S
Munn, Ed, American Sooety for Testing and Materials, Phdadelphta, 1992, pp 113-125
ABSTRACT: A microcomputer-based software package is described that successfully models

polarization curves and simulates redox behawor of a wide variety of electrochemical reacnons It
also enables experimentallyobtained polanzauon scans to be plotted over the computed scans for
companson The paper definesan electrochemicalmodel using estabhshed theoretical foundations
and descnbes the means of achievinggood computer representationsof laboratory data A descrip-
tion Is gwen of the model, some of the apphcauons to analysis of corrosion mechanisms, and
aspects of its use in corrosion control Apphcatlons discussed include the effect of electrolyte
dduaon for the purposesof scale modehng, and the introduction of paint films Use of the model to
invesngate passivatmg systems by the simulation of the electrochemical corrosion behavior of
stainless steels ~s described By rapid mvestigaUonof changes m a large number of system and
environmental parameters, the value of the model for corrosion education and as a research tool for
advancing the theoretical foundations of corrosion wdl be demonstrated
KEY WORDS: corrosion, computer model, electrochemistry,slmulauon, m~crocomputer,polar-

lzauon curves
Electrochemical analysis is a powerful tool in the investigation and comprehension of corro-

sion mechanisms This usually takes the form of polatazatlon, or E/log t, curves in which the net
current density passing between two electrodes is plotted agamst potential measured against an
arbitrary reference electrode The value of such curves stems from the successful combination m
the same diagram of both thermodynamic and kinetic characteristics of systems
The basis of the theory is well estabhshed [ 1] A system may consist of a competing number of
pairs of oxidation and reduction reactions (hereafter referred to as redox processes) The ob-
served behavior is the sum of the various processes over the range of potentials ofmterest Often,
only some of the processes predominate at any given potential, whdst others are negligible
However, the potential domain, together with other environmental parameters, may combine to
produce circumstances m which those processes become significant and considerably alter the
corrosion behavior of the system
Until recently, the analysts of polarization curves has been possible either by laborious calcu-
lauon, simphsttc approxtmaUon, or by quahtatwe representation of the processes by means of
schematic diagrams Some computer programs to calculate polarization curves have been writ-
ten for mamframe, but, because of thzs, have been hmited in their commeroal avadabdity
Often, the programs have considered only one redox process or have assumed such constraining
conditions as to give poor apphcabdity to other systems Several groups have reported the
advanced analysts of laboratory-determined polatTzation scans [ 2-6 ] Other workers have re-
ported the development of software for educational purposes [7] One previous method of
i Royal Naval Engmeenng College, Manadon, Plymouth PL5 3AQ, Umted Kingdom
113
Copyright9 1992 by ASTM International www.astm.org
modeling polanzatton curves was reported [8] to be successful for nickel in molten sodium
carbonate at 1000~
The advent of the microcomputer has brought the low-cost capability of efficiently carrying
out complex calculations and displaying the modeled corrosion behavior in attractive screen and
hardcopy displays, greatly assisting the analysis and understanding of complex lnteractmns
Such a tool makes possible the modehng of polanzation curves and the evaluation of electro-
chemical parameters which may be difficult to obtain by other means The need for a multi-
purpose electrochemical model able to examine a wide range of systems can now be satisfied
This work describes such a model, previously written for mainframe [ 9] and now available in a
much more general form for IBM-compatible microcomputers
Defining the Model

The electrochemical theory of corrosion and other associated reactions is descnbed in stan-
dard texts [ 10,11 ] An excellent source of thermodynamic data is also available [12]
For the purposes of modeling E / l o g t plots, a satisfactory descnptlon is obtained using an
expression for the polanzation of an electrode as the sum of contnbutions from activation
polanzation, diffusion polarization, and resistance polanzation Thus
~total = ~acttvat,on "~ ~d,ffu . . . . -[- 7/........ ( 1)
in which the three terms can be written
,to~, - a z F - - ~ - In 1 - + z(Re + Rf) (2)
where
=polanzation,
R = 8 3143 J K -l mol -I,
T = absolute temperature,
z = n u m b e r of electrons transferred,
t = current density,
to = exchange current density,
tL = limiting current density,
a = transfer coefficient,
Re = resistance of the electrolyte, and
Rf = resistance of the film
The modehng of a redox process requires the initial defimtion of
( a ) Redox equations for the process

(b) Standard electrode potential, E ~
(c) Exchange ( e q u i h b n u m ) current density, lo
The electrode potential, E, is obtained from standard redox electrode potentials, E ~ by

means of the Nernst equatton, and is dependent upon species concentration or, more accurately,
the activity, at the electrode The exchange current density is rather more difficult to quantify
Many measurements have been made of values for a large n u m b e r of processes, but values are
considerably dependent upon environmental condmons A n example is the value of exchange
current density for the process
TRETHEWEY AND KEENAN ON POLARIZATION CURVES 115
H++e-~H (3)
which is strongly dependent upon the electrode surface upon which it occurs Thus, for example,
on platinum in hydrochloric acid it is reported to have the value of 10 -2 A / m 2, whilst on
mercury in aqueous barium hydroxide it is 10 -26 A / m 2 [ 13]
In order to model more general conditions found in corrosion systems xt xs necessary to specify
the following environmental parameters
(d) Temperature
(e) pH
(f) Oxygen concentration
(g) Electrolyte composition
(h) Electrolyte velocity
In the first instance, using requirements ( a ) , (b), and (c) above, it is a simple matter to
calculate polarization curves on the basis of a single redox process, using only temperature as an
additional parameter since it occurs explicitly in the equations In all but the most constrained of
experiments, this does not give a good representation of the general case because of the exclusion
of other parameters Thus values for pH and oxygen concentraUon must usually be Included
because of the involvement of two other common redox processes m aqueous systems, namely
the hydrogen reaction (Eq 3) and the oxygen reaction,
02 + 2H20 + 4 e - ~ 4 O H - (4)
Thms inclusion alone increases the number of redox processes to three and since two curves are
computed for each process, that is, one oxidation and one reduction component, then the total
number of curves is six The summation of the six curves produces a seventh curve representing
the modeled polarization curve for the system
The value of the microcomputer in speedy calculation and summing of curves is now clear, as
well as being a powerful means of assessing the contributions made by each individual oxidation
or reduction reaction and the Influence of a small change in an environmental parameter In
pnnclple, there is no limit to the number of such processes which could be considered
Electrolyte composition is of obvious importance because it determines the conductivity of
the electrolyte and makes a contribution to the resistance polarization In some cases, the elec-
trolyte actively participates in the corrosion system The presence of chloride ion, for example,
considerably influences the corrosion of copper Alternatively, the effect of adding an inhibiting
species to the electrolyte can easily be investigated if the thermodynamic parameters are known
Thus it may be desirable to include further redox reactions In the model
An additional complication is the resistance across the metal/electrolyte interface This may
be caused by the presence of a poorly conducting film which may itself result from the formation
of a corrosion product, oxidation of the metal, or the deliberate application of a surface coating
by way of corrosion protection When this resistance term is sufficiently large, experimental
difficulties with d-c measurements introduce the need for application of impedance techniques
which are outside the scope of this paper However, for the purposes ofmodehng, the contribu-
tion of the resistance polarization term to the model is straightforward, except where it is caused
by time-dependent phenomena
The effect of electrolyte velocity on corrosion systems is very complicated if an accurate model
of the hydrodynamic parameters is needed [ 14 ] and considerations of system geometry become
crucial However, a simple approach often provides acceptable results, especially Ifa quahtatwe
description is sufficient In the s~mplest sense, the flow of electrolyte can be considered as
__AA
.5
--~
- i .5
-2
-3 -2 -i 0 i 2 3 4 5 6 7 8 9
LOG [CURRENT DENSITY (nA/cm^2) ]
FIG. l--Modeled polarization curvesfor Fe ~ Fe 2+ + 2 e - (Curves I a n d 2 ) , H ~- H + + e - (Curves 3 and
4) and 02 + 2H20 + 4 e - ~- 4 0 H - (Curves 5 and 6); overall E/Iog i modeled plot represented by Curve 7. Free
corrosion potential = - 0 . 6 3 V SCE.
providing enhanced transport of the species involved in the redox processes. This transport
would otherwise be limited by the concentration of the species, the appropriate diffusion con-
stants, and the transport coefficients where ions are involved. Shrier [ 15 ] gives a relationship for
limiting current density ( A / m 2) as
DzFc
iL- • 10 -3 (5)
d( 1 - n+)
where z is the number of electrons required for one step of the process involving 1 mol of the
cathode reactant, D is the diffusion coefficient, c is the concentration of reactant (mol / dm 3), d is
the thickness of the diffusion layer (cm), and n+ is the transport number of the cation.
General Requirements of a Computer Model

A DOS-based IBM-PC or compatible system was selected as the computer with which to
design a versatile and comprehensive software package for the modeling of polarization curves.
The language was Microsoft Fortran which, although excellent for numerical calculations (and
does not require a math co-processor), normally does not support modern color screen graphics
or mouse input. This was overcome by means of a commercially available software package
which provided all the library subroutines necessary to produce modern software effects and
mouse support.
0
P
0
T -.2"
E
N -.4"
T
I -.6
A
L -.8"
S - i .2
C _...._--2
E -i.4
- i .6
- i .B
| 1 I I I I I
0 ~ 2 3 4 5 6 7 8
LOG [CURRENT DENSITY (nA/cm^2] ]
FIG 2--Modeled polartzatton curves for zinc (Curves 1 and 2) m 0 5 M NaCI, plus HCI to pH 3, 35
solutton reststance, wtth hydrogen (Curves 3 and 4) and oxygen (Curve 5) processes mctuded, overall E/tog r
plot represented by Curve 6
The requtrement to compare modeled curves with those obtained by expenment introduced
the need to interface the software w~th laboratory hardware, and then to provide output m a
flexible format using overlays of modeled and expenmental curves The mare program was
therefore spilt into two pnnclpal tasks model and hbrary The aim of the model was to generate
by calculauon polanzauon curves for a wide range of multtple redox processes All curves
contributing to the overall curve were to be shown and saved to disk The aim of the hbrary
mode was to recall from hard or floppy disk any polarization curve, whether generated by the
model or recorded by expenment, and display on screen or output to hardcopy m a flexible
format
The Modeling Process

The first goal m the modehng task is to ldenUfy and classify the processes that must be
modeled, and considerable reference to the work of Pourbalx [ 12] was made This behavior is
represented m the software by means of a framework in which the user assembles his own
database using a generahzed form of the Nernst equation
E = E ~ + q [const • p A C T ] + t [const • pH] (6)

r
where E ~ is the standard reduction potential, E Is the non-eqmhbnum potential, const

0
P
0
T -.2
E
N -.4
T
I -.6
A
L -.8
V -t
S -i .2
C
E -t .4 - model
expt "~"
-t .6"
-t .8"
0 t 2 3 4 5 6 7 8
LOG [CURRENT DENSITY {nA/cm^2} ]
FIG 3--Expertmental curve compared wtth the modeled curve (Curve 6) of Fig 2
-0.34,
E (V SCE)
-0,36
-0.30
-0.4 -
-0.42 -
-0.4,4-
-0.46 3 7
-0.48
-0.~
-0.52 0 m/s
-0.54.
-0.56
-0.58
-0.6 ~ s
2 4, 6
Ig I ( n A / c m 2)
FIG 4--E~pertmenlal polarization curves for mtld steel ll'l sea water of dtfferent veloctttes using a rotating
cyhnder electrode
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement.
-0.34.
E ( V SCE)
-0.38
-0.38
-0.4. -
-0.42 -'I
-0.4-r
-0.4.6
-O.t8
,.6 mh
-0.0
-0.52
-O.St
-0.56
-0.58
-0.5 I I l i i
2 '~ 6
Ig i (nA/cm 2)
F|G. 5--Modeled polarizadon curvesfor the experiments in Fig. 4.
= 2 . 3 0 3 R T / F , and pACT is a term used to represent log~0 [activityio,]. The symbols q, r, s, and
t are integers derived from the chemical equation. All parameters for the calculations are con-
tained in an appropriate data file which is totally user-variable.
The user begins by identifying a reaction of interest and creates an appropriate entry in a data
file. Thus, for example, the simple corrosion reaction for iron is written in its reduction sense as
Fe 2+ + 2e- --~ Fe (7)
The Nernst equation is written as
2.303RT,
E = E~ + ~ Jog [actFe2+] (8)
where the values of q and r are 1 and 2 respectively, and s is 0.

Figure 1 illustrates the modeled E/log i curves, both for each component of the system
(Curves 1 to 6) and for the overall process (Curve 7). The graph has considerable educational
value, showing how a laboratory polarization scan is made up from its component parts. The
sequence is easy to create, and parameters can be altered at will. The well-known dependence of
the corrosion of iron on oxygen is apparent from the curves: the concentration of oxygen can be
varied and its considerable influence on the shape of the polarization curve and on E~,~ and i~o~
can be shown. With a little practice the model can be made to illustrate quite accurately a
genuine polarization scan and an attempt made to evaluate parameter values.
Figure 2 shows a modeled polarization scan, together with its component curves, for zinc in
0.5 M NaCI, with HCI added to bring the solution to pH 3. Figure 3 is a comparison of the
0
P
O
T -.t
E
N -.2
T
I -.3
k
L -,4
V -.5=
S -~
C
E -.7
--.8-
n~
0 t 2 3 4 5 6 7 8 9
LOG [CURRENT DENSITY (nA/cm'2) ]
FIG 6--Modeled polartzanon curves showmg the effect o f electrolyte dilution on mild steel in sea water
Curve 1 oxygen reduction process, Curve 2 iron anodtc process m dduted ( 1 / 6 0 ) sea water, Curve 3 polariza-
tion curve resultmg from 1 and 2, Curve 4 iron anodtc process for undduted sea water, Curve 5 polarization
curve resuhmg from 1 and 4
modeled and expenmental curves The modeled curve was prepared in 2 h spent on an IBM PS2
microcomputer, less than the ume taken to obtain the laboratory scan
An early attempt [ 14] to model curves for steel in sea water of &fferent velocities gave the
results shown in F~gs 4 and 5 In the former, the expenmental curves are shown for three
velootles, whilst m the latter the modeled curves are presented Although further improvements
can be made to the modeled curves, they clearly demonstrate the positive shift of free corrosion
potential with increasing velocity, a shift which &mmlshes as the velocity increases A small
increase in the corrosion rate is also apparent in parallel with the increase m oxygen
concentration
In an analysis [ 16 ] of polarization of ship hull matenals and the effect of ddutlon of sea water
as a method for modeling impressed current cathodic protection systems [ 17], the modeled
polarization curves for &luted and natural sea waters were found to compare favorably with
expenmental parameters Introduction of the correct values for the two solution resistances, Re,
gave curves which showed how a posltlve shift in free corrosion potential would be expected
(Fig 6) The effect of dilution on corrosion rate was comparatively small because o f a neghglble
reduction in the diffusion polanzatlon term for oxygen, the controlling factor in the mechamsm
The introduction of a paint film on a steel coupon was also modeled successfully, even though
it is normal to use Impedance techmques Experiment showed that corrosion rate was reduced by
a factor of 100 when paint was applied, whilst the free corrosion potential was hardly affected
The model demonstrated how, with the inclusion of a suitably large value o f R f a n d a reduced
0
P
0
T -.1-
E
N
T
I
A
-.2
-.3
'I/ 1
L
V
-.4
-.5-
i/
S -.6" 2
C
E -.7"
i i i l I I i -
(1 ! 2 3 4 5 6 7 8 9
LOG [CURRENT DENSITY ( n A / c m ' 2 ) ]
FIG. 7--Modeled polarization curves showing the effect of application of a paint film to mild steel in sea
water. Curve 1: oxygen reduction process for bare steel; Curve 2: iron anodic process for bare steel," Curve 3:
polarization curve resulting from 1 and 2; Curve 4: oxygen reduction process for painted steel; Curve 5: iron
anodic process for painted steel; Curve 6: polarization curve resulting from 4 and 5.
transport of oxygen through the film, the observed effects on the polarization curves were ob-
tained ( Fig. 7).
Passivating Effects
The presence or absence of a passivating film in a corrosion system is crucial to the shape of
the polarization curve. In the simplest case, the passive film introduces a significant value for Rf
in the resistance polarization term and leads to lower current densities than would be expected in
the absence of the film. When the film becomes sufficiently protective, an actual reduction in
current density is observed. Classic examples of this behavior are the redox processes of stainless
steels in oxidizing environments which give rise to the well-known S curves. When the control-
ling influence of a reduction process is added to the system the electrochemistry can undergo a
number of changes corresponding to stable and unstable situations in which alternate anodic
and cathodic excursions are observed.
Hines [5] has described a successful mainframe method for modeling such behavior. The
principle involved is a familiar chemical kinetic approach for two competing reactions. The
concept of scanning through different potential domains leads to the idea that the reactions
compete to differing degrees as the free energy profiles change shape and differing proportions of
the active and passive reactions occur. Hines' model for such behavior is an equation of the form
P
0
T t.5
2t
E
N
T ,1
I
A .5-
L
O"
--~
-l"
-I .5"
-2 '1 I I " 'r = i
-3 -2 -~ 0 ~ 2 3 4 5 6 7 8 9
LOS [CURRENT DENSITY (nA/cm*2) ]
FIG. 8--Modeled polarization curve for a passivating nwtat showing single E ~ . Curve 1: modeled S curve;
Curve 2: oxygen process; Curve 3." polarization curve resuhing from 1 and 2.
i, = Si~r ~ + ( 1 - S ) i r , ~ i ~ (9)
where
S= exp[-A,v(E-Eav) e] (10)
A similar approach adopted independently by this laboratory [ 18] has also yielded successful
results. Curve l in Fig. 8 shows a typical S curve in which all the usual electrochemical parame-
ters have been user-determined. The microcomputer model then allows the addition o f a redox
process for oxygen, say, and examines the interaction with the S curve. Figures 8 and 9 show two
such effects leading 1~othe familiar stable and unstable conditions for the stainless steel.
Final Remarks
A number of problems are associated with the modeling of polarization curves because the
experimental determination of reproducible polarization curves for a given system is difficult. A
considerable number of experimental parameters must remain unaltered between scans; changes
in the composition of both electrolyte and metal can occur during the course of the scan.
Dissolved oxygen may be consumed, pH may change, amounts of metal ions in solution may
alter as corrosion proceeds. Thus values of parameters probably change during an experiment.
This is particularly true of the development and breakdown of passive films: uniformity of
surface preparation prior to the scan is another important consideration. The scan rate itself has
2
P
0
T 1.5 ~
E
N
T C-
I
A .5"
L
V O"
S
C -.5
E
-t
-I .5
-2 , , , , , , ,
-3 -2 -I 0 I 2 3 4 5 6 7 fl 9
LOG [CURRENT O E N S I T Y (nA/cm'2} ]
FIG. 9--Modeled polarization curve for a passivating metal in solution of lower oxygen concentration show-
ing triple Eco~r. Curve 1." modeled S curve; Curve 2: oxygen process," Curve 3."polarization curve resuhingfrom 1
and 2.
long been recognized as being a possible source of problems. Where time-dependent phenom-
ena are involved, scan rate is of crucial importance in obtaining reproducible data. Usually, the
use of scan rates of 0.1 m V / s or less provides acceptable results.
The usefulness of such a model in dealing with alloys is perhaps questionable. However, there
are many cases, such as the dealloying of zinc from brass [19], in which different dissolution
processes predominate at different potential domains and so there is no reason to preclude
modeling such cases.
From the theoretical standpoint, the availability of values for the kinetic electrochemical
parameters and the ways in which they vary as the experimental parameters change is often very
limited. However, as has been explained, a successful model is a rapid way of investigating such
behavior. One area of uncertainty is often to be found in some of the minor processes which
contribute to such a small extent that they do not influence the overall curve. In some cases,
however, it is possible to carry out a series of experiments in which a given parameter is varied
such that a minor process becomes significant. This greatly assists in evaluating the overall role
of the reaction.
Opponents of computer modeling often argue that in a sufficiently complicated computer
model any experimental curve can be reproduced with little associated relevance to theory.
However, anyone who has conducted such modeling investigations would surely conclude that it
is usually obvious when a model solution reflects theory with reasonable accuracy. Even small
changes in some calculated parameters produce changes which deviate wildly from experiment.
In addition, it is usually the change of model curve with change in parameter value which is of
most value in determining the validity of the model.
Conclusions
1 A method has been descnbed for modehng polanzatlon curves usmg a modern DOS-based
IBM compatible mmrocomputer and the extent o f its value described by reference to a
number of apphcatlons
2 A software package of less than 350 kilobytes has been produced which possesses all the
features usually expected m modern software such as color, hardcopy and screen displays,
considerable user control over the parameters m the calculations, mampulat~on of data
files, and interfacing with laboratory-derived data
3 The model has considerable advantages for evaluation of electrochemical parameters, elu-
c~datton of corrosion mechamsms, and education
4 The hmitaUons of the model are no greater than those of determining reproducible labora-
tory polarization scans
5 A d d m o n a l factors such as passwlty and time dependency are well within the scope of the
model
References
[/] Stern, M, and Geary, A L. "Electrochemical Polanzatlon I - - A Theoretical Analys~s of the Shape of
Polarization Curves," Journal of the Electrochenncal Soc:ety. Vol 104, No I, 1957. pp 56-63
[2] Pye, E L, Pye, M L. and Brock, F H , "Pol-Plot Basic Electrodlc Software Simple to Complex,"
paper 102, NACE, Corrosion '88, St Lores, 1988
[3] Rochml, G , "Extension of Stern and Geary's Method for Calculating the Electrochemical Parameters
with Interl Code," Paper 103. NACE, Corrosion "88, St Louis, 1988
[4] Rochtm, G , "Determination of the Validity Interval of Linear Approximation Method with Interl
Code." Paper 105, NACE, Corrosion '88, St Louis, 1988
[5] Hines, J G , "Analysis of Complex Polansatlon Curves," Brlt:sh Corroston Journal Vol 18, No 1.
1983, pp 10-14
[6] Mansfeld, F, Corroszon. Vol 29, 1983, p 397
[7] Costa. J M and Vdarassa, M, "Microcomputer Programs for Corrosion Education," Institution of
Corrosion Scmnce and Technology, m Proceed:ngs. U K Corrosion '88, Vol III, 1988, pp 99-110
[8] Devereaux, O F, "Polanzauon Curve Fitting by Computer Modelhng." Corroswn, Vol 35, 1979, p
125
[9] Trethewey, K R . and Keenan, J S, "The SIMPLER Computer Corrosion Modelhng System," Corro-
ston Preventton and Control. Vol 38, No 4, 1991. pp 89-96
[10] Shner, L L, Corros:on, Newnes-Butterworths, London, 2nd ed, pp 1 52-1 110
[11] Relger, P H . Electrochemtstry, Prenttce-Hall, Englewood Chffs, N J , 1987, pp 269-293
[12] Pourbalx, M, Atlas of Electrochemtcal Equthbrta m Aqueous Solutions. Pergamon Press, Oxford, 1966
[13] Shner, L L, Corroston. Newnes-Butterworths. London, 2nd ed. p 21 36
[14] Trethewey, K R , Marsh. D J , Every, P D, Dyson. P. and Roberge, P R , "An Electrochemical
Model of the Corrosion of Steel m Flowing Natural Seawater Using the Rotating Cyhnder Electrode,"
CorrosJon (submitted for pubhcatlon )
[15] Shner, L L, Corrosion, Newnes-Butterworths, London, 2nd ed, p 1 87
[16] Trethewey, K R and Tlghe-Ford, D J , "Polansatlon Charactenstlcs of Ship Hull Materials." Eighth
Inter-Naval Corrosion Conference, Monterey, Cahf, Apnl 1992, to be presented
[17] Ttghe-Ford, D J , "Pre-Deslgn Conslderattons for Impressed Current Cathodic Protection Systems,"
presented to U K Corrosion '90. Oct 1990, lnstltutton of Corrosion Science and Technology, P O
Box 253, Leighton Buzzard Beds, U K
[18] Trethewey. K R . Keenan. J S, and Wilson. I. "Analysis of the Electrochemical Behawour of
Stainless Steels Using the SIMPLER Computer Model." Corros:on Preventton and Control Vol 38, No
5, 1991.pp 115-118
[19] Vennck, E D and Heldersbach, R H, "Evaluation of the Tendency for Dealloymg m Metal Sys-
tems," m Locahsed Corrosion Cause of Metal Fadure. ASTM STP 516, American Society for Testmg
and Materials, Phdadelphm, 1972, pp 303-332
DISCUSSION ON POLARIZATION CURVES 125
DISCUSSION
0 F Devereux I (wrttten dtscusswn)--Your model essentially represents diffusion control as

one o f three resistors m series, with the measured potential drop occurring across the whole
circuit In other models the activation and ohmic terms represent two elements in series, w~th
diffusion entenng as a modified reactant activity m the actwat~on term These differ m that the
latter model Incorporates a reaction order The former also has a problem m describing diffusion
control expenenced simultaneously by two or more reactions Neither method is always effective
in describing the region o f transmon from full activation (Tafel) to full diffusion (vertical)
control
K R Trethewey and J S Keenan (authors" closure)--You raise a valid point There is cer-
tainly plenty of scope for improving the model described in the paper However, we have tried to
show m our applications that considerable success can be achieved even with a comparatively
simple model such as this
Department of Metallurgy, Umverslty of Connecticut, Storrs, CT 06269

Owen F. Devereux i a n d K o o k S u n Yeum 2
Modeling Electron Transfer, Diffusional

Effects, Passivation, and Ohmic Loss
in Multi-Reaction Polarization Curves
REFERENCE: Devereux, O F and Yeum, K S. "Modeling Electron Transfer, Diffusional
Effects, Passivation, and Ohmic Loss in Multi-Reaction Polarization Curves," Computer Model-
mg tn Corroston. ASTM STP 1154. R S Munn, Ed. Amencan Society for Testing and Matenals,
Phdadelphm, 1992, pp 126-142
ABSTRACT: A freely corroding metal may be represented as an electrode under the simultaneous
influence of at least two electrochemical reactions, one anodlc and one cathodic If the corroding
medmm ~smildly acidic, aerated water there are two cathodic reactmns ofslgmficance, reduction of
water and reductmn of oxygen, while addmonal anodlc reactions must be considered ff the metal
has muluple oxidation states or contains alloying ingredients or ff ~ts potential is sufficiently
posture to oxidize water The separate behavior of these reactions may be dehneated by polarizing
the electrode and rneasunng the current that passes as a function of the potentml To a good
approximation these reactions may be regarded as independent In this paper the current canned by
a single electrode reaction at a gwen potentml is expressed by a system ofequauons that incorpo-
rate rate control by electron transfer, dlffusmn, and passlvatlon, and correct for ohmic loss m the
electrolyte, the total current passed by the electrode and measurable m the external clrcmt ~s
expressed as a s~mple algebrmc sum of these values Features of dlustratwe polarization curves
(potentml versus log current) are explained m the context of this model, and the technique is
apphed to two experimental systems, one entadmg seven reacUons with twenty-four parameters
which were fit to the model wa a regresswe procedure
KEY WORDS: electrode, model, polarlzauon, multl-reacuon
Electrode polarization is a c o m m o n l y used, useful tool for the investigation o f electrode

p h e n o m e n a , such as corrosion, where the rate o f reaction is a d o m i n a n t concern In th~s process
the electrode is " p o l a n z e d " away from ~ts e q m h b n u m or " r e s t " potential m the test e n v i r o n m e n t
by passing a current between the test or " w o r k i n g " electrode a n d a n inert or " c o u n t e r " elec-
trode T h e current between these electrodes, representing the net rate o f electrodtc reactmn at
the working electrode, is directly measured with a device m series with these electrodes, the
working electrode is simultaneously characterized by its potential relatwe to a reference elec-
trode placed m close proximity to the working electrode using a high resistance voltage measur-
ing device A " p o l a n z a n o n e x p e r i m e n t " typically entails a stepwtse polarization o f the working
electrode from its rest potentml to the m a x i m u m cathodic potentml desired then, again stepw~se,
increasing to the m a x i m u m anodic p o t e n u a l desired A current charactenstlc o f each step ts
recorded, a n d data from the experiment are typically represented on a seml-loganthmtc potential
versus log I current density I plot T h e history o f the electrode is slgmficant a n d it is customary to
find that the first segment o f the experiment, from rest potentml to m a x i m u m cathodic potential,
is a n o m a l o u s w~th respect to the m a x i m u m cathodic to m a x i m u m anodlc scan, but that subse-

2 Materials Science Laboratory, GTE Labs Inc, Waltham, MA 02254
126
DEVEREUX AND YEUM ON MULTI-REACTION POLARIZATION CURVES 127
1000
800 + Rest-to-cathodicscan (1)
600 o Cothod=c-to-onod=cscan (2)
o Anodx-to-cathodicscan (3)
400
200
.~ 0 o * o ~o + o o
Ooq)
-200 + +++
El_
-400
-600
-800
-1000 , , , , .... i , , ,,,,,,I , , ,, ,,,i , , ,,,,,
.01 .1 1 10 100
Log current (mo/sqcm)
FIG ~_E~er~menta~ r~st p~en~la~-t~-ca~h~dtc-~-an~d~cscan f~r the c~P~ere~ectr~deln aque~us CuS~4~
followed by second scan
quent repetitions of the scan are somewhat reproducible as shown in Fig 1 An electrode
susceptible to anodlc corrosion is frequently polanzed first cathodlcally, as described above, to
avoid severe alteration of the electrode and thus of its subsequent cathodic behavior However,
m systems entailing cathodic lnhlbltors the reverse is true, and it is desirable to polanze the
working electrode first m the anodic direction to avoid the effect of electrode-altering adsorption
of cathodic-active lnhlbltors on the anodlc potential sweep
Polarization diagrams are frequently used as a basis for semi-quantitative comparison of envi-
ronments or electrode materials, when several curves are presented on the same plot, differences
in reaction rate or type are readily discerned In the case of corroding electrodes in simple
systems, a polarization diagram permits evaluation of the equlhbnum or rest potential of the
electrode, and also of the "corrosion current," the magnitude of the anodlc and cathodic
currents which are passed simultaneously by the unpolanzed electrode This determination Is
often ldeahzed as a "Tafel plot," such as shown in Fig 2, where anodIc and cathodic branches of
the curve display simple exponentml behavior and extrapolatwe means to determine these pa-
rameters are both obvious and accurate [ 1 ] More frequently, the stralghthne "Tafel behavior"
m not seen on the semi-logarithmic representation and considerable effort has been given to
numerical evaluanon of such plots [2-6 ]
In general, however, polanzanon plots do not admit to simple lnterpretaUon, but display the
effects of several s~multaneous reactions experiencing a variety of current limiting mechamsms
The curve shown m Fig 3 represents seven dmtmct reacnons characterized by 24 parameters
The authors have developed both subjectwe (repentlve esumanon) and objective (staUstical)
procedures to analyze such plots [ 7,8], but their effective use requires an ablhty to quahtatwely
-300
-400
._. -500
Veq
-600
E
O
-700
-800
-900 .... i I I I I I III I I I I I III I
.001 .01 .1 1 10
Log current (ma/sqcm)
FIG 2--Schematwpolartzattonplotshowmganodwandcathodwreacttonsexperlencmgstmflle Tafelbehav-
lor, and the net current (heavy hne)
analyze the phenomena depicted m a polanzatlon diagram These are descnbed in the following
sections
Model Description
Electron Transfer Control
The net current, ~, that may be measured at an electrode is the difference between a forward
current, t f, which we may regard as the current carried by an anodlc process, e g ,
M---~ M +z + z e - (la)
and a reverse current, iv, wh]ch is c a m e d by that process proceeding in the reverse, or cathodic
direction,
M ~ M +z + z e - (lb)
i e , i = if - - Ir Application o f high field transport theory to the reaction at the electrode surface
yields the following equation for the net current expenenced by the electrode
t = zF{kfcMexp[z( 1 - 3)FAV'/RT] - krcM+z e x p [ - z 3 F ~ V ' / R T ] } (2)
where kf and kr are forward and reverse reaction rate constants, respectively, cM and CM+zare
concentrations,/3 (0 </3 < 1 ) Is related to the symmetry of the free energy bamers, forward and
1800
1500
1200 9176
~176176
900
E 600
.--- 300 ...-~
o,,~
~o 0 9 ~ 9 ~ ~~ 9 ~ 1 4 9 1 7 6 1 7 6 1 4 9
9 ~ 9 1 7 6 1, 4~ 91 7 6 1 7 6 1 7 6 ~ ~
-300
%~
-600
-900 %9
-1200 I I I IIIIf I | I I [llll I I | I IIiil] I I I iiiii I ! i i i ii
.01 .1 1 10 100 1000

FIG. 3--Experimental polarization plot for the nickel electrode in mohen sodium carbonate under an atmo-
sphere of O.5 arm He, 0.25 atm CO, 0.25 atm CO,. and 0.000027 atm H.,S at IO00~ This curve represents
seven reactions described by 24 parameters.
reverse, for reaction ( 1 ); and A V' is the potential drop across the interface. The Faraday con-
stant, gas constant and temperature are given by F, R and T, respectively. When this reaction is
at equilibrium the net current, by definition, is zero, and an "exchange current," io, may be
defined:
io = zFkrCM exp[z( 1 - 1 3 ) F A V ~ / R T ]
= zFkrcM+z e x p [ - z ~ F h V ' ~ / R T ] (3)

t
where z~V'eq is the value o f ~ V ' at equilibrium. Defining overpotential, # -= AV' -- ~V~q, Eq 2
becomes
i = io{exp[z( 1 - O ) F # / R T ] - e x p [ - z ~ F t t / R T ] } (4)
i.e., the Butler-Volmer equation [9]. For large anodic overpotentials (n ~> 2 R T / z F ) Eq 4
approaches
# = b', log (i[io) (5)
i.e., the anodic Tafel equation, and for large cathodic overpotentials (n ~ - 2 R T [ z F ) ;
U = -b'e log ( - i / i o ) (6)

l e , the cathodic Tafel equation The anodlc and cathodic Tafel slopes are given by b'a
= 2 3 0 3 R T / z ( 1 - [3)F and b'r = 2 3 0 3 R T / z I 3 F , respectively, and are shown in Fig 2 The
Tafel constants in this instance are related by
(7)
b. = b~ z F b c _ 2 3 0 3 R T }
Equation 2 is limited in its apphcabihty, there are relatively few practical c~rcumstances in
which the sole current carrying capability of an electrode is represented by a single reaction
which may go forward or backward, e g , Cu in a near-neutral oxygen free electrolyte containing
a significant concentration of Cu ++ More frequently an anodic reaction will be possible, e g ,
Fe---~Fe ++ + 2 e - (8)
along with an unrelated cathodic reaction, e g ,
1~O 2 "~ 2H20 + 2 e - ~ 2 O H - (9)
Equation 2 must now be replaced with
t = zF{k~cwexp[z(1 - 13~)FAV'/RT] - k c c o 2 8 9 1 6 2 (10)
We note that the forward and reverse reaction rate constants may more properly be denoted ka
and kc, respectively, to emphasize that they represent distinctly different reactions, and that the
Tafel slopes are no longer related by the simple expression ofEq 7 being, in fact, unrelated at all
Furthermore, as in any chemical kinetics expression, the pre-exponentlal term has been modi-
fied to represent the product of all reactants, raised to the power of their stoichiometrlc coeffi-
t
cients In addition, the equlhbrlum potentials, A V~q, of the anodlc and cathodic reactions will in
general be different, precluding a simple reduction of Eq 10 to the form o f E q 4 In representing
several electrode reactions occurring simultaneously, therefore, we must express each simply in
the form
nj
tj = sjzjFkj ]-[ a, m' e x p [ ( s j A V ' / b j ) ] ( 11 )
where 2 303 bs is equal to the corresponding Tafel slope as defined in Eq 5 or 6 The parameter sj
has been introduced to enable the use of a single expression to describe both anodlc and cathodic
reactions, s --- 1 for anodlc reactions, s ~ - 1 for cathodic reactions The product of reactant
concentrations has been generalized and more correctly expressed in terms of activities, with the
index i representing the vanous of the nj reactants, m, is the corresponding stoichlometrlc
coefficient
The potential difference, A V', across the electrode Interface may be represented as the poten-
tial, V, of the electrode measured relative to an appropriate reference electrode, less a constant
representing the potential of the reference electrode relatwe to the solution, V~e f
ttj
lj = s F ~ r k j f I a, m' exp[s~(v - Vror)/bA (12)
Now we note that from the standpoint of empirical evaluation we cannot distinguish Vrefllbj from
the pre-exponential constant These may be combined as a single parameter, V~, where
%
V~ =- V , ~ t - s j b j l n ( z j F k j ) - sjbj In ( l - I a, m' ) (13)
l=l
This allows Eq 12 to be written simply as
ts = s~ exp[ss( V - Vf)/bj] (14)
Equauon 14 represents all of the information that can be determined regarding a single anodic or
cathodic electrode reaction under electron transfer control, 1 e , it is the equation of a straight
line in semlloganthmlc space, where bj is the slope and V~ is the potential at which the current
has unit value
Diffusion Control
Equation 12 contains a product o f the activities of reactants involved in reaction j , each raised
to the power of its stoichlometnc coefficient If electron transfer is truly rate-hmitmg, these
activities are those characteristic o f the bulk electrolyte However, if the current is large the
gradient necessary for the diffusion of these reactant species may be significant, e g , for a species
diffusing to the electrode the activity at the electrode surface may have a value appreciably
smaller than the bulk value The current canned by diffusion of such a species is commonly
represented as
w = ~k(ao - a) (15)
where k is a constant, ao is the bulk activity of the species, and a is the value at the surface, given
by
a = ao(l - 55/aok) (16)
Let us consider the case where diffusion of a single species to the electrode is, in part, rate-
limiting Substitution of Eq 16 for its activity into Eq 13 results in the following expression in
lieu of Eq 14
ij = sj( 1 - s f l / a o k ) " J exp[sfi V - VT)lbj] (17)
It is clear that as potential increases in magnitude the current will gradually approach aok in
magnitude, but cannot exceed that value Hence aok represents a limiting current value which
we may denote by i s (1 s > 0), and
tj = ss( 1 - s / / t ~ ) " J exp[ss( V - V ~ ) / b j ] (18)
A similar analysis for reactant species whose activity at the surface is controlled by diffusion
away from the electrode leads to the same formulation The behavior o f E q 18 is shown m Fig 4
for the cathodic reaction For each reaction diffusion control adds two more parameters neces-
sary to the description of the current It is clear that the limiting current, t~, can be determined
with considerable accuracy by inspection o f Fig 4 as the vertical asymptote, in contrast, the
stoichiometnc coefficient, mj, affects the curve only over the narrow region of transition from
Tafel to diffusion-limited behavior, frequently entailing only a few points of the polarization
0
-120
-240
-3(50
>
E -480
J
-1500
Q.)
-i,--,
0 -720
13_
-840
-960
-1080
-1200 I I I I I III I I I 1 I IIII i I I I I Illl I I I I 1 I II
.001 .01 .1 1 10
FIG 4--Schemattc polartzatton plot for two reactJons a cathodw reacnon showing electron transfer and
dtffuslon control, and an anodtc reactton showmg electron transfer control and passlvatlon
scan For this reason m fitting an empirical curve to this model the value of mj is frequently
allowed to default to 1, ~ e , assumption of first-order reaction kinetics We have observed that
aqueous systems often display a very gradual change from Tafel to dlffus~on control, suggesting a
value of mj < 1, but the slgmficance o f this is unclear
eassivallon
A reaction that undergoes an actwe-passwe transmon must be represented by two d~stmct
mechamsms inasmuch as there ~s an abrupt change m the condlUons defining mass transport
Passwatlon may be due to the formation of a sohd reaction product on the electrode, e g , an
oxide, which may or may not continue to grow m thickness m p r o p o m o n to the charge passed In
other instances ofpasswat~on the transluon to passwe behawor ~s manifested m the formation of
a chemlsorbed film of 02 or o f passwatmg ions [10] In the latter case and m the case o f a
non-growing oxide film the resistance to mass transport ~s constant and the polarization curve
should display a passive current that increases with increasing potential In the case o f a growing
oxide film this behavior may be offset by the increase m resistance to mass transport afforded by
the greater thickness of the film In e~ther case, the instantaneous relaUon between current and
potentml may be non-simple, ranging from exponentml (high field transport) for very thm films
to hnear for thick films In the absence of a model o f general apphcabfllty it is usually convement
to model the passwe current as a constant, ~ e ,
tj = t~, V > Vje (19)
where V~ is the passwauon potentml This is represented by a vertical hne on the polarization
diagram Subjectively, most polarization plots do not display a discontinuous transition from
active behavior to full passivity and, on an ad hoe basis, may be modeled more satisfyingly by
reversing the slope of the Tafel line at V = V ; a n d continuing the new line until it intersects with
the line b = t ; The entire model of a reaction initially showing electron transfer control then
becoming passive is, then,
It = st exp[st( V - V~)/bt], V <_ V~ (20)

b : st e x p [ - s j ( V - 2V~ + V;)/bj], V~ < V<~ V tJ (21)
Ij = Iif, Vt) < V (22)
V', =- 2 V ; - V; - btsjln t~ (23)
The anodic reaction in Fig 4 shows electron transfer control and passwatlon, modeled by Eqs 20
through 23.
Ohmw Loss
Sometimes termed resistance polanzauon, ohmic loss represents an error in the measurement
of electrode potential due to placement of the reference electrode within the potential gradient
required to drive the cell current through the electrolyte Although many polarization instru-
ments correct for this error, it is also readily taken into account by subtracting Rt ohmic term
from the apparent cell potential Specifically, substitution of V - sflAR for V m Eq 14 yields
tj = sj( 1 - s~,~llS)m,exp[sj( V - VglbA exp[--lARJb A (24)
where A is the surface area of the electrode and Rj is the effective resistance of the electrolyte
This has the effect of ever-increasing the magnitude of the slope of the polarization curve as the
potential is increased or decreased from the rest potential, but does not cause the curve to
approach the vertical The example shown in Fig 5 contains four reactions a cathodic reaction
showing electron transfer and diffusion control, followed by a cathodic reaction experiencing
electron transfer control with ohmic loss, and an anodic reaction showing electron transfer
control and passivation, followed by an anodlc reaction showing electron transfer control and
ohmic loss In our experience only the anodlc reaction operative at the highest overpotentlal and
the cathodic reaction operative at the lowest overpotentlal are seriously affected by this effect,
however, it is important to note that the "t" in the ohmic factor is total current experienced by
the electrode at that potential, not simply the current carried by reaction j Furthermore, we
frequently find that the optimum value of cell resistance, R, for the anodlc branch of the
polanzatlon curve is not necessanly the same as the optimum value for the cathodic branch
The Polarization Model

The polarization model consists of the following equations to describe the current carried by
individual reactions For a reaction experiencing electron transfer control
b = sj exp[sj( V - V3)lbxl (14)
For a reaction experiencing simultaneous electron transfer and diffusion control
b = sj(1 - sflxi,'j)"' exp[sj( V - V3)/b A (18)

500
250
0
-250
-5oo
.~ -750
~ -1000
Q_
-1250 1
-1500
-1750
-2000 ....
)01 .01 .1 1 10 100
FIG 5--Schematic polarization plot for four reactions a cathodic reaction (CI) showing electron transfer
and diffusion controL followed by a cathodw reaction (C2) experiencing electron transfer control with ohmic loss,
and an anodtc reaction (A 1) showmg electron transfer control and passtvatlon, followed by an anodtc reaction
(A2) showing electron transfer control and ohmw loss The net current is shown as the heavy hne
For a reaction experiencing electron transfer control, diffusion control and ohmic loss
~j = sj( 1 - s / J , 5 ) ' , exp[sj( V - v3)/6,] exp[-tARJbj] (24)
For a reaction experiencing electron transfer control and passivatlon
5 = s j exp[ss(V- V;)lb,], V <__V'; (20)
ij = sj exp[-sj( V - 2V] + VDIb,], v,; < v <_ v$ (21)
5 = t;. V; < V (22)
V~ =- 2Vse- V~' - bsssIn tse (23)
The total current experienced by the electrode is the sum of the currents camed by the
mdwldual reactions
, = I~ ,,I (25)
j~l
Again, the total current is expressed as a magnitude in keeping with its normal representation on
a semdoganthmic
Copyright plot
by ASTM Int'l (all rights reserved); Tue Feb 10 09:33:27 EST 2015
500
250
A1
0
A2
-250
>
-5oo
9~
r
-750
QJ,
"~ -1000
t:)._
-1250
-1500
"1750
-2000 , ...... ,, ....... , ........ 1 ........ , , , ,,,,,,
.01 .I I 10 100 1000
FIG. 6--Schematic polarization curvefor two cathodic reactions and two anodic reactions, all experiencing
electron transfer control. The b-valuesfor the anodic reactions are different, and thefirst cathodic reaction (C1)
also experiences diffusion control
Model Characteristics
The separate contributions of the four individual reactions comprising the calculated polariza-
tion curve in Fig. 5 are shown separately. This curve shows most of the common features seen in
polarization curves. It is important to recognize that there are certain limitations in what can be
resolved from the net current curve. If there are two reactions, one anodic and one cathodic,
their individual contributions to the net current can clearly be distinguished provided that the
polarization scan has included an adequate potential range on either side of the rest potential to
define both the anodic and cathodic portions of the curve. ( W e have not, in this paper, discussed
the merits of linear polarization, which can be used for detailed examination of electrode behav-
ior a few tens of millivolts on either side of the rest potential.) However, if the anodic portion of
the polarization curve is comprised of two reactions which have similar Tafel slopes or bj values
and which experience only electron transfer polarization, their contributions cannot be resolved,
i.e,, the contributions of the two reactions are indistinguishable from that of a single reaction:
i~.onic = e x p [ ( V - VT)/b~] + e x p [ ( V - V~)/b2]
= e x p [ V - ( V ~ + V~)/b] (26)
if bl = b2 = b. The separate contributions of the reactions may be clearly discernible if the b

values are substantially different, as in the anodic curve shown in Fig. 6, or if the smaller
overpotential reaction experiences diffusion-limited control or passivation, as in the cathodic
curve by
Copyright ofASTM
Fig. 6.Int'l (all rights reserved); Tue Feb 10 09:33:27 EST 2015
TABLE l--Classlficatton o f electrode reactions

Type Elec Trans PasswaUon Diffusion Ohmic Parameters
l yes be, V;"

2 Yes Yes bj, V~, V;, ,;
3 Yes Yes be, Vj,, m~, t}
4 Yes Yes bj, Ve , Rj
5 Yes Yes Yes be, V;, "e, ';" Re
In examining an empmcally-determmed polarization plot, the first step is to determine, by

inspection, the number of anodtc and cathodic reactions Next, each reaction must be catego-
rized as shown m Table 1 In our experience ~t has not been necessary to revoke more complex
permutations of these rate-hmltmg mechanisms
After estabhshlng the n u m b e r and type of electrode reactions, mmal esUmates must be made
of the relevant parameters These can be done by mspectton The b values represent Tafel slopes
(Tafel slope = 2 303b) on the semdoganthmlc plot, the V* values, intersections of the electron
transfer control hne (Tafel hne) wtth the t = 0 axis, and t e, t s, and Ve values are apparent from
the plot It is necessary to recognize that ff there are two diffusion controlled or passwatmg
reactions on etther branch of the curve, then the net current m the region of influence of the
second, higher overpotentml reaction includes as well the h m m n g current of the first, lower
overpotentml reaction as shown m Fig 7 Values for m may usually default to 1 while values for
~176176
420
I
- oo
-480
\
-1020 / '~
-1200 ........ i ........ i ........ i ' , I I I IIII
.001 .01 1 1 10
Logcurrent(ma/sqcm)
FIG 7--Schematic polartzatton curve for one cathodtc reactton and two anodw reacttons The cathodw
reactton expertences electron transfer and dlffuston control The first anodlc reactzon (,41) experiences electron
transfer control and dtffuston control the second anodtc reactton (,42) e,cpertenees electron transfer control and
passlvatton The apparent passtve current ts represented as the sum o f t~ and t~
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further rep
1200
960 / J
720
480
E 240
t~ 0
-E
q)
o -240
(3..
-480
-720
-960
-1200 i I IIIIII
.001 .01 .1 1 10 100 1000

FIG. 8-- Empirical polarization diagram for 304 stainless steel in O.1 N sulfuric acid equilibrated with air
with a superposed model curve and the contributions of the individual reactions.
R may be estimated from the known resistivity of the electrolyte. Given these characteristics and
estimates, accurate curve parameters may be determined by one of the two methods described
earlier. In one~ an interactive graphics program is used to display both experimental and calcu-
lated curves on the same plot, enabling a visual estimate of degree of fit. As each curve parameter
has a unique effect on the polarization curve, this provides a basis for estimating new parameter
values. The process is repeated until a visually acceptable degree of fit is obtained [7]. In the
second method a statistical technique is used to improve the initial parameter estimates to any
desired degree of accuracy. This is a non-simple method that had been described in detail {81
and entails dividing the data into groups of points that are dominated by a single reaction, then
holding the parameters for other reactions constant while fitting a single reaction to those data.
Both procedures are quickly and easily performed on 80286 processor machines.
Applications
Stainless Steel/O.l N H2S04
Figure 8 shows the empirical polarization diagram for Type 304 stainless steel in 0.1 N sulfuric
acid equilibrated with air. The optimum model curve is shown superposed on the data, and the
currents carried by the individual reactions are shown as well. The first (smallest overpotential)
cathodic reaction, C 1, is reduction of oxygen, experiencing electron transfer and diffusion con-
trol. At larger, more negative, overpotentials reduction of water with evolution of hydrogen is
seen, reaction C2; this reaction experiences electron transfer control and ohmic loss. The first
(lowest overpotential) anodic reaction, A1, is anodic oxidation of the electrode and shows
TABLE 2--Reaction parameters for Fig. 8.

j Type s] V7 bj i~ Ve i~ Rj
1 4 -1 -200 53.3 . . . . . . 3.0
2 3 -1 -350 36.7 "210" . . .
3 2 1 250 216.7 . . . -15() ().()4
4 4 1 900 25.0 . . . . . . . . . "610"
passivation. The second anodic reaction, A2, is oxidation of water, experiencing electron
transfer control and ohmic loss. The parameters for these reactions are shown in Table 2. Figure
8 exemplifies an important limitation of the model, assumption of a constant current for a given
reaction above its passivation potential. In fact, most passivating reactions show a non-constant
current in the passive region; that shown in Fig. 8, a slow decrease with increasing potential
followed by a slow increase, is not uncommon.
Nickel in Molten NaeS04

Figure 3 is an empirical polarization plot for the nickel electrode in molten sodium carbonate
under an atmosphere of 0.5 atm H2, 0.25 atm CO, 0.25 atm CO2, and 0.000027 atm H2S. This
plot is repeated in Fig. 9 with a superposed calculated curve and the current contributions of the
individual reactions. These data have been fit to a model containing seven reactions: a cathodic
reaction and six anodic reactions [ 11]; the reaction parameters are shown in Table 3. Careful
1800
1500
1200
9O0
600
"e 300
o
g_
-300
-600
-900
-1200 , ,, ..... , .... ,,,,, ........ , ........ , .... ,,,,
901 .I I 10 100 1000

FIG. 9--Experimental curve of Fig. 3 with a superposed model curve and the contributions of the individual
reactions.
TABLE 3--Reactwn parametersfor Ftg 9

./ Type sj Vj* bj t; V] t; Rj
I 4 -1 -1800 1500 287
2 3 1 - 190 0 36 9 2 93
3 3 1 44 49 4 14 89
4 2 1 262 6 19 8 295 4 0 20
5 2 1 513 3 62 2 627 8 0 23
6 2 1 630 0 56 7 775 0 5 00
7 4 1 739 6 48 3 3 74
study of this system using the techniques described above has shown that the cathodic reaction is
reduction of CO2
2 e - + 2CO2 ~ CO + COy (27)
i e, Vet/bet for this reaction was shown to be a simple hnear funcuon of In Pco2 Similarly, a
hnear relation between F*l/ba~ and In PH2 showed the first anodlc reaction to be oxidation of H2
H 2 + COy "-~ H20 + CO2 + 2 e - (28)
In the absence o f H 2 and H2S, the second ano&c reaction was seen to be oxidation of a chemi-
cally &ssolved CO, e g , CO~,
CO~ --~ CO2 + 2 e - (29)
with the concentration of chemically dissolved CO being determined by the e q u l h b n u m
CO + O = -~ CO~ (30)
or
C O + C O 3 --~ C O 2 + C O 2 (31)
as evidenced by a hnear relation between V*a2/ba2and In Pco/Pco~ In the presence of H2S,

however, the parameter t~: was found to be proportional to 0~/2
IH2S Thts could only be attributed
to the enhancement of the solubility of CO via the reaction sequence
H2S"~H + + HS- (32)
H S - + CO --~ C O H S - (33)
and the complex C O H S - taking the place of CO2 m reaction ( 2 9 ) (At higher CO pressures
than employed m this example oxidation of physically &ssolved CO was seen as a distinct
reaction ) Environmental independence and diffraction analysis of reacUon product strongly
suggested that the third, fourth, and fifth anodm reactions were
N1--~NI ++ + 2 e - (34)
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) purs
1800 /
1500 i.
i
9
9
1200
PH2S = 0.0 ~ . 9:~:.'::9
900
. . . . -
0.000027 ~ . ~ i .: / --'u.uz/ 9
E 600
B
.2 300 : ~9 f ...9
E Q J, / " '- ;.,.
, . ~f"l 9.".':. 9
O 0
13_
9..-.', .4,
-300 9~ 9 9 9 ~ 1 7 6 1 4 9 1 4Z9~ " ~ % , ~ 9
"9 9 .~ . . .
-600 "".'.'.".-........
.... ~...... 9
-900 9 9149
9~149 9 . 9149
9 .9 ~176
-1200 I I I IIIII I I I I IIIII I I i i i iiii I | I Illlll I I I I IIII
.01 .1 I 10 100 1000

FIG. 10--A family of curvesfor the system depicted in Fig. 3. showing the effect of increasing Pn2s.
passivating through NiO formation,
2NiO + CO3 --~ Ni203 -}- CO 2 + 2 e - (35)

and
Ni:O3 + C03 -"* 2NIO2 + CO 2 "~-2 e - (36)
respectively. Finally, the sixth anodic reaction was shown to be
CO~ --~ 89 + CO2 + 2 e - (37)
again via environment independence and the potential range over which it occurred. The use of
the above technique was especially valuable in being able to reduce the series of polarization
curves shown in Fig. 10, in which a drastic change in appearance and apparent anodic activity
occurred with a change in H2S pressure, to the variation of a single parameter, i~,2, with H2S in
accord with reactions (32) and (33) as shown in Fig. 11.
Conclusions
Polarization curves may be modeled by summing the currents carried by individual electrode
reactions experiencing electron transfer control, diffusion control, a n d / o r passivation. The indi-
vidual characteristics needed to describe each reaction may be readily inferred from subjective
analysis of the polarization behavior. Parameter values may be determined by subjective or
20
E 15
(/.')
E
-E
10
O
<:
0
0 1 I I l I
-0.05 0.00 0.05 0.10 0.15 0.20 0.25
Sqrt(PH2S(atm))
FIG l l--Correlatton of the t~2 values of Ftg 10 wtth P~2s
objectwe computer analysis, performed on desktop instruments, enabhng the routine fitting of
even complex polarization curves by a meaningful electrode model
References
[/] Wagner, C and Traud, W Z,ElectrochemwaActa, Vol 44, 1938, p 391
[2] Barnartt, S, Corroswn, Vol 27, 1971, p 467
[3] Jankowskl, J and Juchnlewlcz, R, Corroston Scwnce, Vol 20, 1980, p 841
[4] Mansfeld, F, Corroston, Vol 29, 1973, p 397
[5] Reeve. J C and Bech-Nlelsen, G , Corroston Sctence, Vol 13, 1973, p 351
[6 ] Greene, N D and Gandhi, R H, Materials Performance, Vol 21, 1982, p 34
[7] Devereux, O F, Corroston. Vol 35, 1979, p 125
[8] Yeum, K S and Devereux, O F, Corroswn, Vol 45, 1989, p 478
[9] Bockns, J O'M and Reddy, A K N, Modern Electrochemtstry. Plenum Press, New York. 1970
[10] E g, H H Uhhg, Corroswn and Corroswn Control Wiley, New York, 1963
[11] Yeum, K S, Kam, K Y, and Devereux, O F, CorroslonSclence. Vol 25, 1985, p 1127
DISCUSSION
S Turgoose I (wrttten dlscusslon)--Your paper d~scusses a diffusion hm]ted c u r r e n t for a

metal d]ssoluUon process How does this arise, since the actwlty of the reactant (the metal)
cannot change with potential (or current)9
Corrosion and ProtecUon Centre, U-MIST, Manchester, Umted Kingdom

0 F Devereux and K S Yeum (authors' closure)--We beheve that our discussion of diffusion
control (1 e , our "Type 3" reaction) has been restricted to generahzed anodlc and cathodic
reactions, without specific reference to metal dissolution, and therefore, ~s correct Although the
model per se does not specifically preclude it being couched m general terms, we would not
expect to observe diffusion control of a simple metal dissolution reaction In fact, this type of
subjectwe reasoning is very important m determining the identity of the electrode reactions
comprising the net curve, were we to observe d~ffUSlOncontrol of a particular reaction we would
not consider metal d~ssolutlon as a candidate
U. Bertocci 1 a n d R. E. R i c k e r I
Modeling Polarization Curves and Impedance

Spectra for Simple Electrode Systems
REFERENCE: Bertocci, U. and Ricker, R. E., "Modeling Polarization Curves and Impedance
Spectra for Simple Electrode Systems," Computer Modeling in Corrosion, ASTM STP 1154, R. S.
Munn, Ed., American Society for Testing and Materials, Philadelphia, 1992, pp. 143-161.
ABSTRACT: A method for modeling the behavior of electrochemical systems based on electrode
kinetics instead of equivalent circuits is developed, and examples of the application of this model-
ing method to three electrochemical systems are presented. It is shown that the behavior of simple,
as well as relatively complex, electrochemical systems can be modeled on desktop computers
yielding impedance spectra as a function of input quantities that describe steady-state electrode
kinetics and the electrode potential. This approach, since it is based on quantities that describe the
kinetics of the actual processes that occur at the electrode, has the advantage over other approaches
of having a built-in physical interpretation. The impedance plots produced in this way can give a
feeling of what to expect experimentally and can be useful in testing hypotheses, in establishing
reasonable ranges for quantities not easily accessible to measurement, and in suggesting experimen-
tal strategies.
KEY WORDS: corrosion, impedance, modeling, polarization
Computer programs, through modeling, curve fitting, and plotting routines, can be extremely
useful in the analysis of impedance spectra of electrochemical systems, where the interplay of a
large number of factors makes interpretation of the experimental results difficult. The approach
most commonly taken, both for modeling and curve fitting, is that of constructing an equivalent
circuit that is an assembly of passive elements, such as resistors, capacitors, and inductors, which
approximate the desired impedance spectrum [ 1]. This approach suffers from a number of well
known problems; the main one is that simple circuits made of a few elements seldom provide a
satisfactory fitting, but when the number of circuit elements is increased until fitting is good, the
physical meaning tends to be lost.
The approach presented here is that of modeling the electrochemical behavior by using rela-
tively simple schemes based on electrode kinetics. This type of approach is certainly not new,
and the scientific literature [2] contains several outstanding examples of impedance spectra
derived from models of the chemistry and electrochemistry of systems. Nor will this approach, at
the present level of complexity, overcome the first of the problems mentioned above for the
equivalent circuit approach, namely that of poor fitting. Therefore, its main advantage is thai of
having a built-in physical interpretation so that when fitting calculations to experimental data,
the values selected convey an immediate meaning to the operator that relates to the physical
processes occurring in the system.
We would like to point out that the examples presented here were developed and imple-
mented on desktop computers by experimentalists with no special training in computer pro-
gramming or numerical methods. Therefore, the actual codes could be easily improved by experi-
Corrosion Group, National Institute of Standards and Technology, Gaithersburg, MD 20899.
143
Copyright 9 1992 by ASTM International www.astm.org
enced programmers, on the other hand, the programs should be easily intelligible to people
involved m corrosion and electrochemical studies
In this paper, the conceptual basis for such computer programs will be described, and some
examples taken from the implementations used In our laboratory will be presented and
discussed
Conceptual Framework
The pnnclpal concept on which our modeling is based is that of calculating first the steady-
state behavior of a given electrode/electrolyte system Relatively simple schemes, based on
electrode kinetics coupled to transport m solution, can generate polarization curves and then the
corresponding impedance spectra as a function of the electrode potential The impedance plots
produced by such programs are able to give the operator a feeling of what to expect experimen-
tally By observing the effects of varying the input parameters, attempts can be made to approxi-
mate the experimental curves In this way it is possible to test hypotheses, to establish reasonable
ranges for some quantmes not easily accessible to measurement, and to derive suggestions for
experimental strategies This can make a useful contribution to the interpretation, however
partial, of the results, with a relatively small expenditure of effort and equipment
Another of the general concepts used in developing these computer programs was to mesh as
much as possible the modeling and the analysis of experimental data Therefore, although
convenience may dictate to have separate programs for data acquisition, for data analysis, and
for computer simulations, it is desirable that the same analysis routines be applicable to the
expenmental as well as the simulated spectra In this paper, however, we will discuss only model
data, and not experimental data
Among the aids available for data analysis in our implementation we will discuss two m
particular
A large selection of possible plotting schemes They include the famlhar Nyqulst and Bode
plots, but also phase angles and admittances as a function of various parameters Some of
the plots are particularly useful when applied not to the raw data, but to the values ob-
tained after deconvolvmg some of the circuit elements, such as the solution resistance The
types of plot available are hsted m Table 1
Ability to subtract the solution resistance R~ol, obtaining the impedance of the electrode
interface, as well as to deconvolve the double layer capacitance Col, obtaining what is
commonly called the admittance of the faradaic branch It should be pointed out that these
deconvolutlon operations might seem trivial when applied to simulated data, since the
values of R~ol and Cd~ are known However, it has been found mstructwe to deconvolve
with values slightly above or below the actual ones, in order to learn what distortions one
can expect when the operation is carried out on expenmental data, where the exact values
are not known
Description of Model
The outline of the system described by the model is as follows a metal electrode ofumform
surface characteristics is immersed m an electrolyte Transport m solution occurs perpendicu-
larly to the metal surface, so that the only parameter necessary is the &ffuslon layer thickness 6
It should be pointed out that ifa rotating disk electrode is considered, it is quite easy to enter the
rotational speed and have the program calculate 6
BERTOCCI AND RICKER ON SIMPLE ELECTRODE SYSTEMS 145
TABLE 1--Dzfferent ways of plomng trnpedance spectra

No X Y Remarks
1 Z' Z" X- and Y-scale identical
2 wZ" Z'
3 Z"lo~ Z"
4 I/1/~ Z'
5 1/r z"
6 log l Z I phase
7 Y'e) Y~l After subtracting R~ol
8 Y'Jw Y'~J,., After subtracting R~l
9 l/V~0 Y'e~ After subtracting R~ol
10 log w:~ Y'et After subtracting R~o~
11 log w~ Y~) After subtractmg R~ot
12 log u S log Y'l After subtracting R~o~
13 log w~ Y~j/w After subtracting R~ol(High frequency limit Is Cd~)
14 log w~ log (Y'~/~o) After subtractmg R~ol(High frequency hm~t is Cdl)
15 log ~o:~ log (Y'~l/~oY'~)) After subtracting R~ol(Time constant)
16 log ~o1: phase
17 log w'~ Z'
18 log w:~ log Z'
19 log ~ Z"
20 log w~ wZ"
21 log w:[: log Z#
22 log oaJ~ JZ J
23 log w:t: log [ Z [
24 log w~ log I Z [ & phase Double plot
:[: The frequency may be plotted as log ~0(rad/s) or log u (Hz)
The relationship hnklng the steady-state current density to charge transfer and transport 1s of
the general form
t = t + + I- = z a k + F ( C ~ ) o e x p l - - - ~ ) - zck-F(Co,)o exp - (i)
where k § and k - are rate constants for the ano&c and cathodic reactions, and ( C ~ ) o and ( Cox)o
are the concentrations of the electroactwe species at the interface, which are related to their bulk
concentrations through a &ffUSlOnal transport equation, of the form
tx nFDx
= ~ [ ( G ~ , - (CAo] (2)
where x is a generic index, and n is the number of charges exchanged m the electrode reaction
Depending on the speofic circumstances simulated, the equattons can be slmphfied or made
more complex to accommodate particular reaction schemes Once the necessary input values are
entered, the total as well as the partml current densmes, the concentrauons at the interface, and
the zero-frequency electrode resistance can be calculated as a function of the electrode potential
and displayed m various kinds of plots Slmulauon of the &stortlon caused by an ohmic drop is
possible by entenng a value for R~o~ and then, at every electrode potential, summmg to it the
product of R,o~ by the current density
For every value of E It is then possible to compute the impedance spectrum within a chosen
frequency range by &fferentlatmg Eqs 1 and 2 under the customary assumption of small pertur-
bations [3]
F I+ l-
AI = ~ ( O / l + ~- ( l -- a),-)AE + ~ ACid + ,-7-7---7-,ACox (3)
('-- ,~)o t Cox)o
and
6
A(C~)o - - - Alx (4)
nFDx
From Eqs 3 and 4 the expression for the electrode impedance Z = AE/At as a function of the
frequency of the modulating voltage can be obtained, given some specific case concerning the
electrode reaction For instance, for a redox reaction of the form, where n = 1,
(C~.r "~= (Cox) ~+' + e - (5)
The electrode impedance is
Z = F [ a t + + (1 - a ) , - ] 1 + --~ [ ~ f . ( w ) + (---~o~)of~(w) (6)
where the first term is the charge transfer resistance and the second the transport or diffusion
resistance The functions of the frequency ~0 have the form [4,5]
- ,
(7)
where the index x indicates either the reducing or the oxidizing species When the frequency
tend to zero, the hyperbolic tangent becomes equal to its argument, so that
,o--.olImf~-2-~( 6 ~ - j 6 j~)_ 6D,, (8)
These formulae allow the computation of the impedance spectrum, at equilibrium or at any
other potential Choice of different electrode reactions modify the expressions, sometimes slm-
phfylng them, as in the case of a metal/metal ion reaction, where the activity of the metal at the
interface can be considered constant, or comphcatlng them to various degrees, depending on the
complexity of the reaction modeled
Examples
~ m p l e Redox Reactton
An electrode on which reaction ( 5 ) is the rate determining step affords the simplest, if not the
most interesting case, for the calculation of the polarization and impedance curves The input
quantities which determine the steady state values are the concentrations and diffusion coeffi-
cients of the reacting species in the bulk of the solution (C~d)b, (Cox)b, Dred and Dox, and the
valency z, dlffUSlOnal transport is then determined by selecting the diffusion layer thickness 6,
while charge transfer is determined by giving the rate constant k and the symmetry factor a I f a
specific redox system is modeled, the value of its standard potential E ~ has to be known in order
for the value E o f t h e electrode potential to simulate the expenmental data Very often, however,
for generic modeling purposes, one can set E ~ --- 0 so that it IS also k + = k - = k, that is, the
forward and backward rate constants have the same numencal value as the formal rate con-
stant k
Polarization Curves--A system of four first-degree equations, two denved from Eq 1 for each
partial current and two from Eq 2 for the two reactants, where the unknowns are t + and l - and
the concentrations are ( C~o)o and ( Cox)oat the electrode surface, can be solved for every value E
of the potential, so that polarization curves, as well as concentrations at the electrode and
electrode resistance, the total as well as its partition between charge transfer and diffusion
resistance, can be plotted as a function of potential Even for a simple system such as this one, it
can be quite instructive to see how changing stimng rate, reactant concentrations, or potential
can affect the magnitude of the zero frequency limits of the electrode impedance
hnpedance Spectra--The impedance spectrum can then be computed for every value of E,
using Eqs 6 and 7 to calculate the faradalc branch The operator must supply the values of the
solution resistance R~ot and of the double layer capacitance Cdt m order to simulate the results
which would be obtained from a galvanic cell As examples, two polarization data sets were
calculated, changing the concentration of the reduced species from being the same as that of the
oxidized species to one tenth of it, so that the equilibrium potential is shifted m the positive
direction Figure 1 shows the current/potential curves for the two cases, together with their
respective partial current densities, and Fig 2 shows how the concentranons at the interface vary
with potential From the point of view of Impedance analysts, the most interesting plot is that of
Fig 3. where the zero-frequency values of the total, charge transfer, and diffusion resistance are
plotted against potential From this it can be seen under which circumstances either charge
transfer or transport In solution is rate determining Correspondingly, the Nyquist plots of Fig 4
show how the charge transfer and diffusion loops vary with potential
To illustrate the usefulness of manipulating the impedance spectra for analysis purposes, Figs
5 and 6 show Nyquist plots of the faradalc branch, after deconvolutlon of the solution resistance
and of the double-layer capacitance If the values of R~ot and Cat are exactly those used in the
modeling calculations, of course the charge transfer loop collapses into a single point, and only
the &ffUSlOnloop is left, as seen in the right-hand side of the plot in Fig 5 However, if the value
of the capacitance is more or less than the exact one, additional loops are generated, whose
position with respect to the horizontal axis is diagnostic Conversely, as shown m Fig 6, use of
the Incorrect value for ]{sol generates curves which may go to the left of the vertical axis, if the
value subtracted is greater than the correct one
As another example of data analysis, Fig 7 plots the imaginary part of the electrode admit-
tance (that IS, after subtraction of R,oj), divided by w, which would give the double-layer capaci-
tance at the high frequency limit versus the log of the frequency Again, values of R~otother than
the correct one were used Figure 7 shows that the high frequency hmlt is distorted, but it is still
possible to obtain the value of Cat reasonably well, as well as the imaginary admittance con-
nected with the Warburg term, for frequencies at which Cat does not play any role
Copper
Among the vanous electrochemical systems for which modeling programs have been devel-
oped in our laboratory, a rather complicated one concerns the behavior of copper In the absence
of oxide films The case of copper in acidic, non-complexingsoluUons has been studied by many
workers [ 6, 7], who have shown that two electrode reactions
{ |
-
-.:-.- . - , ~ I# 9 ,
"= =1o -e.. 'i"
/./" %1
ui i .,'- .-'- II
9-'8 "-5 -4 ~i -2
LOG CURRENT DENSITY. A/om 2

FIG l - - C u r r e n t - p o t e n t m l curves o f a redox electrode for two dtfferent C o J C , ~ rattos Rate constant k
= 10 -~ c m / s ~ = 0 0 l cm D t f f Coeffs = 10 -~ crne/s
Cu = Cu + + e - (9)
and
Cu + = Cu ++ + e - (10)
take place at the electrode A similar situation is believed to occur m solutions containing large
concentrations o f c o m p l e x m g agents, such as ammonia, although detailed electrochemical stud-
les of this system have not been published [8] Since m our laboratory there has been a long-
standing interest m various aspects of the corrosion of copper-base alloys m ammonia, it was
considered useful to develop a computer modeling program which could produce polanzation
and impedance data for reactions ( 9 ) and ( 1 0 ) m ammonia complexmg solut]ons Since the
reaction order of ammonia m the rate determining step ( R D S ) for both reactions is not known,
the scheme adopted considers as RDS the following equations
Cu + aNH3 = C u ( N H 3 ) + + e - (11)
and
C u ( N H 3 ) + + cNH 3 = Cu(NH3)~ + + eNH3 + e - (12)
and the operator enters the coefficients a, b, and d as arbitrary values, subject only to the
a. s
9 I
- ~ . ~:
I
-2. s
o.,,,..,f
J*@- I
-z. o
I
-a. s
t
-a. a
i
5
LOG CONCENTRATION, mol/L

FIG 2--Concentratton o f the oxMtzed ( Cox)o and reduced spectes ( Crcd)o at the electrode interface as a
functwn o f potenttal for the same electrode systems as gJven m Fag 1 Index I ( Cox)b = ( C ~a)b = 0 1 M Index
2 (Cox)b= 0 1 M, (Cr~d)b = 00I M
avadabdlty of the stablhty constants of the relatwe ammoma complexes [ 9,10], so that a, b, and
c can vary between 0 and 2, and d and e between 0 and 5 Stolchlometry &ctates that (b + c)
equals (d + e), and either c or e equals zero
The total concentrations, complexed and uncomplexed, of the two copper species m solution
(written in round parentheses) can then be expressed as a function of the activities of their
uncomplexed ions, written in square brackets, and of the ammonia concentration
2
(Cu +) = [Cu +] E UkINH3]k (13)
0
and
5
(Cu ++) = [C u++] Z Vk[NH3] k (14)
0
The actlvmes [ Cu + ] and [ Cu ++] are important, because they appear m the Nernst expressions of
the eqmhbnum potentmls, where their standard values are 520 mV and 159 mV versus NHE,
respectwely
P o l a n z a t t o n C u r v e s - - T h e steady-state polarization data can be calculated by solving a system
of four first-degree equaUons, two of which are the Tafel equanons for the current densmes 11
and t2 corresponding to reactions (9) and (10) and denved from the general expression (Eq 1),
9, :/ ",, f :
....'><,,\ .....Y
n. t /" ] li~" r - - - ~
i "% -
w ~ i do ,I~ "~'~s -.'5 .o
LOG ELECTRODE RESISTANCE. /l*cm a

FIG 3--Zero-frequency electrode resistance as a funcnon of potennal for the san,e electrode systems as gtven
m Ftg 1 (Riot = total. Rot = charge transfer. Rd,er=dtffuston reststance) Index 1 (Cox)b = (C~d)b = 0 1 M
Indo: 2 (Co,,)b = 0 1 M. (Cr~)b = 0 01 M
while the second two descnbe the transport in the diffusion layer of thickness 6 and are derived
from Eq 2, taking into account that Cu + ions participate in both reactions The four equations
therefore are
[ {aiFE~
q = k+FtNH3] ~ lexp/~] (15)
Uk[NH3], e x p ~ ~ ) exp RT
0
(Cu+)o [ ot2FE~
12= Fk'~Ub[NH3] b+c 2 exp~)
E Uk[NH3]*
0
[ FE~ (Cu++)o
exp( (I-a2)FE]IRT ]J (16)
- exp/-'R--T-} ~ V,[NH3]*
0
DIF
t, - t~ = - - 7 [(Cu+)~ - (Cu+)"] (17)
and
D 2 F , , ~ ++.
12 = - - - 7 [ f L u )o - (Cu++)b] (18)
--5
:ll -15 112 jHIz

C
0 E'- 0 mY
-2D
" E! E - 1 D O mV
N ..~ ~) E-20O mV
* a. i t a I I I
o n 1o 1. m 2n am Jn 4o
Z" (:C~*om~')
FIG 4--Impedance of the electrode system gtven m Ftg 1 ( C o x / C ~ = 1) at three dtfferent electrode
potenttats R ~ = 5 f~ • cm z, Cd~ = 30 ~F/em e
In the descnpUon of &ffus~onal transport, it is assumed that all Cu + complexes have the same
diffusion coefficient Dr, and all Cu ++ complexes the value D2. The concentrattons tn the bulk of
the solution are marked with the subscript "b," the ones with index 0 correspond to the electrode
interface.
In conclusion, the operator, after selecting the RDS of the two reactions, must define the
composttlon of the solution by entering [NH3 ]b, (Cu +)~ and (Cu ++~o, the dtffuston condtttons
by entenng the value ofr and the charge transfer kinetics by entenng the forward rate constants
k~ and k~ The values of the dtffuston coefficients and of the symmetry factors al and a2 are also
arbitrary, but our practice has been to fix them beforehand Both a's are taken as 0 5, and whtle
the dtffuston coeffictents DI and of free ammoma D~r are assumed to be 10 -9 m2/s, D2is set at 0 8
X 10 -9 mZ/s, in accordance with the experience that divalent ions m general diffuse more slowly
than monovalent tons
From the solution of the 4 • 4 matrix generated by Eqs 15 to 18, where the four unknowns are
J,, t2, (Cu+)o and (Cu++)o, it is possible to ~alculate at every electrode potential the parttal
current densmes t~', t~-, ~" and t ; of the two electrode reactions, as well as the total current, to
obtain the concentrations at the electrode surface of the two ,onlc specws and, as a hnk to the
~mpedance dmgrams, the values of the total, charge transfer, and diffusion reststances at zero
frequency These quantities can be obtained both for a bulk solution composttlon where the
metal is m eqmhbnum w,th respect to both electrode reacUons (whtch m aqueous ammonm,
corresponds to having practically all copper ions m the monovalent form), as well as m solutions
made mainly of cupric complexes, in which copper metal is known to undergo rapid corrosion
It should be pointed out that the same program can be apphed to uncomplexed solutions not
containing ammonia (m th]s case, of course, the RDS are reactions ( 1 ) and (2)), but also to an
I F 1" T '11"
C >Cdl
5
%./
~ C~~<cdl
ID 5 ,,IO 15 2D
Z Cn*em z)
FIG 5--Effect of uszng dtfferent values for Ca) to deconvolve the faradazc branch
electrolyte not contammg any copper In thts case, at any electrode potential selected, both
electrode reactions can only proceed in the anodlc &rect~on
One of the advantages of this modeling approach is that adding detads for a more reahstic
description of the phenomena ~s m general not too difficult, and often entads very httle cost in
terms of computation times An ad&tlon, which we have implemented, concerns the transport
ofammoma m the &ffuslon layer the preceding treatment ignores the posslblhty that an ammo-
nm gradient may be present For instance, dunng catho&c deposmon, NH 3 is transported to the
elecrode by the Cu-NH3 complexes and, when copper metal Is being &ssolved, NH3 ss being
consumed at the electrode to form the Cu-NH3 complexes Therefore, lfzj or z2 are posmve, an
reward decreasing concentratson of ammonia ss required to provsde the NH3 which goes into the
complexes, and vice versa NH3 will be larger at the electrode if the currents are negatwe When
l t and z2 have opposite stgns, the two transports tend to compensate each other, and the ammo-
nm gra&ent is small In parhcular, at the corrosion potentml 1 tool of Cu ++ flows in and 2 mol of
Cu § flow out Smce the average number of NH3 cawed by Cu § is about 2 and that cawed by
Cu ++ ~s about 4, close compensauon results
If we assume that all Cu § species have the same d~ffus~oncoefficient Dl, and the Cu ++ species
D2, their gradients wdl be constant The NH 3 gradient, however, ~s not constant, since m more
concentrated NH3 the average number ofNH 3 carried is larger than m more &luted ammonm In
order to take that into account, the following approximate method for calculating [NH3] at the
electrode by successive approximations has been developed
In the bulk of the solution the ammonia concentratton [NH3]b is constant and known After
calculatmg z~and z2 by solving the 4 • 4 matnx for constant NH 3 m the &ffuslon layer, the flux
ofammoma at the bulk end of the &ffuslon layer, cI,b, reqmred at steady state, can be calculated
by mult~plymg the average number of NH3 cawed by Cu + and Cu ++ by their respecuve currents
t | . | t
R~'Rwl R~<R=I
N --113 -
--15
il'$ ,~ J" I t "" l
- O 5 10 15 213
Z" Cfl*cm
F1G 6--Effect of using different valuesfor R~ol to deconvolve the faradaw branch
':I't, = - --~
{2 E,IU,[NH3]{,
o
2
X , U,[NH3]{,
(/1__12)..i '
E ,1V,[NH3]~
05
X , V,[NH3]~,
12 1 (19)
0 0
The concentration profile is then hneanzed up to t5/2 The ammonia concentration there 1s
[NH3]~/2 = [NH3lb 2DN (20)
where D N Is the ammonia &ffuslon coefficient The value of [NH316/2 is then introduced in a
formula like Eq 19 to obtain 4,~/2, which in turn, using a formula hke Eq 20 can give [NI-{3]o, the
ammonia concentraUon at the electrode The new value of [NH3]o is used to solve again the 4
• 4 matnx, giving new values for Ii and 12 The process is repeated until no further changes
occur Since the values calculated at a certain electrode potential E are used as starting vaues for
the next E, dlffenng only by 1 or 2 mV, very few iterations are required, and the [NH3] flux can
be estimated with httle increase m computation time
Additional comphcatlons occur m the case of oxygenated solutions, which are often used in
stress corrosion cracking expenments, where no monovalent copper is present in the bulk of the
solution, since it reacts with the &ssolved oxygen In spite of the more comphcated transport in
the diffusion layer [ 11 ], which generates a system of equations of degree higher than three, ItS
n u m e n c a l solution requires a very modest increase m computation t~me
As examples of the data obtainable from the calculanon of the current/potentml curves,
| ! I | |
-a R SUBTRACTED
............ R~R~l
-4 ~ R . R ~ I
._...___R~R~ 1
I I
-4 -2
Io 9 FREQUENCY. Hz
FIG 7--hnagmary electrode admtttance (after subtracting R~o,) dtvtded by w as a functton of frequency
Htgh frequency Ilmtt is Cm Subtraction of etther htgher or lower value of R~o=has about the same effect in
dtstortmg the curve
which precede the computation of the impedance spectra, Fig 8 shows the case of an ammoma
solution of non-equlhbrlum composmon, showing not only the total current density as a func-
tion of the electrode potential, but the currents due to reacuons ( 9 ) and (10) separately, as well
as their partial currents The changes m electrode resistance wtth electrode potentmls, and the
effect of varying the diffusion layer thickness on the relative importance of charge transfer and
&ffuslon, are illustrated in Fig 9
Impedance Spectra--For an arbitrarily chosen electrode potential E, the faradam admittance
can be calculated, by differentiating Eqs 15 to 18 under the assumption of small perturbations,
and &sregardmg the effect of the smusmdal signal on the ammonia concentration, since it is in
general present in large excess The expression, however, is rather complicated, since the two
reactions do not simply occur in parallel, but are linked together through the Cu + concentration
The four &fferentmls which correspond to the schematic Eqs 3 and 4 are
F + tT
All = ~ - ~ ( l l + II)AE-- (Cu +) ACu+ (21)
F + d lz ACu++ (22)
at2 = ~ 02 + ~ ) a E + ~ aCu +
(Cu ++)
tanh (~ ~ l l )
a ( C u +) = F jVj~l~ (All -- A12) = e l ( A l l -- AI2) (23)
i
-II~
. .-"-"~,~ . ._
"" ~X" :(Z )I /
.......- /
ic cu+ ....
..J l . Id''~ II - I ~ '~

!,1 -15 --B -4 -a - -1~ -
LOG CURRENT DENSITY. h/cm ~'

FIG 8 - - T o t a l current current due to rear/tons ( 9 ) a n d ( 1 0 ) , as nell as all parttal currents f o r C u m 10 M
N H ~ Concentratwns tn the bulk Cu + total = 2 • 10 -~ M, Cu ++ total = 0 1 M, 6 = 0 12 c m R a t e constants k t
= 2 48 e m / s , k2 = 2 21 • 10-4 c m / s
and
tan,,(, {24)
A(Cu ++) = F jD~zw At2 = P2AI2
where P~ and P2 are complex numbers Simple algebraic mampulatlons on these four equations
yteld the farada~c admtttances for the two reacttons as well as the total one The operator must
provide values for the double layer capacitance and for the solution resistance, so as to generate
the impedance spectrum for copper immersed in the soluUon of assigned bulk composmon, with
the assigned diffusion layer thickness 6
For the sake of brewty, we wdl illustrate the results of the impedance calculations wtth only
two examples Figure 10 is a Nyqmst plot showing how the impedance vanes with potential, for
the same system which produced the data m Fig 8 One of the more interesting pomts here is
that, at suffioently negative potentials, posmve values of the imaginary ~mpedance can be gener-
ated, without the need of postulating an adsorption process
Corrodmg Metal
In companson with the preceding example, the program generating the impedance spectra of
a corroding metal is very simple We assume that the cathodic reaction has a RDS involving one
electron, with a reactant in solution, which is meant to be e~ther 02 or H + (or O H - ) , while the
anodlc reaction ,s metal oxidation, again w,th the RDS revolving one electron It Is also assumed
that the backward reactions can be neglected
1-21~
. . . . . I VP, "1
d 0 0,5 1.0 1.5

LOG ELECTRODE RESISTANCE, N*c:m 2
FIG 9--Zero-frequency resistance as a function of potential for the electrode system given in Fig 8for two
values of the diffusion layer thwkness, calculatedfor two rotational speeds of a rotating disk electrode ~ = 0 0124
and 0 0062 cm
Polartzatwn Curves--The values to be given are the following number of equivalents per
mole m the ano&c and cathodic reactions & and zc, diffusion layer thickness (3, diffusion coeffi-
cient D of the catho&c species, concentration Cb in the bulk of the cathodic species, and cathodic
rate constant kc It is also assumed that the transfer coefficients aa and ac are 0 5
If only one set of input parameters has to be considered, the corrosion potential Eor is arb]-
tranly set equal to zero, so that choice of any other value implies immediately either ano&c or
catho&c polanzanon However, if it is desired to compare more than one set of input values, so
that their polanzaUon curves are properly placed with respect to each other In the voltage scale,
the computations can be carried out so that, while a reference set has Eo~ = 0, subsequent sets,
where, for example, the concentration of the cathodic species Cb or the diffusion layer thickness
is different, will have Eoc different from zero, displaced according to the effect of the altered
input parameters
Neglecting the backward reactions, the anodtc current density is given by
[ oqFE~
,+ = z, F k , exp~----R-~ ) (25)
and the cathodic current is
acFEI (26)
i- = zr162 exp - RT )
where Co is the concentration of the cathodic species at the electrode Transport in the &ffuslon
layer gwes
.... -2~mV
.~ -291 mV
%J
9 r149
'%. ...... _~..s
" _ _ . - " ;% .
Z/
i',,I -5 "'" tojb o~latt j" "'"
5 10 15 20 25 20
Z" Cfl*cma)
FIG l 0--Impedance o f electrode system gtven tn Fig 8 at various potentmls E = 291 m 1/versus N H E Is the
corroston potenttal Cdl = 40 ~ F / c m 2, Rsol = 5 fl • o n e
_ zr DF
l - ~- [ C b - C o ] (27)
At open circuit ( E = Eor --- 0), the anodic rate constant ka ]s obtained by equating (25 ) to (26)
and using (27) to ehmlnate the concentration Co at the electrode
k. = zckcCbD (28)
za[ D + k ~ ]
Under the assumption of small perturbations, the faradalc impedance can be obtained by
differentiating Eqs 25, 26, and 27 and proceeding as outhned above in the conceptual frame-
work section
AI = 2 ~F [O/a/+ ~- O/cl-]AE _ ~ o A C (29)
and
A C -- zcDF Al- (30)
The zero-frequency faradalc impedance is then

>
V-
ttl
LOG CURRENT DENSI TY. Alomz
FlO 1l--Current/potenttal curvesfor a corroding electrode for two values of the dtffuston thickness Bulk
concentratton of the cathodw spectes= 2 • 10 -4 M
RT z~FCo + l- -~
(31)
Zv=o = 7 [ a . t + + aj_lzr + ,+_
lfdlffUSlOnal processes can be neglected--that is, lf(z~DFCo) ts much greater than (l-/~)--Eq
31 is simplified to
RT 1 (32)
Zv-o F [aJ + + ad-]
which is the usual expression of the charge-transfer resistance Vice versa, when (zcDFCo) is
much less than (l-d0 , Eq 31 becomes
RT (33)
Zw0 = Fl+
The cathodic current, now in hmmng condmons, does not appear m the expression for the
impedance
-I00
C
1.4"/ 14~
,, , I013 mV
9 ~. 37 mV
4~ OmV
-10!:3 mV
C - 1 5 0 mV
I I I I I I I
Z" tq~-cm 2
FIG 1 2 - - I m p e d a n c e o f the electrode syslem given m Fig 11 (6 = 0 002 cm) at various potentials The
corrosion potential ts 3 7 m V Cdl = 30 t~F/cm e R~o I = 5 ~2 X cm e
Figure 1 l shows polanzauon curves for a corroding electrode, calculated for two values of the
thickness iS, everything else being equal In the example, the concentration of the catho&c
species is 2 • 10 -4 34, simulating an aerated solution Depending on stlrnng, when 6 is 200 #m
( Curve 1 ), at E~o~the rate is controlled by oxygen avallab]hty, while when 6 is 20 tLm (Curve 2 ),
the rate is controlled by the ano&c reacUon Stlmng also affects the corrosion potential
hnpedance Spectra--As m the preceding example, once partial currents and mterfaclal con-
centraUons are computed, to obtain the frequency dependence of the impedance, Eq 7 is substi-
tuted for 6[D m Eq 31 The final result is
2RT[ z~FCo+ t-(SR-j~) ] (34)

Z = --F--- [ad + + ad-]z~FCo + t+I-(~ - J ~ )
where
Jt - ] ~ = [smh/3 + s m / 3 ) - j ( s m h / 3 - s m / 3 ) ]
(35)
2~ [cosh/3 + cos/3]
and
/3 = 6 ~ (36)
As m the previous examples, the values of Cdt and R~, have to be entered by the operator m order
to simulate the spectra which would be produced by a galvamc cell
i . i i i
-1. n
E - - 1 5 0 mV
(0
.'=4
el
I'~ -1.5
>- E- 0 mV \\
\8
%
E" 3 7 ,mV ~ k
9 -2.13 _ i t% 1 , , ,
"x-
0 E,- I O0 m V
,| , , , l ,J , , )i ,
" - i ..p.. 5 ,
I ! ~L 1 I
-4 -2 0 2 4
1o 9 FREQUENCY, Hz
FIG 13-- Ratto of the tmagmarv admittance to real admtttance dlvtded b v o~for the same tmpedance data of
Ftg 12
Using the same input parameters as one of the curves in Fig 1 1, the impedance spectra
calculated at vanous potentials are shown in Fig 12 Changes in the charge transfer loop, as well
as the development ofa dllTuslon loop, can be recognized Even more clearly, the existence of
one or two relaxation times, and their evolut:on w:th potential, is v:s]ble m F~g 13, where the
electrode imaginary admmance Y" divided by c0Y' is plotted as a function of frequency Here,
the low frequency time constant :s determmed by the dlffUs:on process, wh:ch becomes impor-
tant at cathodic potentials The high frequency ume constant, on the contrary, ~s proportional to
the product Ca, • Rot Keeping in mind that C d , 1S constant, the changes show that the charge
transfer resistance is the greatest close to the corroston potential, and tends to decrease if the
electrode :s polanzed in etther dtrecuon
Summary and Conclusion
The preceding examples have shown that an approach to impedance modehng based on
electrode kinetics is implementable on desktop computers and does not require large invest-
ments in either software or hardware The time necessary to generate polarization curves and
impedance spectra can be contained within reasonable hmlts, of the order of a minute at most,
even for the most comphcated systems such as copper m aqueous ammonia
The obv:ous advantage of such an approach is that, since the meaning of the input quantmes ~s
known, matching the calculauons of the model to experimental data can contribute s~gnlficantly
to the understanding of the system Also, considerable insight can be gamed by examining how
the impedance spectra vary when the values of the various input quantmes of the model such as
concentrations, rate constants, and the d:ffusion parameters are vaned
References
[1 ] Boukamp, B "Computer Aided Acqmsltlon and Analysis of Corroston Data," Proceedings of The
ElectrochemtcalSoctety. Vol 85-3, Penmngton, NJ, 1985, p 146
[2] Epelbom, l . Gabnelll, C, Keddam, M, and Takenoutl, H, Comprehenstve Treattse on Electrochemts-
try, Vol IV, Plenum Press, New York. 1981, p 151
[3] Genscher, H, ZettsehrtftjChr Physlkahsche Chemte. Neue Folge, Vol 1, 1954. p 278
[4] Schuhmann, D, Comptes Rendus de l',4cademte des Scwnces. Pans, Vol 262C, 1966, p 624
[5] Sluyters-Rehbach, M and Sluyters, J H m Electroanalytwal Chemtstry. A Bard, Ed, Vol 4, Marcel
Dekker, New York, 1970, p 1
[6] Mattsson, E and Bockrls, J O'M, Transacttons of the Faraday Socwty, Vol 55, 1959, p 1586
[7] Bertoccl, U and Turner. D R , Encyclopedia of Electrochemistry of the Elements. Vol II, Marcel
Dekker, New York, 1974, p 383
[8] Randles, J E B and Somerton, K W. Transacttons of the Faraday Socwty. Vol 48, 1952, p 951
[9] Smith. R M and Martell, A E. CrmcalStabdttyConstants. Vol 4, Plenum Press, New York, 1976
[ 10 ] Bertoccl, U and Wagman, D D , Standard Potenttals m Aqueous Soluttons, Marcel Dekker, New York.
1985, p 287
[11 ] Bertoccl, U . Electrochlmlca Metallorum, Vol 3, 1968, p 275
D a v i d B. Anderson 1
Evaluation of Corrosion Data: A Review

REFERENCE: Anderson, D B, "Evaluation of Corrosion Data: A Review," Computer Model-
mg m Corroston. ASTM STP 1154, R S Munn. Ed. American Society for Testing and Materials.
Philadelphia, 1992, pp 162-173
ABSTRACT: The needs, objectives, and techmques for evaluation of material property data are
reviewed with respect to their apphcablhty to certain types of corrosion data Examples of ap-
proaches that have been taken for data generated from exposures in natural environments and
industrial processes are described to dlustrate methods used for charactenzlng the materials, the
environment and exposure condmons, the measurement techniques used to descnbe these compo-
nents, and the delineation of controlling factors with respect to specific forms of corrosion
KEY WORDS: corrosion, evaluation, data classification,atmospheric corrosion, electrochemical,

pitting, crevice corrosion, field testing
The basic concept of scientific data evaluation is defined as the process of estimating the
quahty or reliability of the data using documented procedures In basic terms, the primary
funcUon is to turn chaotic experimental data into useful knowledge The key steps revolved m
data evaluation are listed in Table l Implementauon of these steps involves the appraisal and
assessment of the value, quality, and integrity of numerical and factual data which have been
generated by experimentation, by theoretical analysts or mathematical models, or by any other
appropriate means [ 1 ] This process includes the cntlcal assessment of the validity of data and
related reformation, the materials and test procedures used and associated errors, resolution and
reconciliation of disagreements in conflicting data, correlation of data m terms of various control-
ling parameters or using theoretical or emplncal equations, and companson of experimental
results with theoretical predictions or with results from generahzed empirical correlations [ 2 ] It
may also include recalculation of derived results, comparisons with service experience, selectwe
acceptance, statistical manipulation and modeling, and assignment of probable error or rehabd-
lty qualifier The goal of this process is to seek improvements in both the data quahty and
integrity and the methods used for generating data, and to select best values that are internally
consistent and cover as wide a range of each of the controlling parameters as possible Ap-
proaches vary from staUstlcal analyses and subsequent modeling in relation to estabhshed soen-
tlfiC pnnclples to the development of expert consensus with a conscious group effort to ehmlnate
bias m data selectton and interpretation This latter approach, often accomphshed through
research groups, technical committees, data centers and boards of editors and authors, places
emphasts on comprehensive judgmental appraisal to determine the quahty, rehabdlty, and ade-
quacy for a speofied purpose or application When applied to corrosion data, these appraisals
often center on comparisons with known service experience and all too often do not gave ade-
quate consideration to the soentlfiC pnnclples involved
Stnct guldehnes have been estabhshed for qualification of physical and mechanical property
data for enganeerlng matenals as a step in the evaluation process and classifications such as
typical, mtmmum, handbook, or design data have evolved [3] Other qualification schemes
t National Institute of Standards and Technology, Gaithersburg, MD 20899
162
Copyright9 1992 by ASTM International www.astm.org
ANDERSON ON EVALUATION OF CORROSION DATA 163
TABLE I--Process of data evaluation

Critical assessment of the vahdlty of the data and related
9 Step 1--Vahdatlon reformation-materials, lest procedures, etc
9 Step 2--Resolution Reconcdmtlon of disagreements in conflicting data
Relate to controlhng parameters
Use of theoretical or empmcal equations or models
Comparisons of expenmental data with theoretical
predtctlons
9 Step 3--Correlauon Comparison with service experience
9 Step 4--Assignment of best value
consider categories of hmlted use data, qualified data, and highly qualified data [ 4 ] Classifica-
tion schemes and quahty indicators are important to the majonty of data users who are not
experts in data measurement and are not Inclined to expend the time and effort to determine the
quahty of data from onglnal sources but remain challenged to assess nsks for matenals options in
structural designs The importance Is further enhanced by the frequent lack of adequate docu-
mentation in avadable data compdatlons for independent data quality determinations
Corrosion is generally relegated to a category of"performance properties" where there are few
gmdehnes for evaluation and classification with the resulting acceptance of corrosion data of
unknown or questionable value The complexmes of the time-dependent corrosion matenal-
environment interactions and the multitude of corrosion processes and manifestations tend to
&scourage attempts to undertake the type of rigorous corrosion data analysis needed to estabhsh
clear guidelines for data classification and to the defining of corrosion hmlted hfe prediction
design data in relation to cnUcal applications
Although a number of standard corrosion test procedures have been developed, results are
often controversial, reflecting differences of oplmon as to which test parameters and data are
critical for any given application Corrosion tests are often designed with overly aggressive
environments selected to accentuate specific corrosion mechamsms (e g, stress corrosion crack-
rag, pitting, corrosion-fatigue) in one class or subclass of matenals, often under the guise of
"accelerated tests" whose predictability of performance for longer term exposures under less
stringent conditions ~s often suspect and can result m rejection of vmble materials for a gwen
application Despite stnct guldehnes for specimen preparation, test environment, and exposure
conditions, there is a general acceptance of sigmficant vanability between multiple specimens
exposed under what are considered tdenttcal exposure condmons (e g , the discussions on Stgmfi-
cance and Use in ASTM G 16-88) This is frequently evident in the vanabfllty of results
obtained from traditional round-robin tnals of new test methods and IS reflected in the Precision
and Bias statements which are part of most ASTM standard test methods The degree ofvarlabd-
lty IS often considered to be dependent upon the seventy of the environment relative to the
inherent corrosion resistance of the material being evaluated and the dominant form of corrosion
revolved For example, (1) the femc chloride pitting test (ASTM G 48~ prowdes more
consistent results with highly pit resistant and pitting prone alloys than for alloys ofmtermedmte
pitting resistance, and (2) the 3 5% alternate immersion test for high strength aluminum alloys
(ASTM G 47-90) identifies excellent reproduciblhty for materials of high and low susceptlbthty
with significantly higher vanabihty for matenals with intermediate susceptlbihty Perhaps this
varlabihty ~s to be expected for time-dependent tests involving mhomogeneous materials ex-
posed in equally lnhomogeneous environments Equally plausible is a realization that the critical
factors for designing reproducible corrosion tests are not well defined One could also question
whether reproducibdity of test results should be a pnmary goal of any standar&zed corrosion test
procedure or whether we should accept the vanabdtty and study the data statlstmally to try to
gain a better understanding of undefined factors and thus provide guidelines for data evaluation
Evaluation Techniques for Corrosion Data

The hmltatlons of data used to quantify environmental interactions with engmeenng mate-
nals challenge researchers to apply established data evaluation techmques developed for me-
chanical and physical property data The challenge becomes particularly difficult when assessing
data generated from exposures m natural enwronments and industrial process streams Despite
the lack of guldehnes, corrosion researchers have been persistent m addressing the challenge
using a variety of evaluation procedures which tend to follow common themes These evaluation
processes have generally evolved over a number of years, prompted by the need to define and
measure critical parameters which are considered relevant to engmeenng applications The
studies described below illustrate a variety of evaluation techniques and were selected to serve as
guides to aid researchers in establishing evaluatlon processes for different types of corrosion data
Atmospheric Corrosion
Systematic atmospheric corrosion testing under ASTM aegis began m 1908 [ 5 ] Early studies
emphasized material comparisons, followed by attempts to develop laboratory tests to simulate
atmospheric corrosion processes Although the latter have helped isolate specific atmospheric
factors, they have been singularly unsuccessful in providing rehable predictions of corrosion
over a wide range of exposure condition in natural atmospheres
As standard test methods and test sites evolved, voluminous data compdat~ons were acquired
and evaluation centered on statistical data analyses based on alloy composmons, particularly
with respect to the growing family of low-alloy weathenng steels These challenges have been
addressed by Larrabee and Coburn [ 6 ], Legault and Leckle [ 7], Townsend and Zoccola [8] and
others and they identified the need to
( 1 ) Assess the differences in seventy of corrosion at different exposure locaUons

( 2 ) Define mathematically the changing slopes of the corrosion rates as a function to expo-
sure time
( 3 ) Identify and measure environmental parameters
Typmal data relating to needs 1 and 2 are shown in Fig 1 [ 7] Dehneatlon ofcntlcal factors
for data evaluation have evolved from these studies As examples, Table 2, from ASTM G
92-86. hsts cntlcal atmosphenc factors and techniques for monltonng them, while Tables 3 and
4 detail an atmosphere classification scheme based on sulfur dioxide and chlonde deposition
[ 9] Use of these gmdehnes to develop predictive methods for long term corrosion performance
is detailed in ASTM G 101-89 This guide includes a linear regression model for extrapolation of
short-term exposure data based on loganthmlc plots of corrosion losses versus time These plots
are good fits as straight lines and can be represented by equations in slope-intercept form
log C = A + B l o g t
where
C = corrosion loss,
t = time, and
A and B = constants
6
/
O
M.
z 4
O
w
t/I
O
~3
O
U
m u
I.-
STATE COLLEGE,Pa.o(RURAL SITE~ ,O

1'---'--O
I I I I I I I I I
0 2 4 6 8 10 12 14 16 18
YEARS
FIG. I--Changeinre~tiveatmo~herictestsitecorrosivi~ withtime[7].
References for the derivation of the A and B constants are given in ASTM G 101. This Standard
Guide also details a method for determining corrosion indices based on chemical compositions
of the steels of interest. Figure 2 provides an extrapolation of 10 year data to a projected 50 year
exposure for A242 steel in five industrial atmospheres. The corrosion rates indicated by these
generalized indices are based on freely exposed coupons where corrosion occurs on both the top
and bottom surfaces. Thus it is difficult to translate these data to predict performance of struc-
tural components where a variety of exposure conditions are incurred.
These studies provide a valuable record of the changing approach to evaluation of corrosion
data from exposures in natural environments as better understandings of the material/environ-
ment interactions evolve. Early studies emphasized comparisons of simultaneous exposures in
test sites characterized as "marine", "industrial", or "rural". Subsequent studies addressed iden-
TABLE 2--Monitoring devices to characterize corrosivity

of natural atmospheres (ASTM G 92-86).
Atmospheric Factor Monitoring Device
Sulfur dioxide Sulfation plate
Chloride ion Wet candle
Temperature/humidity Hydrothermograph
Precipitation Rain/snow gauge
pH Periodic samples from rain/snow gauge
Time of wetness Cu/Au sensor (see ASTM G 84)
Climatologicaldata National weather service
TABLE 3--Classtficatwn of atmospheres (ISO/TC 165) [9]

Atmosphenc Factor Environmental Classes
Ttme of wetness T l-T5
%time wet
Hours wet per month
Sulfur dxoxlde P0-P3
Deposition rate (mg/m2/day)
Chlorides S0-$3
Deposmon rate (mg/m2/day)
tlficaUon of critical atmospheric factors and, subsequently, techmques have been developed for
m sttu measurement of these factors With the important data generated using these techmques
our understanding of atmosphenc processes has improved as has our abdlty to evaluate atmo-
sphenc corrosion data relatwe to a broad range of atmospheric condmons
Plttmg of Stamless Steels

A recent study by Marek [ 10] analyzed data extracted from over 40 pubhshed reports in the
academic hterature relaUve to corrosion ofnon-sensmzed, non-stressed austenmc stainless steels
exposed to aqueous chlonde soluUons The goal was to undertake a comprehenswe evaluaUon to
identify the parameters that describe localized corrosion behavior and the major variables re-
volved The predominance of the compded data related to electrochemical parameters for pit-
ting corrosion (e g, breakdown potential Eb [also called rupture or pitting potential] and pro-
tectlon potential Ewot [also called repasswatlon potential D Eb represents the potenUal of a
passwe electrode above which the passwe film breaks down locally and stable pits develop Eprot
represents a potentml value below which the potentml of an electrode must be lowered to
repasswate existing p~ts The values of these potentmls are often taken as m&cators of the
relatwe susceptlbdlty of materials to pitting m aqueous environments Both of these parameters
can be obtained using &fferent electrochemical test condmons or techmques, and there are
substantial &fferences m the reported values obtained by different techmques or test conditions
The Eb data, collected from many different sources, were examined to attempt to identify
correlations with chloride ion concentration, temperature, and pH as independent variables A
TABLE 4--Atmosphertc corroswn classesfor unalloyed steel (ISO/TC 165) [9]

T2 T5
S0-S 1 $2 $3 S0-S 1 $2 $3
P0-P 1 1 2 3-4 4 5 5
P2 1-2 3-4 3-4 5 5 5
P3 2 3 4 5 5 5
Class Corrosion Rate, mm/yr
1 05
2 0 5-2
3 2-10
4 10-35
5 >35
2000
1OOO
s 8
sss S . U.K
500 s@S ,~ 9
300 ,,sss S ,,,,,,,.s"
200
~' SO00
lOO / / ----.-"~ oo ~ .-" u.s.
5o ~ "~'s''~
3o
20
L I I I Ii1~, l ,
101 2 3 5 10 2 0 3~0 5 0
EXPOSURE TIME, YRS.

FIG 2-- Projected corrosion penetrations for ASTM A242 Type 1 steel m mdustrtal enwronments (ASTM G
101-89) Test sites are ( 8 ) TeesMe, UK, (9) Battersea, UK, ( 10) and ( 11 )Ptttsburgh, PA, ( 12 ) Bethlehem,
PA. and (13) Newark, NJ
strong effect ofchlonde concentration ofa loganthmlc relationship was observed with a negative
coefficient between the breakdown potential E b and the loganthm of chloride concentration
This is illustrated in the X - Y-Z scatter plot shown m Fig 3, which includes temperature as the Z
vector Figure 4, limited to data from near neutral solutions at room temperature, shows a clearer
correlation with chlonde concentration The results of these and many other hnear and multiple
regression calculations used to evaluate the compiled data led Marek to the following significant
conclusions
1 The compilation and retrieval of the type of data examined present a serious problem
because of the nonstandardization of test conditions and the large quantity of possible
alloy and environmental variables
2 The available data were not systematic and comprehensive enough to determine general-
lzed quantitative relationships between the vanables and electrochemical parameters for
ptttmg corrosion
3 A substantial fraction of the available data were found to be deficient w~th respect to the
completeness of the descnptlon of the matenals and test condlUons
Clearly, these deficiencies m a data compilation of this type are impediments to a successful
evaluation attempt
In-Plant Coupon Tests

Evaluation of coupon exposures in process equipment is comphcated by a number of factors
Including specimen geometry, measurement of the process environment at the exposure point,
,_1"I
~0.5
0 100
-0.5 ~ m
i!iiIlIll I..................
p [C)
0 0
log CI [M) 1
FIG. 3--Breakdown potentials for Type 316 stainless steel as a function o f chloride ion concentration and
temperature [ 10 ].
variations in the process environment during extended exposure times, and nonuniformity of
exposure conditions for the individual coupons.
An extensive field test program was initiated in 1976 under the auspices of the Metals Sub-
committee of the Technical Association of the Pulp and Paper Industry (TAPPI) Corrosion and
I . . . . I . . . . I . . . . . . . . . . . . "'
0.81-'.~ 9: ...............
,,, ":
9 .................§. ..................: .................~: ................. .."-
:
k, "- : :. " : :
9 ~ i : :
Cl 9d-4. ....... ",r.,j.~..,,, ........ ,................... ~ ................. ~ ................. <..
0.4 .................... :................ = . . . . " ~- .............. : " -
,,, ~ ~ " i "-.~k

~ :" '1~. '~ :
i i i i ":" '
i 9 -.j
0 "'i""":"';";" ......:";'":'":"'":'".".'": ......"":'":"." ......2"".":"'::'~'-

-4 -3 -2 -1 0 1
log CI [M)
FIG. 4 - - L i n e a r regression analysis of breakdown potentials for annealed Type 304 stainless steel as a
function o f chloride ion concentration in near neutral NaCI solutions at room temperature [ 10 ].
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further rep
Materials Englneenng Committee [11 ] Initial tests included 18 alloys exposed in the highly
oxidizing aqueous environments in bleach plant washer vats in l0 cooperating pulp and paper
mills Test racks, using the guidelines of ASTM Standard Method G 4, were prepared with
duplicate specimens of each alloy with each specimen insulated from the test rack and compan-
ion specimens through the use of TFE-fluorocarbon spacers and washers The washers, in turn,
provided a controlled crevice on each face of each specimen Exposure durations in individual
locations ranged from 3 to 16 months and were generally dictated by access dunng scheduled or
unscheduled shutdowns Multiple test racks were exposed and, where possible, racks were re-
moved at different times After exposure, specimen mass losses and depths of pitting and crevice
corrosion were determined
Initial data evaluation concentrated on measured depth oflocahzed corrosion, since this was
the anticipated limiting factor in assessing the relative merits of the various alloys Tuthlll [ 11 ]
reviewed the data relative to ( a ) the relationship between time of exposure and the maximum
depth of localized corrosion, (b) differentiation between the tested alloys using localized corro-
sion depths, and (c) the use of maximum localized corrosion on coupons as a predictor of service
performance Contrary to the original assumption that depth of localized attack (bold surface
pitting and crevice corrosion) would increase with exposure duration, the measured depths of
localized corrosion on Individual coupons bore little relationship with exposure time Statistical
analysis of the data for all 18 alloys showed that while maximum depth oflocahzed corrosion for
duplicate specimens of any gwen alloy exposed at the same time had a high correlation coeffi-
cient, the relationship with exposure period was essentially random It was also observed that
there was little statistical relationship to support extrapolations between seventy of localized
corrosion on the coupons and service life of bleach washers fabricated from the same alloys (Fig
5) and, somewhat surprisingly, there was no clear relationship between specific environmental
variables and the relative seventy of pitting versus crevice corrosion
Subsequent analyses of these same datasets were conducted using a variety of statistical tech-
tuques [ 12,13 ] Standard analysis-of-variance techniques were used to establish the variance of
the data due to specific alloys, paper mills, exposure periods, and duplicate specimen errors
Importance of measured environmental parameters and parameter interactions were assessed by
linear regression analysis Finally, cluster analysis procedures were used to rank a n d / o r group
alloys by relative resistance to corrosion These studies confirmed the earlier conclusion that
incidence and depth of localized corrosion is not a simple function of exposure penod but did
find that localized corrosion could be expressed as a function of specific environmental
vanables
Useful alloy ranklngs were obtained in subsequent tests with welded coupons by companng
totals oflocahzed corrosion depths for all 38 specimens of each alloy after exposure in 19 bleach
plant washers [ 14] The order of merit obtained in this manner was found to be consistent with
field experience Significantly, alloy ranklngs were not consistent with indices based on expo-
sures of similar alloys in seawater [ 15] and illustrate the problems arising when attempts are
made to apply corrosion data from one environment to another
Crevice Corrosion lll Seawater

The w~despread incidence of severe corrosion damage in seawater in areas of metal surfaces
shielded by gaskets, seals, lap joints, pipe threads, fouling, and other deposits, all too often with
unpredictable seventy, has led to extensive studies of geometncal and environmental factors
relative to alloy composition with a common goal of developing reliable evaluation techniques
[16] Test procedures developed by Anderson [ 17] used a statistical approach to study geometri-
cal and alloy composition factors with respect to both oxygen and metal ion concentration cells
with specimen exposures in natural seawater The evolution of the multiple crevice test assem-
9 Washer replaced - drum leaking

E) Age of washer still in service - little or no corrosion observed
1.5
E 1.25
E
i
t-
O
"~ 1.0
0
"D
.N_
-~ 0.75
O
.J
Q.
0.5 9 4 9
~D
a
X
~3
:~ 0.25
1. 1 I I I I
5 10 15 20 25 30
Service Life of Washers

FIG. 5--Service life of stainless steel bleach plant washers compared with maximum depth of localized
corrosion on test coupons [ 11 ].
bly, as shown in Fig. 6, was based on a perceived need for a test that can provide a meaningful
discrimination between various alloys within a relatively short exposure time without external
electrochemical or chemical stimulation. A maximum exposure period of 30 days was consid-
ered a necessity for natural seawater exposures to reduce complications from crevices formed by
fouling organisms and seasonal variations in water temperature and dissolved oxygen. This basic
method has been used in extensive testing programs designed to ( a ) isolate initiation and propa-
gation stages, (b) study seawater temperature effects, (c) assess the combined effects of surface
finish and crevice tightness as a measure of crevice geometry, and ( d ) to quantify the effects of
the ratio of creviced to boldly exposed surfaces. Much of the data scatter observed in early tests
was subsequently shown to reflect the inability to reproduce the same degree of tightness in each
crevice, a critical factor in defining the geometrical conditions for the crevices, more than mate-
rial inhomogeneity at the different crevice sites. Some degree of control of these factors has been
achieved by specifying a controlled torque to tighten the crevice formers and a laboratory-
produced surface finish. The test results, however, relate to these unique conditions and are
difficult to relate to alternative crevice conditions that may be encountered or anticipated in any
given service application.
7mm
, _, -_
I I \~x -r ~//~""'q~"6~ Slot

~~/ ~'~"~-12 ~Plateau
I~ 22 mm_1
2-s ram, ',t._ 17 ..u I
~ll~ mm-l,
ul~ tJ id ~ ~ Llu
T F---%--I . . . . .
t... --I
~ 25.4 mm vl
FIG 6--Mulnple crevice washer (ASTM G 78-89)
The criticality of crevice geometry, within the range incurred in service with gaskets, pipe
threads, seals, etc, has been further defined by crevice modeling studies conducted by Oldfield
and Sutton [ 18], Critical crevice gaps and depths for the most widely used stainless steel alloys
vary with specified environmental parameters which cover the ranges incurred in many cooling
water systems Thus it was clearly shown that evaluation of crevice corrosion data must consider
both the detailed chemical composition of the environment and a precise delineation of the
crevice geometries involved Evaluation of both the initiation and propagation stages of crevice
corrosion are equally important to gaining a better understanding of the corrosion processes
involved Reference ! 9 provides an excellent review of useful test methods
Summary
Corrosion data are dynamic representations of interactions of materials and environments that
can be used to characterize matenal performance and to assess the effectiveness of corrosion
control options The dynamic nature of corrosion data is in contrast to mechanical and physical
property data for engineenng materials which are represented numerically by results obtained
under specified standard test conditions Evaluation of corrosion data requires careful consider-
ation of
(a) the matenal involved, including composition, metallurgical condition, surface condition
and mechanical properties,
(b) the environment and the exposure conditions within the environment with particular
emphasis on the t~me-dependent e n v i r o n m e n t a l conditions at the m a t e n a l / e n v ~ r o n m e n t

interface,
( c ) the corroston test m e t h o d used,
( d ) the m e t h o d s a n d m e a s u r e m e n t t e c h m q u e s used to describe these c o m p o n e n t s , a n d
(e) the d e h n e a t l o n o f c o n t r o l h n g factors with respect to specific forms o f corrosion for the
material a n d e n v t r o n m e n t o f interest
All o f these factors have been addressed, in turn, by a n u m b e r o f researchers, a n d the frutts o f
their efforts can provide i m p o r t a n t guldelmes for e s t a b h s h m e n t o f data evaluation programs to
meet the needs o f the multitude o f corroston data users
References
[1] Barrett, A J , "'On the Evaluatton and Vahdauon of Englneenng Data." Computer Handhng and
Dtssemmatton of Data, Proceedings of 10th Internauonal CODATA Conference, P S Glaeser. Ed.
Elsevier-Science, Amsterdam, 1986, pp 121-125
[2] Toulouklan, Y S, "Twenty-Fwe Years ofPloneenng Accomphshments by CINDAS - A Retrospec-
twe Review," lnternattonal Journal ofThermophys~cs. Vol 2, No 3, 1981, pp 205-222
[3] Northrup, C J M , McCarthy. J L. Westbrook. J H , and Gratudge, W , "Matenals Information for
Soence and Technology (MIST) A Prototype Material Properties Data Network System," MaterJals
Property Data Apphcattons and Access. ASME Pubhcatlon MPD-Vol I, PVP-Vol I11, 1986, pp
167-174
[4] Kotam, M, "Report of Task Group on Accessibility and Dissemination of Data for Science and
Technology," Study on the Problems and Accesstbthty and Dlssemmatton of Data for Sctence and Tech-
nology. CODATA Bulletin No 16, 1975
[5] Coburn, S K , "Introduction," m Atmospherw Factors Affecting the Corroston of Engmeertng Metals.
ASTM STP 646. American Society for Testing and Materials. Phdadelphla, 1978, pp 1-4
[6] Larrabee, C P and Coburn, S K , "The Atmospheric Corrosion of Steels as Influenced by Changes m
Chemical Composmon," in Proceedmgs. First International Congress on Metalhc Corrosion, London,
1962, pp 276-285
[7] Legault, R A and Leckle, H P, "Effect of Alloy Composition on the Atmospheric Corroston Behav-
ior of Steels Based on a Statistical Analysts of the Larrabee-Coburn Data Set," in Corroston tn Natural
Enwronments. ASTM STP 558, American Society for Testing and Matenals, Phdadelphta, 1974, pp
334-347
[8] Townsend, H E and Zaccola, J C , "Eight-Year Atmospheric Corrosion Performance of Weathenng
Steels m Industrial, Rural and Manne Environments," in Atmosphertc Corrosion of Metals, ASTM STP
767, American Society for Testing and Materials, Phfladelphm, 1982, pp 45-59
[9] Dean, S W , "Corrosion Testing of Metals under Natural Atmosphenc Conditions." m Corroston
Testmg and Evaluatton Sdver Anmversary Volume. ASTM STP 1000, American Society for Testmgand
Matenals, Phdadelphm, 1990, pp 163-176
[10] Marek, M . unpubhshed data
[11] Tuthdl, A H , "Progress Report Corrosion Test Results - Phase 1 Bleach Plant C, D, & H Stages,"
Pulp and Paper Industry Corroston Problems~Vol 3, NACE, 1982
[12] Rushton, J D , Gelssler, J J , Heasley, R H , Tuthdl, A H , Edwards, L L, "StatlsUcal Analysis of
the Effects of Chloride, Residual Chlonne, Temperature and Exposure Penod on the Corrosion of
Bleach Plant Materials, Pulp and Paper Industry Corrosion Problems. Vol 3. NACE, 1982
[13] Beetham. M P, "A Statistical Review of Corrosion Rate Values for Twenty-Six Alloys Exposed m
C-D/C, D and H Stages During the TAPPI Phase II Study," m TAPPI Engineering Conference Proceed-
rags. Vol 9, 1982, pp 665-681
[14] Tuthlll, A H , "Resistance of Highly Alloyed Materials and T~tamum to Locahzed Corros|on in
Bleach Plant Environments," Materials Performance. Vol 24, Sept 1985, pp 43-49
[15] Strelcher, M A , "Analysis of Crevice Corrosion Data from Two Sea Water Exposure Tests on Stare-
less Alloys," Matertals Performance, Vol 22, No 5, May 1983, pp 37-50
[/61 Kam, R M , "Crevice Corrosion Testmg m Natural Seawater Significance and Use of Multiple Crev-
ice Assembhes," m NACE Corrosion/88, Paper No 405, 1988
[ 17] Anderson, D B, "Statistical Aspects of Crewce Corrosion m Seawater," m ASTM STP 576. American
Society for Testing and Materials, Phdadelphm, 1976, pp 231-242
[18] Oldfield, J W and Sutton, W H . "New Techmque for Predicting the Performance of Stainless Steels
in Seawater and Other Chloride Containing Environments," British CorrostonJournal, Vol 15, No 1,
1980, pp 31-34
[19] Kam, R M, "Evaluation of Crevice Corrosion," Metals Handbook, 9th ed, Vol 13, pp 303-310
DISCUSSION
Ann Van Orden ~ (wrttten dtscusston)--What is NIST doing in the area o f evaluatton of
corrosion data9 From the content of paper, ~t is clear that th~s ~s a cnt~cal area of importance to
engineers, scientists, and designers It is also of Importance to A S T M and standards writing and
use
D B Anderson (author's closure)--The procedures outlined m Table l are apphed to mdwld-
ual data sets on a case by case bas~s reflecting ( a ) the llm~tatlons of the documentation of the test
method, material, environment, and exposure condmons, (b) the particular material/environ-
ment interactions reflected m the anticipated and observed corrosion processes involved, (c)
applicability of estabhshed theoretical concepts and models, and ( d ) comparabdlty with docu-
mented service experience Although the overall objectives are the same for any corrosion evalu-
ation study, there is no universal cookbook procedure that can be applied to each and every data
set
Standar&zatlon efforts are underway within A S T M Committees G-1 and E-49 to provide
gmdehnes for data recording to facd~tate corrosion data comparisons as a step m the evaluation
procedure A long range goal is better quality corrosion data to ~mprove service hfe
pre&ctabthty
AS&M - NASA Langley Research Center, Hampton, VA 23665

H. Shih I a n d F. Mansfeld I
Software for Quantitative Analysis of

Polarization Curves
REFERENCE: Shlh, H and Mansfeld, F, "Software for Quantitative Analysis of Polarization
Curves," ComputerModehngm Corrosion,ASTM STP 1154, R S Munn, Ed, Amencan Society
for Testing and Materials, Phfladelphm, 1992, pp 174-185
ABSTRACT: A computer program (POLFIT) has been developed for the analysis of polanzatlon
curves that provides full graphics functmns and has both stmulanon and fitting procedures Electro-
chemical parameters such as anodlc and cathodm Tafel slopes, polarization resistance, corrosion
current denstty, and corrosion potential, the errors for each of these parameters, and the results of
the statistical analysis are displayed m tabular form The expenmental and fitted polanzatlon data
are plotted on the computer screen and can be obtamed as hard copies A umque feature is the
possibility of ehmmatmg the uncompensated ohmic resistance (R.) m the data analysis Inspec-
tion of the current devmt~on between the expenmental and fitted data points at each potentml
allows ehmmat~on of data points w~th excesswe scatter and detectmn of systematm errors such as
those anslng from the neglect o f R . m the data analysis The performance V of the program has
been evaluated for theoretical data with vanous random normal noise levels and for expenmental
data (Cu/artlficml seawater)
KEY WORDS: software, polanzatlon curves, Tafel slopes, corrosion rates, polanzaUon resistance,
uncompensated resistance, data analysis
Polarization data determined m the vicinity of the corrosion potential (E~o.) have been used
for a long time to determine corrosion rates o f electrochemical systems This approach is based
on the mixed-potential theory descnbed by Wagner and Traud [ 1 ], the Stern-Geary equation
[ 2 ], and the polanzatlon resistance technique as summanzed by Mansfeld [ 3] Vanous methods
have been proposed to analyze the expenmental results assuming that the Butler-Volmer rela-
tion ts valid [4-16] The C O R F I T method of Mansfeld [ 13] published in 1973 was the first
program to determine the electrochemical parameters such as Tafel slopes and corrosion current
densttles from data obtained m the non-Tafel reg,on close to E~or, Gerchakov et al developed
the computer program P O L C U R R for the analysis of polanzatlon resistance data [ 14 ], and the
performance was evaluated with actual and theoretmal data The results showed a significant
improvement for corrosion parameter estimation in comparison with C O R F I T , which is a sub-
routine in the improved program, and the mathemattcs Is essentially an adaptation o f N O N L I N
[ 17-19] It runs on the VAX system with a maximum o f 51 data points m a narrow potential
region around Er A hneanzed least-square method ( L L S M ) has been developed recently by
Jensen and Bntz [ 15,16] for the analysis o f polanzauon data A quantitative comparison o f
published methods [6-13] has been presented by Jensen and Bntz [ 16] based on 100 runs for
synthetic polanzatton curves with 2% random normal noise around corrosmn current Most
recently, analysis of polarization curves has been extended to systems with complex electrode
reactmns by Devereux and Yeum using an lteratwe method by Devereux and Yeum [20,21]
t Corrosion and Environmental Effects Laboratory, Department of Materials Scmnce and Englneenng,
Umverslty of Southern Cahfornla. Los Angeles, CA 90089-0241
174
SHIH AND MANSFELD ON SOFTWARE 175
Since none of these programs has considered the ohmic drop due to either low conductwzty of
the electrolyte and]or due to large currents, the fit results may contain errors m the esUmaUon of
the kinetic parameters In particular, the fitted values for the polarization resistance contain a
contribution from the uncompensated resistance ( R . ) that will lead to a value of the corrosmn
rate which is too low
A study of the present methods suggests that an improved approach is necessary to ehmmate
the uncompensated solution resistance ("IR drop"), to handle more data points m a wider
potentml-current range, to improve the accuracy and precision of the analysis, and to provide
better graphics functions The new program has been developed to satisfy these reqmrements Its
mare features are hsted below
POLFIT Program
The POLFIT program is written in Microsoft Fortran 4 1 and Microsoft C 5 0 combined with
Cornell Scientific Graphics Tool Kits for graphics purposes The program runs on IBM and IBM
compauble computers
Due to the selection of a larger potential region and the use of more data points than m most
other methods, a math coprocessor is necessary to accelerate the calculation
Simulation
Using the program, simulated polanzaUon curves can be obtained It reqmres the input of the
surface area of the electrode (A), anodlc Tafel slope (ba), cathodic Tafel slope (be), mmal
potenual (E,.), final potential (E~.), total data points (less than 401 points), corrosion current
(Icon), corrosion potentml (Eeoc), and uncompensated soluUon resistance (Ru) The program
wdl generate a theoreUcal polanzaUon curve according to the Butler-Volmer equauon
I = Ico~{exp(2 3 0 3 [ ~ - I R . ] / b a ) - e x p ( - 2 303 [z~tE - I R . ] / b r (1)
where I is the current measured at 2rE = E - Er and E is the apphed potentml

The polanzatlon resistance (Rp), corrosion current density tr = lr and the parameter
B = 2 303babr ~ + be) can be calculated A wide region ofpotentmls can be selected, and E,.
can be negatwe or posture m companson w~th En. The s~mulatlon results are tabulated, and the
polarization curves are plotted on the computer screen Random noise w~th normal &stnbut~on
can be added to the simulation data by means of MINITAB [22]
Fitting
The fit procedure is straightforward and easy to use After inputting the experimental data file
name and the potentml region In which the fit is to be performed, fitting will start IfRu ~s to be
considered m the fit procedure, an mmal guess for Ru has to be made The program output has
been designed to provide a convement d~splay of the calculated electrochemical parameters Rp,
b., be, 1r Ir Er and B with their corresponding error terms as well as the staUstlcal
evidence of the fit quahty Both expenmental and fitted polanzatlon curves are plotted on the
screen The results of analysis and the polanzatlon curves can be pnnted out as hard copies
Data Edttmg and Error Plots

After completion of the data analysis, the devlauon of the current between the fitted and the
experimental curve at each potential value ~s shown on the screen Data points w~th excessive
83 i , i i ~ "ll'l ' ,
.... exptl curve
.... s curue
29
-25
E ( mq )
-79 u s Ecox'x',
-133
- 187
-241 i i i 1 i
-5 -4 -3 -2 -1 8 1 2 3 4
log(i) (i i n uA)
FIG 1--Stmulated polartzatton curves for I co,~ = 10 t~t, R ~ = 0 0 fl, b= = 40 m V, b~ = 120 m V, A = 1 cm 2,
E,. = - 2 4 0 mV, Eh. = 80 mV, E~o~ = O 0 m V
experimental scatter can be ehmmated by input of an error hma, and a new data file can be
generated for further data analysis Inspecuon of the statistical data wdl show whether significant
improvements are made by this procedure
Representative D a t a
To dlustrate the stmulatlon procedure, the following parameters have been chosen ba = 40
mY. bc = 120 mY, Ico. = 10 pA, E~o~ = 0 0 v e r s u s Eref, R u = 0 or t000 ~ , A = 1 c m 2, and Rp
= 1302 9 f l / c m 2 R a n d o m noise levels of 0%, 1%, 2%, 5%, 10%, 20%, 50% and 75% with normal
distribution were added to I~o~ [16]
Figure 1 shows the simulated and fitted curves m a E-logt plot for Ru = 0 0 fl and a potential
region from - 2 4 0 mV to +80 mV As expected, excellent agreement between simulated and
fitted data is obtamed Since the perfect fit has been observed, the dots which represent the
simulated data have been fully covered by the fitted curve The results o f the analysis are shown
m Table 1, which lists the reformation such as E,., E~., Ru, data file name and number of
iterations and fit results such as ba, be, R v, I~o~, B , t~o,~, R p * A , E~o. and the errors of each of these
parameters The staustlcal analysis o f the fit is gwen by the parameters
SSO = ~(I, - 1,,,~)2 (2)
SSD = Z ( I , -/fit) 2 (3)
R 2 = (SSO - S S D ) / S S O (4)
SD = X(I, - I , ~ r - 1) (5)
where I, is the observed current at a given potenual, l.v~ is the average value of the measured
currents, Int is the fitted value of current, N is the number o f total data point, SSO is the sum o f
squared observations. SSD is the sum of squared devmuons, SD ~s the standard devmuon, and R 2
TABLE l--Resuhs o f analysts for the stmulated polartzatlon curve wtth R u = 0 ft,
E,. = - 2 4 0 m V, and E,. = 80 m V
Initial Potential= -240mU; Final Potential= 88mU
Estimated Solutxon Resistance Ru = .888 ohms
N u n b a ~ os I t e r a t i o n s : 3
Results E~ror
=====~=
Rp = 1382.9 .20782E-66 ohms
ba = 48.000 .50606E-88 nO
be = 128.08 .89060E-88 nO
I corr = 18.888 .27589E-08 m i c ~ o a n p s
B = 13.820 mU
icorr = 18.888 .27589E-08 microanps/sq cm
Rp * a r e a = 1302.9 .20782E-06 ohnc-aq cn
Ecorr = ,88008 .76948E-12 mU (E_res
Sun os Squared Observations = .44297E+08

Sun os Squared Deviations = .36034E-18
R-squared = 1.0008
Correlation = 1,0008
Standard Deviatxon = .30166E-86 with 396 d.s
indicates the quality of the fit, where R 2 = 1 0 indicates a perfect fit [ 18,19,23,24] It should be
n o t e d that the standard deviation can only provide information a b o u t the quality o f the expen-
mental data Large noise levels will produce large values o f the standard deviation Therefore tt
c a n n o t be used to evaluate fit quality that might be affected by systematic errors
W h e n a narrower potential region from - 3 0 m V to 30 m V versus Eoo,~, which is usually
dtsplayed in a h n e a r E-t plot was selected, n o adverse effect o n the quahty of the fitted results was
observed T h e increasing r a n d o m noise levels to the simulated polarization curves in a potential
range between - 2 4 0 m V a n d + 8 0 m V by using a regression software package called M I N I T A B
was introduced, the r a n d o m noise levels were added to corrosion currents (I~o,~) that h a d been
used by J e n s e n a n d Brltz [ 15,16] Due to the limitations o f the noise generator, the r a n d o m
noise had high frequency, this was not the case o f the noise in electrochemical m e a s u r e m e n t
Therefore a low frequency noise generator will be considered for further evaluation T h e fit
results in Table 2 were obtained T h e relative errors for Rp, ba, be, a n d I~or~at a noise level o f 1%
TABLE 2--Resuhs of analysts o f stmulated polartzatton curves wtth vartous random norse levels
Noise Level
Parameter 0% 1% 2% 5% 10% 20% 50% 75%
ba (mV) 40 0 39 99 39 96 40 04 39 96 39 77 39 82 40 82
+00 +003 +005 +014 ___027 +054 +139 +262
bc(mV ) 1200 12002 11991 12030 11981 11917 11993 11866
+00 _+005 _+009 +024 • • +249 •
Rp (~2. cm 2) 1302 9 1302 9 1305 5 1296 7 1306 3 1320 0 1336 0 1445 4
9+ 0 0 -+173 +301 +776 -+1528 +3135 -+8281 -+1424
tco,~(#A/cm 2) 10 0 10 00 9 98 10 06 9 96 9 81 9 72 9 13
9+ 0 0 _+001 _+003 +_007 • • _+075 + 1 16
SD a 0001 181 3 16 8 16 1599 3248 8234 12611
a SD = Standard DewaUon
83 ........ I. . . . . . . . I. . . . . . . . I. . . . . . . . I .~. . ./. . ~ - t .......

.... expt] c u ~ u e ' ~ ~ "
s curue . ~ . : . "
29
-25
9 . .. ~ < . .
E (toO)
-79 us: Ecor.,x',
-133
-187
-241
-2 -1 8 1 2 3 4
log(i) ( i in ufl)
FIG. 2--Simulated polarization curves as in Fig. 1. with 75% random noise level.
were 0.04%, 0.07%, 0.04% and 0.16%, respectively. At 50% random noise level, the relative errors
of Rp, ba, bc and I~o. had increased to 6.35%, 3.47%, 2.08% and 7.47%, respectively9 Figure 2
shows the polarization curve with 75% random noise added and the fitted curve. The current
deviation between the two curves at each potential value is shown in Fig. 3, which indicates that
in spite of the large scatter caused by the random noise, the new program can still provide the
electrochemical parameters with less than 11% error. When the noise level was raised to 75%, the
relative errors of Rp, ba, be, and I~o. were about 10.0%, 6.0%, 3.0%, and 11.0%, respectively.
These results show that the use of POLFIT will result in a satisfactory analysis of experimental
polarization data even in the presence of significant experimental scatter of the individual data
points.
141
95
49
deviation
(~)
3
-43
-89
- 135
64 127 190 253 316 379
n u m b e r os data point
FlG. 3--Currentdeviationsofsimu~tedandfitteddatapointsofF~.2.
84 rl,,,,: , [,l,l,,, , [,,,,,, , ,
.... e x p t l curve
.... s curve
30
-24
E (mU)
-78 us Ecorr
-132
-186
I 1 I I
-248
-5 -4 -3 -2 -1 0 1 2 3
log(i) (i in uA)
FIG 4 - - S t m u l a t e d polartzatton curves as tn Fzg 1, wtth R . = 1000 ~2 added
W h e n Ru = 1000 ~2was added to the simulated polarization curve and the analysis was carried
out assuming Ru = 0, the fit errors were very small in a potential regaon from - 2 4 0 mV to +80
mV The agreement between the simulated and fitted curves seemed to be very good (Ftg 4)
and the simulated dots and fitted curve are very close and ddticult to separate, but the results o f
the analysis showed large errors for all the parameters (Table 3) This result shows that it is
dangerous to evaluate the accuracy of the analysts solely by a quahtatwe inspection of the
agreement between experimental and fitted curves A more quanutatlve analys~s discovered that
the current deviations o f the experimental and fitted currents at each individual potentml
s h o w e d a s m u s o l d a l s h a p e ( F l g 5) Addmonalanalyslssuggestedsuchsystematlcerrordlstnbu-
tmon to be typical for contributions from R. When a larger potentml regaon from - 6 0 0 mV to
+ 2 0 0 mV versus E~o,rwas selected for the same parameters, a larger dewatlon between simulated
TABLE 3--Results of analysis for the stmulated polarlzatton curve wtth Ru = 1000 fl,
E,. = - 2 4 0 rn V, and En. = 80 m V
Inltial Potential= -240mU; Final Potential= 8~V
Estimated Solution Beslstance Ru = 888 ohms
Number os Iterations : 4
Results Error
Rp = 2374.8 le.e68 o~s

ba = 139.28 1.8369 mU
bc = 283.92 1.6482 mO
l__corr = 17.838 .18682 microamps
B = 48.582 mU
zcorr = 17.030 .18682 microamps/sq cm
Rp * a r e a = 2374.8 10.868 olm~q cm
Ecorr = .888fl0 .30897 mU ( E _ r e f )
~um os Squared O b s e r v a t i o n s = .43SSTE+e6

Sum os S q u a r e d D e v i a t i o n s = 388.81
B-squared = .99911
Correlation = .99927
Standard D e v i a t i o n = 1.4268 w i t h 191 d . s
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale
180 C O M P U T E R MODELING IN CORROSION
14
10
6
deviation
2 (~)
-2
-6
I I I I I
-10
1 34 67 100 133 166 199
numbelr" o s d a t a p o i n t
FIG. 5--Current deviations of simulated and fitted data points o f Fig. 4, with Ru = 1000 9.
and fitted curves was observed (Fig. 6). The current deviations of simulated and fitted current
values at each potential still showed a sinusoidal distribution (Fig. 7 ). The absolute values of the
deviation in Fig. 7 were much larger than those in Fig. 5, indicating a large effect of Ru when a
wider potential region was selected. Inspection of the fit results in Tables 3 and 4 shows that the
surprisingly good agreement between the simulated and fitted curves for Ru = 1000 ~2 and an
input ofRu = 0 fZ (Figs. 4 and 5) was achieved by a large increase ofba and be. As pointed out
elsewhere [3 ] the curvature of the polarization curve decreases as the Tafel slopes become larger.
Therefore a reasonable fit can be achieved for a polarization curve that contains the linear term
I R ~. This situation is dangerous if the quality of the fit is only determined by a comparison of the
experimental and fitted curves in E-log/plots. However, as shown in Figs. 5 and 7, plots of the
200 iiiii i i jllllll i , iiiilll i i l~Zlll i i i rllll i I i [ I H I II l .lllJ

~ l I I 4 I I I Z
.... exptl curve
.... s curve
67
-66
E (mU)
- 199 vs Ecox'x'
-332
-465
I , ,I I I I
-598
-5 -4 -3 -2 -1 8 1 2 3
log(i) (i in uA)
FIG. 6 - - Polarization curves of Fig. 4 in wider potential range.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further r
32
22
I
12
-8
-18
!deviation
I I I I I
-28
1 52 183 154 285 256 387
n u m b e r os d a t a point
FIG 7 - - C u r r e n t d e v t a t l o n s o f s l m u l a t e d a n d f i t t e d d a t a p o m t s o f F t g 6
dev:atlon between the measured and the fitted current at each apphed potentml are very sensi-
tive to systematic deviations between the two sets of data and can therefore detect problems with
the fitting procedure
In general, it is expected that neglect ofRu m the data analysis leads to a value of/co, which is
too low since the expenmental value of Rp,exp = Rp + R. [3] However, the results shown in
Tables 3 and 4 indicate that due to the increase of the fitted values of the Tafel slopes the
parameter B also Increases in a m a n n e r that leads to a value of tcorr which lS too large
To evaluate the program further, expenmental data for a copper rotating cylindrical electrode
( R C E ) at rotating speeds between 100 and 1600 rpm in artlficml seawater were analyzed The
TABLE 4--Results of analysts for the stmulated polarlzatton curve wtth Ru = lO00 f~,
E,. = - 6 0 0 rn V, and E~. = 200 rn V
Initial Potential= -688mU; Final Potential= 288mU
E~tlmated S o l u t i o n Resistance Ru = .888 ohms
Humber o s Iterations : 7
Results Error
Rp = 2195.3 34.984 ohms

ba ~ 261.25 18.883 mU
bc = 518.38 6.248? .U
I_corr = 35.268 1.1716 wicroamps
D = 75.846 wU
icorr = 35.268 1.1716 microamps/sq cm
Rp * area = 2195.3 34.984 o h m ~ q om
Ecorr = .88888 2.$915 mU (E_res
Sum of Squared O b s e r v a t i o n s = .56248E+67

Sum of S q u a r e d D e v i a t i o n s = .18671E+86
R-squared = .98183
Standard D e v i a t i o n = 18.987 with 296 d . s
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Fed
130 I I I
exptl curve
.... fitted curve
96
62
28
i
(u A )
-6
-48
I
-74
-38 -28 -11] I] 11] 21] 31]
potential (mU v s E c o r r )
FIG. 8--Experimental polarization curve and fitted curvefor copper RCE in artificial seawater at 900 rpm.
potential scan rate was 0.1 mV/s. The potential region was selected at Er - 30 mV. The fit
parameters b,, be, Ir Rp, E~o~and their errors were obtained for different rotation speeds. The
functional relations between these parameters and r ~176(r in rpm) [ 25 ] were evaluated using a
regression software package called MINITAB [22-24].
The regression analysis showed a linear relation between r 0"707 and Ir
l,o,~(r) = 10.20 + 0 . 3 6 0 , r ~176 (pA) (6)
where SD = 3.586 and R 2 = 97.6%.

Regression analysis also showed the linear relation between r ~176 and be:
be(r) = 94.6 + 0 . 3 9 0 . r ~176 (mY) (7)
where SD = 6.997 and R 2 = 92.7%. Linear relations between ba and r 0"707 ( R 2 = 89.6%) and Rp
a n d r 0"707 ( R 2 = 74.6%) were also obtained. The relation between Er and r 0"707is given by
E ~ , ( r ) = -242.735 - 0.00985,r ~176 (mY) (8)
where SD = 0.6715 and R 2 = 46.9%.

The regression equation shows that E~o~is independent of rotation speed. The increase of i~o~
with increasing rotation speed combined with the independence of Er on mass transport can
only be explained by assuming that both the anodic and cathodic reactions are influenced by
mass transport. In the first case increased transport of CI- will increase the anodic reaction
according to
Cu + 2C1- --~ CuC12 + e -
while increased transport of O2 will increase the rate of the cathodic reaction. Since both Tafel
slopes are also mass transport dependent, it can be concluded that the corrosion reaction occurs
in a region of mixed charge transfer and mass transfer control.
The experimental and fitted polarization data for copper RCE at a rotating speed of 900 rpm
are shown
Copyright in Fig.
by ASTM Int'l8.
(allThe error
rights plot inTue
reserved); Fig.Feb
9 did not show
10 09:33:27 the
EST sinusoidal shape discussed for Figs.
2015
SHIH AND MANSFELD ON SOFTWARE "183
39 "r 1 T r r
27
15
deviation
3 (z)
-9
-21
-33
1 43 85 127 169 211 253
n u m b e r os d a t a point
FIG. 9--Deviation between experimental and fitted data points for data of Fig. 8.
5 and 7, which indicates that the effect of R, can be neglected. The results of analysis and their
errors are shown in Table 5. The relative errors for Rp, ba, b, and I~o~are very small and equal to
0.19%, 0.98%, 2.42%, and 1.54%, respectively. The mixed control processes for the anodic and
cathodic reactions of Cu in NaCI has been discussed by Picketing et al. [26] and Nobe et
al. [27].
Conclusions
A new software program for the analysis of dc polarization data has been developed. It pro-
vides high accuracy and high precision even for very noisy experimental data. It provides full
graphics functions, data editing and deviation plots, and has the capacity of handling large data
TABLE 5~Results of analysis for the polarization curve of copper RCE in artificial seawater
at 900 rpm rotating speed.
Initial Potential= -273mU; Final Potential= -213mU
Estimated Solution Resistance Ru = .880 ohms
Number o f I t e r a t i o n s : 8
Results E~ro~
Rp = 317.88 .59476 ohms

5a = 58.918 .57838 mU
bc = t47.89 3.5797 mU
I..corr = 57.669 .89B72 microamps
B = 18,296 mU
icorr = 19.223 .29691 microamps/sq cm
lip ~ area = 951.25 1.7843 o ] ~ s q cm
Ecorr = -243,79 916891E-81 mU (E_~ef)
Sam os S q u a r e d O b s e r v a t i o n s = .72756E+86
Sum os S q u a r e d D e v i a t i o n s = 153.37
R-squared = .99979
Standard Deviation = .78482 with 249 d.f.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pur
files (up to 401 points) A special feature of the program allows ehmlnation of data that exceed a
certain level of experimental data scatter
Since the program allows the elimination of the ohmic drop, it is applicable to systems with
high solution resistance a n d / o r high currents in which neglect of the ohmic drop in the fitting
procedure would produce erroneous values o f the Tafel slopes and the corrosion rates
The program can be used m large or narrow potential regions around Er Therefore one can
select the most suitable potential region for the fitting procedure and can compare results ob-
tained in different potential regions
References
[1] Wagner, C and Traud, W, Zettschrtftfi~rElektrochemle, Vol 44, 1938, p 391
[2] Stern, M and Geary, A L, Journal of the Electroehemwal Socwty, Vol 104, 1957, p 56
[3 ] Mansfeld, F, Advances in Corrosion Science and Technology, Vol 6, Plenum Press, New York, 1976, p
163
[4] Butler, J A V, Transactions of the Faraday Society, Vol 19, 1924, p 729
[5] Erdey-Gruz, T and Volmer, M, Zettschr~J~r Phystkund Chemic, Vol 150A, 1930, p 203
[6] Barnartt, S, Electrochuntca Acta, Vol 15, 1970, p 1313
[7] Jankowskl, J and Juchnlewlcz, Corrosion Science, Vol 20, 1980, p 841
[8] Bandy, R , Corrosion Scwnce, Vol 20, 1980, p 1017
[91 Fehu, V and Fehu, S, Corrosion, Vol 42, 1986, p 151
[10] Greene, N D and Gandhi, R H , MatertalsPerformance, Vol 21, 1982, p 34
[11] Mansfeld, F and Kendlg, M, Materials Performance, Vol 22, No 12, 1983, p 40
[12] Greene, N D and Gandhi, R H, Materials Performance, Vol 26, 1987, p 52
[13] Mansfeld, F, Corrosion, Vol 29, 1973, p 397
[14] Gerchakov, S M, Udey, L R , and Mansfeld, F, Corrosion, Vol 37, 1981, p 696
[15] Jensen, M and Bntz, Corrosion, Vol 46, 1990, p 111
[16] Jensen, M and Bntz, Corrosion Science, m pnnt
[17] Metzler, C M, Technical Report No 7292]69/7292/005, The Upjohn Company, 1969
[18] Draper, N R and Smith, H, Apphed Regression Analysis, 2nd ed, Wiley, New York, 1981
[19] Neter, J , Wasserman, W, and Kutner, M H, Apphed Linear Statlstwal Models, 2nd ed, Rxchard D
Irwin, Homewood, Ill, 1985
[20] Yeum, K S and Devereux, O F, Corrosion, Vol 45, 1989, p 478
[21] Devereux, O F and Yeum, K S, "Modeling Electron Transfer, Dlffus~onal Effects, Passlvatlon, and
Ohmic Loss m Multi-Reaction Polarization Curves," in Computer Modehng m Corrosion, ASTM STP
1154, American Society for Testing and Matenals, Phdadelph~a, 1992, pp 126-142, th~s pubhcatlon
[22] Ryan, T A , Jr, Joins, B L, and Ryan, B F, Minttab Reference Manual Minltab Release 5 1, 1985
[23] Hogg, R V and Tams, E A in Probablhty and Statlstwal Inference, 2nd ed, Macmillan, New York,
1983
[24] Burden, R L, Falres, J D, and Reynolds, A C, Numerwal Analysis, 2nd ed, Pnndle, Weber &
Schmldt, Boston, 1981
[25] Mansfeld, F, Kendlg, M, and Lorenz, W, Journal of the Electrochenucal Society, Vol 132, 1985, p
290
[26 ] Kato, C and Plckerlng, H W , Journal of the Electrochemwal Society, Vol 131, 1984, p 1219
[27] Shen, W and Nobe, K, 170th Meeting of The Electrochemical Society, Extended Abstracts of 170th
Meeting, Paper No 166, 1986
DISCUSSION
J C Fan ~ (written dtscusston)--An Initial estimation of the solution resistance is required In

the program POLFIT As the authors indicated, an under-estimation or an over-estimation o f
W R Grace & Company, Dearborn Division. Lake Zunch, IL 60047

DISCUSSION ON SOFTWARE 185
th~s value would result m a poor fit However, most recent potent~ostats are eqmpped w~th
current interrupt IR compensation How would POLFIT respond to this potentially fluctuating
IR compensat,on9
H Shth and F Mansfeld (authors" closure)--If the current interrupter techmque is used
correctly, it is unnecessary to compensate the soluUon resistance in the POLFIT program The
analysis can be c a m e d out by simply inputting R u = 0 The devaatlon plot of the POLFIT will
not show a systematic devmtlon If the current interrupter technique ~s not used correctly and a
residual Ru remains, systematic deviations with a smusoldal shape will be observed after using
the POLFIT program This is an indication that an addmonal estimate of Ru is required
U Bertocci 2 ( written dlscusston)--You have shown that your fitting program is msensmve to
the addition ofnome to the simulated data However, the noise added is high frequency, meaning
that its autocorrelatlon function ~s about zero It would be interesting to see how your program
performs if lower frequency noise is used The test would be a more reahstlc one, since a large
part of the fluctuations in experimental electrochemical cells is not caused by instrumental
noise, but by other processes, such as convective transport and surface changes which are inher-
ently much slower
H Shth and F Mansfeld (authors'closure)--We agree that a test of software programs such as
POLFIT using low frequency noise would be more reahstlc We will investigate this matter
further and wdl test POLFIT with a statable noise function
0 F Devereux 3 ( written dlscusswn)--Programs used to determine corrosion current based on

detaded evaluation of the contnbuUons o f two reactions cannot accurately describe systems that
experience a second anodlc or cathodic reaction which makes a slgmficant contribution near the
rest potentml Care must also be taken to avoid always treating tCORRas a corrosion rate, ~t may
descnbe reactions that are not corrosion.
H Shth and F Mansfeld (authors'closure)--Professor Devereux raises an important point and

we agree with his comments We have discussed these problems as early as 1970 [1] and in a
rewew article m 1976 [ 2 ] with respect to the polanzatlon resistance techmque While the contri-
butions o f a d d m o n a l cathodic and anodlc reactions to the polarization curve are of great theoreu-
cal interest, we have encountered very few corrosion systems for which a real problem with
determining leo. correctly has occurred
Discussion References
[/] Mansfeld, F and Oldham, K B, Corrosion, Vol 26, 1970, p 207
[2] Mansfeld, F, Advances m Corroswn Scwnce and Technology, Vol 6, Plenum Press, New York, 1976, p
163
2 National Institute of Standards and Technology, Ga~thersburg, MD 20899

F. Mansfeld, 1 C. H. Tsai, l a n d H. Shlh 1
Software for Simulation and Analysis of

Electrochemical Impedance Spectroscopy
(EIS) Data
REFERENCE: Mansfeld, F, Tsm, C H, and Shlh, H, "Software for Simulation and Analysis
of Electrochemical Impedance Spectroscopy (EIS) Data," Computer Modehng m Corroswn,
ASTM STP 1154, R S Munn, Ed, Amencan Sooety for Testing and Matenals, Phfladelphm,
1992, pp 186-196
ABSTRACT: The software program BASICScan be used for the slmulaUonand analysisof simple
corrosmn systems which are under charge transfer or mass transport control Data for systems
under charge transfer control (one-time-constant model ) can be analyzed with the Bodefit method
using Bode-plots, the Cirfit method using complex plane plots, and the lntfit method using plots of
- Z " versus logf Data for systems under mass transport control can be analyzed with the Warfit
method using complex plane or Randles-plots Systemsfor which an mductwe loop is observedcan
be analyzed with the lndfit method Examples are gwen for the slmulaUonand analysisof Imped-
ance data for the three d~fferentsystems
KEY WORDS: charge transfer control, mass transport control, corrosion systems, software pro-
gram, slmulauon, analysis, Cu-NI alloy
The evidence demonstrated m the ever increasing number of papers reporting results obtamed
with electrochemical impedance spectroscopy (EIS) makes it clear that EIS is a very valuable
tool for the study of a large number of corrosion systems However, it also has become quite
evident that the successful appllcaUon of EIS reqmres careful design of the experimental ap-
proach for the collecUon of the EIS data and the use ofappropnate hardware as well as suitable
software for the analysts of the experimental EIS data Such software has been developed in
ANALEIS, which is a software library for the simulation and analysts of EIS data BASICS is part
of ANALEIS and addresses the simplest cases of corrosion systems Other modules are devoted
to the analysis of EIS data for polymer coated metals (COATFIT), anodized aluminum (ANO-
DAL), locahzed corrosion of A1 alloys (PITFIT), and general aspects of EIS (K-K
Transforms)
This paper will discuss the models used for the slmulaUon and analysts of EIS data for the
s~mplest cases of corrosion reactmns under charge transfer control or mass transport control
Systems for which an inductive loop is observed wall also be discussed Examples for the analysts
of experimental EIS data will be presented for the three different cases
Models for Simulation and Analysis of EIS Data

Charge Transfer Control
Simple corrosion systems entirely under charge transfer control and the cases of uniform
corrosion on homogeneous surfaces can be described by the simple eqmvalent circuit (EC)
Department of Materials Science, Umverslty of Southern Cahfornm, Los Angeles, CA 90089-0241
186
MANSFELD ET AL ON ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 187
Cdl
H
,,I
Bs I
Rp
I I
Rp
Z=Bs+
1 + (,JwCdlBp) Q
FIG l--Equtvalent ctrcutt (EC) for a stmple corroston system under charge transfer control
shown in Fig 1 This EC allows the estabhshment of correlations between electrochemical

system parameters and charactenstlc Impedance elements [ 1 ] In Fig l, Col is the capacitance of
the electrode surface and Rp is the polarization resistance which is reversely proportional to the
corrosion current density (c d ) tr
Rp = B/too~ (1)
where B is a combination of the Tafel slopes ba and bc
B = b.bc/2 3(b. + br (2)
All ohmxc resistances in the system under study, such as the electrolyte resistance, cable resis-
tances, etc, are contained m R s
The impedance modulus Z ( j w ) for the E C m Fig 1 can be expressed as a function of
frequency f = w/21r as follows
Z(J6o) = R s + Rp/(1 "bJ6OCRp) (3)
The values of Rs and Rp can be determined from the high ( Eq 4) and low (Eq 5 ) frequency hmlts
of the measured impedance spectra, respectwely
Rs = hm IZI (4)
f~oo
and
R, + Rp = hm IZI (5)
f~o
Vanous approaches can be used to determine the experimental value of Ca~as will be descnbed
below
In the following the &fferent methods most commonly used for the display of experimental
tmpedance data and the corresponding analysis routines wdl be described in general terms A
more detailed description of the use of BASICS will be given in the following section
Complex Plane Plots and Analysts by Ctrfit

A number of different methods are used at present for displaying the experimentally deter-
mined complex impedance Z ( j w ) = Z ' + j Z" [ 1 ] In a complex plane plot o f - Z " versus Z ' a
1200 I I I I I
i000
E
.c: 800
0
C
-r-I
N 600
1
E
N 400
I
0 I I
0 200 400 600 800 ~.000 200
Zr"eal (Z in ohm )
FIG 2--Complex plane plot for the EC m Ftg l for ot = 1 (Curve 1) and o~ = 0 8 (Curve2), R, = 10 fl, R p
= 1000 fl, Cat = 100 t~F
semicircle is obtained with a radms of Rp/2 (Fig 2) The values of Rs and Rp can be determined
from the intercept of the semicircle on the real axis according to Eqs 4 and 5 The capacitance Cdl
can be obtained from the maximum of the Imaginary impedance Z " and the corresponding
frequency fm~x
C~= (2rf~Rv)-' (6)
In most reported cases impedance data obtained at the corrosion potential Er have the shape
of depressed semlorcles with the center of the circle below the real axis (Fig 2) [ 1 ] Kendlg and
Mansfeld [ 2 - 5 ] have accounted for such deviations from the ideal behavior (Eq 3) by introduc-
ing an exponent a which leads to
Z ( j o ~ ) = R s + R p / ( 1 + ( j o : C R p ) =) (7)
It is important to recognize that the use of the exponent a in Eq 7 is only a formal description
of the expenmental data and that the physical meaning of a is not clear However, the use o f a m
the analysis of EIS data allows a quahtative evaluatton of a corroding system and its changes with
exposure time and other expenmental variables The inhomogeneous surface model proposed
by Juettner, Lorenz, Kendlg, and Mansfeld [6 ] probably descnbes such experimental data bet-
ter, however, very few applications of this complicated model, which combines charge transport
with mass transport, have been given [ 7]
The determination of the expenmental values of Rs, Rp and Cdl IS greatly facilitated by the
apphcation of numencal fitting procedures such as the computer program CIRFIT, which was
MANSFELD ET AL ON ELECTROCHEMICALIMPEDANCE SPECTROSCOPY 189
90
75
E
U 3 ' '
E _2
60
o
(D
C 10
2 45 m
r
t'-'
N
30
O 03
_.1 t0
i-
t n
t5
0 ~ 0
-3 -2 - t 0 1 2 3 4 5
Logf (f in Hz)
FIG. 3--Bode-plots for the EC in Fig. I for ot = 1 (Curve 1) and a = 0.8 (Curve 2); R,, Rp and Ca1as in
Fig. 2.
first developed by Kendig and Mansfeld [8] for the evaluation of complex plane plots. Cirfit is
an improved version of CIRFIT. The advantages of Cirfit become apparent when a complete
semicircle cannot be determined in the measured frequency range, when the experimental data
show scatter, or when deviations from the ideal behavior occur.
Bode-Plots and Bodefit

One disadvantage of the display of experimental data in complex plane plots is that the
dependence of the impedance on the frequency of the applied signal is not shown directly [ 9].
Therefore Bode-plots are used increasingly for the display of EIS data, In Bode-plots, log [Z [
and the phase angle are plotted versus logf. The Bode-plots for the EC in Fig. 1 are shown in Fig.
3 for a = 1 and a = 0.8. One advantage of such Bode-plots is the possibility of detecting the
regions that are dominated by resistive elements such as Rs and Rp, in which a slope of zero is
observed, and regions dominated by capacitive elements, for which a slope o f - 1 is observed in
the ideal case.
The elements of the EC in Fig. 1 can be determined from the high and low frequency regions
of Bode-plots according to Eqs 4 and 5. The capacitance can be calculated from the impedance
at f = 1/2~r since at this frequency log I Z I = - l o g Cdl for a = 1. The analysis of Bode-plots is
facilitated and made more accurate by the use of the program Bodefit. One of the advantages of
Bodefit is the possibility of determining Rp even if a clear d-c limit does not occur in the mea-
sured frequency range, which allows calculation of Rp according to Eq 5.
The Integration Method and lntfit

For systems with high values of Rp it is often not possible to collect sufficient data points in the
frequency range which can be used in realistic times for carrying out the experiment. Many
600
1
500
E
r
o 400
C
N
300
N
O~
E 2OO
N
loo
o I
-3 -2 -I 0 ~ 2 3 4 5
Logf [f in Hz)
FIG, 4--Plot of - Z " versus log f for the EC in Fig. l for a = 1 (Curve 1) and a = 0.8 ( Curve 2 ) ; R s, R e and
Cdl as in Fig. 2.
corrosion systems are not stable due to changes in the corrosion kinetics with time which can
cause changes in the numerical values of the elements of the EC in Fig. 1 during the time which
is needed to carry out the measurement in the mHz region. Kendig and Mansfeld [ 10] have
therefore proposed the integration method, which has the advantage that only the data in the
frequency region above fm~x (Eq 6) need to be recorded. As in all applications of analysis
routines, the user has to make sure that the data to be analyzed agree with the model on which
the analysis is based such as the simple model shown in Fig. 1 or its modification in Eq 7. The
integration method is based on one of the elements in the Kramers-Kronig relationships [ l 1,12 ]
which assumes a symmetric dependence of Z" with respect to f ~ . According to Eq 8, Rp can be
determined from a plot o f - Z " versus log f :
Rp = (9.2/7r) f~"~" Z " ( f ) d l o g f (8)
The capacitance Cd~ and the value of a can also be obtained with the integration method
according to:
C~ = ( 2 r f ~ R p ) -~ (9)
a = ( 4 / l r ) arctan ( 2 Z ~ , x / R p ) (1o)
where Z ~ is the imaginary part of the impedance at f~ax.
MANSFELD ET AL. ON ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 191
File:testl.dat
Cdl = 1 . 9 9 9 E - 8 5 F.
Rp = 1.888E+87 oI~
LoglZI
Rs = 3 . 8 8 8 E + S 8 ohm
(ohms)
alpha = 9,?88E-B[
1
-3 -Z -1 B 1 2 3 4 5
Log f (Hz)
5.888E+86 , 5.61~!E+66
-Z" (ohm) -Z" (ohm)
8 i t i i i i i i t
8
8 5 . 8 8 8 E +86
-3 -2 -1 8 1 2 3 4 5
Z' Coh~) Los f ( t l z )
FIG. 5 - - 1 m p e d a n c e p l o t s for E C in Fig. 1 with R s = 3 f~, R e = 10 z fl, Ca1 = 3 . 1 0 -5 F, and a = 0.97.
The integration plot ( - Z " versus log f ) is shown schematically in Fig. 4 for a = 1 and a = 0.8.
A sharp maximum of Z~,x is observed at f,.~x. One of the main advantages of the integration
method is the independence of the value of R, [ 1 3 ] . The curve shown in Fig. 4 does not change
as R, increases with increasing resistivity of the corrosive medium. Therefore the integration
method becomes most valuable for those systems for which R, approaches or even exceeds Rp. In
these cases the use o f Bode-plots for the analysis o f the EIS data would not be very useful, since
the spectra would be dominated by R,.
Cirfit and Intfit can only be used if the imaginary part of the impedance Z " has reached a
~
7 file name: -98 Call -- 1.99ZE-85 F.
6 -88 lip = 9 . 2 7 5 E + 8 6 ohm
-78 Rs = 3 . 8 8 7 E + 8 8 ohm
5 -68 a l p h a = 9.6cJgE-81
LoglZI 4 ANGI,E
Cohms ) 3 - (DEG.)
-38
2
-28
1
-18 Cdl = 1 . 9 9 2 E - 8 5 F/cruZ
8 ..................................................... 88 lip = 9.275E+86 ohm.cruZ
-3 -2 -I 8 1 2 3 4 5
...... Exp Log s (Hz)
-- Fit
Error.z = 3 . 0 4 3 E - 8 1 Y. f o r t h e i m l m d a n c e c u r v e
E r r o r p = 2.749E-81 ~. f o r t h e phase a n g l e c u r ~
i ~ r o w ](etjs t o Move C u r s o r , e l " P r e s s "C" kmj t o C o n t i n u e . .
FBF~UENCu 1.847E+821 ,Z, : 6.268E+81] IPItfk~E NtGLE : - 8 9455E+81
1. 847E+82J 6. 275E+81 -8. 454E+81
FIG. 6 - - R e s u l t s o f analysis o f impedance data in Fig. 5 with Bodefit.
Cdl
Rp
Rp §
Z = R s §
I § ( J . C d l t R p § W))a
FIG 7--Randles ctrcutt
maximum in the measured frequency range However, if the phase angle has reached a maxi-
m u m in this range, Bodefit can often be used for the analysis This case is illustrated for theoreti-
cal data for which R s = 3 fl, Rp = 107 ~, Cdl = 3" 10 -5 F, and a = 0 97 The complex plane and
Integration plots (F,g 5 ) show that Z " has not yet reached a maximum at l mHz, which was the
lowest frequency used for the simulation However, it can be seen from the Bode-plot that the
phase angle has a well-defined maximum Neither the Intfit nor the Clrfit method could be used
to analyze the data, but excellent fit results were obtained with Bodefit (Fig 6)
Mass Transport Control

One o f the basic reaction schemes in electrochemistry is described by the Randles circmt
shown in Fig 7, which descnbes the response o f a single-step charge transfer process with
diffusion o f reactants a n d / o r products to the interface [14,15] The Warburg impedance W zs
given by
w= ~-'/2(1 - j ) (Zl)
3 -98
File :tes~ .dat
~ -78 Cdl = G.OOeE-O4 F. ]
-68 lip = 8.6aBE§ oI~ ]
LoglZl -58 lq-~SE
(ohms) I~N;LE Jls = 2.888E§ ohm /
alpha = 1.608E~
8 1-28-1e (Deg) s i g m a = 6 . ~ 0 E 4 6 0 ohw' s~-~-e~J
1 -88
-3 -2 -1 8 1 2 3 4 5
Log s (Hz)
2.888E§ , , , , , , , , , 2.888E+82
/
/
f
-Z" (otto) Z' (ohm) f f
~ 0 I I 1 I I I I I I
e Z' (ohm) 2.000E+SZ 0 1/,[w (~,r-u-'c) 1.299E§
FIG 8--Complex plane plot (Ftg 8a), Bode-plots (Ftg 8b), and Bandies plotfor Randles ctrcutt (Ftg 7)
MANSFELD ET AL ON ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 193
File:D:%I~SPLOT%BIOTe30.CC
Z -78
Los: Z ' -so lqtRSE
(ohMs) 1 NIGLE
o (peg)
-2 -1 9 1 2 3 4
Log f (Hz)
2.S88E+SZ , , , , , , , , , 2.888E§
-Z" (okra) Z' (okra)
0 i i i t I I l I I 0
O Z" (ol~) 2.888E§ O 1/~'w ( ~ ) 4
FIG 9--1mpedance plots for 70Cu-3ONt after exposure to seawater medium (from Ref / 7)
where ~rIs the Warburg coefficient The charge transfer resistance Rot has been used by Epelbom
et al [ 16] for cases such as that shown m Fig 7 Rot is usually defined as the impedance at low
frequencies extrapolated to Z " = 0 (see Fig 7)
Figure 8a gwes a typical complex plane plot for the E C m F,g 7, whde Fig 8b shows the
corresponding Bode-plots Figure 8 c is a so-called "Randles plot" m which Z ' lS plotted versus
~o-I/2 According to Eq 1 1, the Warburg coefticlent ~r can be determmed from the slope of the
straight hne m a Randles plot Spectra such as those shown m F~gs 8a-c can be simulated as well
as analyzed w]th the appropriate routines m BASICS
The complex plane plot m Fig 8a ]s characterized by a capacmve arc at h]gh frequencies
s i l e name :D :%l~PLOl%B I 0 7 8 3 8 .CC

Z. 888E +02 I I I I ! I I I I Cdl = 5.737E-83 F. I
Exp Rp = 8,165E+81 ohm
-- Fit Pa = 1.965E-81 ohm
alpha = 8.997E-B1
sigma = 6.5t7E~88 o]m/~6-~
-Z" (ohm)
[Cdl = 2.868E-84 F/cm2 ]

Rp = 1,633E+83 ohm.cruZ |
0 J , i I I I I I I J
0 2 . 8 8 8 E *82
Z' (olin)
RrZ-OZ~Z = 2.116E+88~ f o r t ~
inpBdance c u r v e
E ~ o r p : 5.888E+88~. f o r t h e p h a s e a n g l e c u r v e
Use Arz,ou ](eVs t o I1oue C u r s o r , o r P r e s s "C" ke y t o C o n t i n u e . . .
IFREqUENCV : 3 .Z57E§ 1.965E-81 Z" :

3.257E+, I Z" : 1,998E-81 [ -9.588E-831
-2.187E-82
FIG lO--Resuhs of analyszs of data m Ftg 9 wtth Warfit

Cdl! Cdl2
I ' B8 '
Hc't Rp-Ret
Bc~ Rp - Rc~
Z = Hs § +
1 + (JwCdI1Ro~) Q1 1 + ( j w C d l 2 l R p - B e t l ) Cl2
FIG 1l--Equivalent ctrcult (EC) for system wtth mducttve loop
followed by a straight line with a slope of 45 ~ at the lower frequencies Depending on the relative
values of the elements in the EC of Fig 7, the capacitive arc might be less pronounced than
shown in Fig 8a, which could make the analysis of such data more difficult The intersection of
the straight line in Fig. 8a with the Z'-axls is gwen by R, + Rot - 2tr2Cd~ which shows that the
expenmental impedance plots according to the model in Fig 7 depend on the relative values of
Rot , Cdl and tr
The spectra shown in Fig 8 have been calculated under the assumption of a diffusion layer
with infinite thickness It can be shown that for a diffusion laye- f finite thickness the Imped-
ance decreases again at the lowest frequencies [14,15]
Expenmental data agreeing with the Randles circuit (Fig 7) are presented in Fig 9 for a
70Cu-30NI alloy which had been exposed for two weeks to a seawater medium containing a
copper-tolerant micro-organism [ ! 7] The analysis of these data with the analysis program
Warfit, which is part of BASICS, is shown in Fig l0 for the experimental and fitted data in a
complex plane plot The fit parameters R,, Rot, Cdl, ~rand a are also displayed Figure l0 is the
final step of the analysis of data corresponding to the Randles circuit using Warfit It will be
noted that the analysis of the expenmental data was possible despite the fact few data had been
collected In the low-frequency region where the mass transport process can be clearly
recognized
The Inductive L o o p
The interpretation of the inductive loop is one of the most difficult problems in the apphcatlon
of EIS for corrosion systems from an expenmental as well as from a theoretical standpoint Most
experimental impedance spectra containing an inductive loop in the low-frequency region have
been determined for iron-based matenals at Eoo~ in acid media in the presence of lnhlbitors
Occasional attempts to analyze such spectra on the basis of an inductance or negative capaci-
tance and resistance values cannot be taken seriously, since such analyses have no physical
meaning
Lorenz and Mansfeld [ 18] have reported impedance data obtained at Er for iron and steel in
acid media containing inhlbltors In the case of an iron rotating disk electrode ( R D E ) in 0 5 M
H2SO4 containing tnphenylbenzylphosphonlum chloride (TPBP +) R p determined according to
Eq 5 as the d-c limit of the impedance agreed with the R p-values calculated from d-c polarization
curves and solution analysis by atomic absorption For iron in 0 5 M H2SO 4 containing propar-
gyhc alcohol, which was one of the first systems investigated with EIS by Epelboln et al [ 16],
the Impedance data at the lowest frequencies showed an inductive loop The dimensions of this
loop were found to depend on the magnitude of the applied a-c signal This result shows that the
experimental data cannot be considered to be real impedance data, since the system is not linear
Additional complications for this system have been discussed by Lorenz and Mansfeld [ 18]
Simulation and analysis of impedance data for systems with an inductive loop are performed
with the
Copyright byEC shown
ASTM Int'lin(all
Figrights
l 1 reserved);
For the simulation of09:33:27
Tue Feb 10 Impedance
ESTdata
2015such as those shown in Fig
MANSFELD ET AL. ON ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 195
Cdll= 3.080E-84 F.
CdI2= 5.999E-82 F.
1.588E+01 Rct= Z.888E§ ohm
Rp = 8 . 0 8 8 E ~ 8 8 ohm
IRs = 3.OOOE§ ohm
lalpha1= 9.188E-81
[alpha2= 9.888E-81
-Z" (ohM) 8
-1.580E+81 , , i , , , , , ,
8 3.008E+81
Z" (o}m)
FIG. 12--Complex plane plot for EC in Fig. 11.
12 the charge transfer resistance Rot has to be larger than Rp and the time constant RpCdl2 has to
be larger than RetCdl I . These requirements mean that Cdl2 has to be much larger than Cdll.
Figure 13 shows experimental impedance data for Mg AZ31 for which an inductive loop
occurred during exposure to 0.5 N NaCI. Severe pitting was observed after only short exposure
times. The results of the fit of these data to the EC in Fig. I l using Indfit are also shown in Fig.
13. It should be noted that the EIS data for Mg in solution for which localized corrosion occurs
are very different from those for A1 alloys for which the pitting model applies [ 1 ]. Such data can
be analyzed with the PITFIT program which is part of BASICS.
In carrying out the simulations and analyses with the program Indfit it has to be remembered
that so far no satisfactory explanation for the occurrence of an inductive loop has been given.
Cdll= 3.912E-B4 F.
1.880E+01 I I I I I I [ I I [Cdl2= 4.316E-82 F.
[Bct= 1.787E+81 ohm
]Rp = 8.828E+88 o k . ~
[Rs = 3.Z48E~B8 ohm
[alpha1= 9.143E-81
-Z" (o)m) ~a |phaZ= 9.89~E-81
...... Exp Cdll= 1.956E-BS F/cruZ I

-- Fit Call2= 2.158E-83 F/cruZ
-1.888E+81 I t I I I
Z' ( o h m )
[ I I I
Z.OOOE+81
[Rct= 3.414E+82
IRp = 1.6~-E+82
okm.cm2
ohm.cNZ
t
Errorz = 3.813E§ for t h e impedance ctLrue
F,r,eox,p = 2.349E+81:< for. t h e phase a n g l e cut-me
U s e Az,z-ow ](e,.js t o Nove C u r s o r j o r P]Pess "C" key t:o C o n t : i n u o . . .
FREQUENCV: 3.257E-84 Z" : 3.248E+88 Z" : -?.888E-82

3.257E+84 II 3.243E~88 I
t -2.264][-82
FIG. 13-- Experi,nental impedance data and results of their analysis with Indfit for Mg AZ31 exposed to 0.5
N NaCI.
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further r
The analysts of data such as those m Fig 13 should, at the present stage of knowledge, be
considered merely as a mathematical operation However, the determination o f R v m the usual
definmon according to Eq 5 should provide rehable data for the calculation of corrosion rates
References
[1] Mansfeld, F, Corrosion, Vol 37, 1981, p 301
[2] Mansfeld, F, Ken&g, M W , and Lorenz, W J, Journal of the Electrochemwal Soctety, Vol 132,
1985, p 290
[3] Mansfeld, F and Ken&g, M W, WerkstoffeundKorroswn, Vol 34, 1983, p 397
[4] Mansfeld, F and Ken&g, M W, presented to 6th European Symposium on Corrosion Inhlbltors,
Ferrara, Italy, 1985
[5] Mansfeld, F, Kendlg, M W, Allen, A F, and Lorenz, W J, in Proceedings, 9th International
Conference on Metalhc Corrosion, Toronto, Canada, Vol 1. 1984, p 368
[6] Juettner, K, Lorenz, W J, Ken&g, M W, and Mansfeld, F, Journal of the ElectrochemicalSociety,
Vol 135, 1988, p 332
[7] Juettner, K, Manandhar, K, Selfert-Kraus, U , Lorenz, W J, and Schmldt, E, WerkstoffeundKorro-
ston, Vol 37, 1986, p 377
[8] Ken&g, M W, Meyer, E M, Llndberg, G , and Mansfeld, F, Corrosion, Vol 23, 1983, p 1007
[9] Mansfeld, F, Corroswn, Vol 44, 1988, p 558
[10] Ken&g, M W and Mansfeld, F, Corroswn, Vol 39, 1983, p 466
[11] van Melrhaeghe. R L, Dutolt, E C, Cardon, F, and Gomes, W P, Electrochtmwa Acta, Vol 21,
1976, p 39
[12] Macdonald, D D and Urqul&, M, Journal of the ElectrochemwalSociety, Vol 132, 1985, p 2316
[13] Mansfeld, F, Lln, S, Chen, Y C, and Shlh, H, ASTM STP 1065, American Society for Testing and
Materials, Phdadelphm, 1990, p 95
[14] Macdonald, J R, hnpedance Spectroscopy Emphastzing Sohd Materials and Systems, Wiley-
lntersclence, New York, 1987. Chapter 2
[15] Gabnelh, C, Identtficatwn of Electrochemwal Processes by Frequency Response Analysts, Solartron-
Schlumberger. 1980
[ 16 ] Epelboln, I, Keddam, M, and Takenoutl, H, Journal ofApphed Electrochemistry, Vol 2, 1982, p 71
[17] Little, B, Wagner, P, and Mansfeld, F, "An Electrochemtcal Evaluation of Blofilms and Calcareous
Deposits Formed in Natural Seawater," presented to International Congress on M~croblologlcally
Induced Corrosion, Knoxvdle, Tenn, Oct 1990, pp 5-9
[18] Lorenz, W J and Mansfeld, F, CorroswnScwnce, Vol 21, 1981, p 647
[ 19] Mansfeld, F, Lm, S, Kam, S, and Shlh, H, Journal of the ElectrochemicalSociety, Vol 137, 1990, p
78
DISCUSSION
S Turgoose ~ (wrttten dtscusswn)--It seems that the eqmvalent circuit used is slmphfied In
the aqueous case there exists parallel ano&c and catho&c branches In the case of coatings
corrosion often occurs with separated anodes and cathodes The use ofslmphfied circuits surely
affects the numbers obtained)
F Mansfeld et al (authors" closure)--We have used the simple clrcmt (Fig 1 ) commonly
discussed m the hterature for simple reactions under charge transfer control The comphcatlons
due to the use of the parameter a have been discussed We have also used the classical Randles
clrcmt (Fig 7), which has been accepted for a long time Comments on the EC for the inductive
loop (Fig 11 ) can be found in the last paragraph of our paper
Corrosion and Protection Centre, UMIST, Manchester, Umted Kangdom

P. R. Roberge I
Analyzing Electrochemical Impedance

Corrosion Measurements by the Systematic
Permutation of Data Points
REFERENCE: Roberge, P R, "Analyzing Electrochemical Impedance Corrosion Measure-
ments by the Systematic Permutation of Data Points," Computer Modehng m Corrosion, ASTM
STP 1154, R S Munn, Ed, American Society for Testing and Materials, Phdadelphm, 1992, pp
197-211
ABSTRACT: The stat~sucal vahdatton of a reststance-capacttance (RC) model from a hm~ted

number of data points can be achieved by systemaucally permuting the three data points that are
chosen to extrapolate the centers of semlorcular impedance dmgrams An earher version of the
geometric analysis techmque, which consisted of finding geometrically the center of an arc formed
by the successwe data points on a complex impedance dmgram, had been successfully apphed to
the study of erosmn corrosion mechamsms of some copper mckel alloys submitted to highly
turbulent condluons
A senes of results obtained with a combmatmn of alloy composmon, exposure condmons, and
environments seems to indicate that the nonadherence to a perfect RC model by electrochemical
impedance data provides lnformatton concerning the types of corrosion processes occurnng on a
metalhc surface The analytical method developed to reveal these fundamental charactensttcs of
impedance patterns wall be critically detaded w~th pamcular emphas~s on the parameters control-
hng ~ts resolution and on its ease of ~mplementatlon
KEY WORDS: electrochemical impedance spectroscopy, locahzed corrosion, corrosion momtor-

rag, carbon steel, copper-mckel, erosion corrosion
Since the early work by Epelboln and co-workers [ 1] on the system iron-H2SO4-propargylic
acid, electrochemical impedance spectroscopy (EIS) has been successfully applied to a multi-
tude of systems [2] Impedance techniques are finding increasing applications in corrosion
research because of the possibility of obtaining information on the chemical mechanisms In-
volved An important advantage of EIS over other laboratory techniques is the possibility of
using very small amplitude signals without disturbing the properties being measured Another
major quality of EIS is the possibility of working in low or variable conductivity environments
EIS has thus been successfully applied to study the corrosion o f iron and carbon steel in neutral
waters [ 3-6 ] or deoxygenated formic acid [ 7]
But even with many fundamental advantages over other electrochemical techniques, EIS
remains difficult to use for field corrosion monitonng The time required to obtain a full imped-
ance diagram imposes a serious limitation to the technique when the specimens under study are
modified relatively rapidly Additionally the difficulties in interpreting a-c Impedance data [8] is
another obstacle that has overshadowed the application o f EIS to field situations Serious investi-
gators have even come to the limiting conclusion that EIS is only valid for uniform corrosion
problems [9]
Department of Chemistry and Chemical Engmeenng, Royal Mdltary College of Canada, Kingston,
Ontarto, Canada K7K 5L0
197
~ (xo,y8 ) X
FIG l--Graphwal method used to extrapolate the center of a depressed semwwcle
Geometrical Extrapolation
In order to overcome these difficulties, a method was recently developed which consisted of
geometrically finding the center of an arc formed by three successwe data points on a complex
impedance &agram [10] The three experimental data points a, b and c (Fig 1), with their
corresponding coordinates (xl ,Yl ), (x2 ,Y2), (x3 ,Y3 ), are linked by the segments ab and bc with
calculated points (x4,y4) and ( x s , y s ) as centers From the slopes of the perpen&cular hnes to
the segment ab and bc which can be calculated using Eqs 1 and 2 it is possible to find the
intercepts y6 and y7 (Eqs 3) with the Y axis made by the perpen&cular hnes passing through
(x4,y4) and ( x s , y s ) respectwely
Pl Y2 - Yl (la)
X 2 -- X 1
P2 Y3 - Y2 (lb)
x 3 --X 2
P3 = tan (my tan 191 + 90 ~ (2a)
P4 = tan (my tan P2 + 90~ (2b)
Y6 = Y4 - P3x4 (3a)
Y7 : Y5 -- P4x5 (3b)
By merging Eqs 3a and 3b it Is possible to find (Eq 4) the intercept (xs,ys), between the two
straight hnes, which also corresponds to the center of a semicircle made by the original data
points used for these calculations, 1 e , ( x t , y l ) , (x2,y2) and (x3,Y3)
ROBERGE ON ELECTROCHEMICAL IMPEDANCE CORROSION MEASUREMENTS 199
1500
~ 01 HZ
I000
500
-r-
0
9 e ;d.c .b
I
a
-500
| a.
-1000
-1500 , , , ~ [ , , , , I , J , L [ , L i , I , , , , | , , , ,
0 500 1000 1500 2000 2500 3000
RE(Z) (OHMS)
FIG. 2--Evolution of the impedance diagrams and of the projected centers for a l O-day passivated 70-30
Cu-Ni cylinder rotating at 5000 rpm. ( a ) Complete diagram in quiescent condition (0 rpm). (b), ( c ), (d) and
( e ) Diagrams made of four frequency measurements after 30, 45, 150, and 300 rain of rotation at 5000 rpm.
Y7 - Y6 (4a)
x8- P3-P4
Y8 = Y6 - P3x8 (4b)
If an impedance diagram had a slightly depressed semicircular shape, the projected centers
would be found in the fourth quadram. This simple observation can be translated into a rejec-
tion criterion that will help further calculations of impedance parameters. One obvious advan-
tage of using a limited number of frequencies during impedance measurements is the gain in
speed. By additionally avoiding the use ofpotentiostatic control it was thus possible to study the
partial breakdown of passivation films on copper-nickel alloys when they are suddenly submit-
ted to erosion conditions [ 11 ]. A typical example of the evaluation of the polarization resistance
(Rp) during the Cu/Ni film breakdown is illustrated in Fig. 2.
The analysis of EIS measurements was further developed by systematically permuting the data
points involved in the projection of centers. This mathematical treatment is schematically iltus-
1 2 3-~Rp
2 3 4-~ 2Rp
135
5 345
2 4 6-~ 3Rp
147
Z 456
O 3 5 7-~ 4Rp
um~
N 258
159
567
4 6 8 -~ 3Rp
369
0 2000 4000 6 7 8 -~ 2Rp

579
RE (z) OHMS
7 8 9-~Rp
16 Rp
FIG. 3--Schematic representation of the results (Rp's) obtained by symmetrically permuting a limited
number of data points.
trated in Fig. 3, which shows the symmetrical combinations of three points that are possible for a
certain n u m b e r of data points (frequencies). By generating a population of centers, it becomes
possible to evaluate semi-quantitatively the fit made by all considered data points and the simple
RC model. It is also possible to estimate with a certain degree of confidence the impedance
parameters behind the apparent RC behavior such as: ( 1 ) the arc diameter (or Rp), ( 2 ) the
depression angle made with the abscissa, ( 3 ) the double-layer capacitance (C in RC), and ( 4 )
the solution resistance (high frequency intercept of the circle with the abscissa).
Experimental Procedure
Erosion Corrosion
The results obtained with two high strength 70-30 Cu-Ni alloys thought to be suitable for
seawater piping systems will be presented in this paper: a 70-30 Cu-Ni modified with niobium
and a 70-30 modified with chromium. Their chemical composition is presented in Table 1.
TABLE 1--Analyzed chemical composition

of two high strength 70-30 Cu-Ni alloys.
Element 70'30 + Nb 70-30 + Cr
Cu 67.7 65.7
Ni 29.3 30.8
Fe 1.0 0.77
Mn 0,81 0.75
Si 0.2 0.31
Nb 0.42
c 0.005 o.o
Cr . . . 2.1
S . . . 0.006
Ti ... 0.06
p . , . 0,005
ROBERGE ON ELECTROCHEMICALIMPEDANCE CORROSION MEASUREMENTS 201
The specimens were machined from cast samples in cyhndncal shapes having a dmmeter of
1 2 cm and a height of 2 6 cm for a total exposed surface of l0 cm 2 The cyhndncal speomens
were pohshed to 600 grit, then washed m turn wtth methylene chloride, acetone, and distilled
water The samples were then immersed in an aerated saline solution for a period of ten days
before making any measurements Macdonald et al' had shown [ 12] that the corrosion potenttal
ofstmtlar alloys reached a stable value after five days when exposed to a saline solution, indicat-
ing a steady state in the film formatton
The one compartment cell [ ! 1 ] was a closed 2-L beaker containing l L of a 3% NaC1 solution
made up with distilled water and ACS-grade NaC1 The cell was left at room temperature (21 ~
and constantly purged with air
The EIS measurements were made with an AC generator/analyzer Solartron Model 1250
controlled by a Hewlett Packard Model HP86 microcomputer The cyllndncal spectmens were
screwed into the rotatmg assembly (Pine Instrument Co ) and the electrochemtcal measure-
ments made at 0 and 5000 rpm (equivalent surface velocity 3 1 m s -~) The corrosion potential
was left floating and the EIS measurement made m a two electrode configuration following a
techmque described elsewhere [13] Two htgh surface area carbon electrodes were used as
counter electrodes in order to mmlmtze the impedance contnbutlon of this part of the circuit
The floating corrosion potenttal was measured between the Cu-Nt cyhnders and a saturated
calomel reference electrode (SCE) with an IEEE controllable multlmeter
lnhtbttton of Carbon Steel Corrosion

The same EIS arrangement was used to make the measurements wtth AISI 1020 C-steel fiat
specimens exposed to a 3% NaC1 solution with/or without a mild inorganic inhtbltor ( 1 2%
Na-Molybdate) The cell used in this study was also eqmpped with a gas purge and a SCE
reference brought m close electrolyttc proxtmlty to the steel specamens by a Luggin capillary
The two metallographlcally mounted specimens (600 gilt), separated by 2 5 ram, were kept in a
stable parallel position with plastic screws in an arrangement described elsewhere [14] The
probmg a-c stgnal was apphed directly between the two steel specimens, thus avoiding the
necessity of a separate counter electrode Such an arrangement is comparable to the commercial
probes available for various apphcations
Results
Eroston Corrosion
Figures 4 and 5 represent two series of measurements made respectively with a 70-30 Cu-Nt
alloyed with 0 4% Nb and a 70-30 alloys with 2 1%Cr Rotating these prepasslvated alloys seems
to temporarily cause a decrease of their polanzatton resistance which eventually reverts to mmal
good values after a few hours of rest The corrosion resistance of the 70-30 alloyed with Nb
seems even to be improved by such a treatment Table 2 summarizes the results calculated
systematically from the large number of projected centers obtained by permuting data points of
individual curves presented in Figs 4 and 5 Whale the results corresponding to the 70-30 Cu-N1
alloyed with Nb correlate well with the visual examination of Curves 4a, 4b, and 4c, the high
standard deviation (SR) calculated for the mean of centers projected from Curve 5a indicates a
difficulty m testing that alloy This behavior was reproduced for many specimens of the same
cast sample
Two other interestmg charactensUcs revealed dunng the analysts of curves of Figs 4 and 5 are
(1) the major difference between the steadily low depression angles observed for the 70-30
alloyed with Nb (22~ ~) and the higher angles ( 330-37 ~) calculated for the patterns belong-
20000
t=
u
i5000
t=
t-
o
I0000
I
5000
, = = l i , , I , , , I , J
00 10000 20000 30000 40000
RE(Z) (Ohm cm 2)
FIG 4--Impedance dtagrams made wtth a lO-day passtvated 70-30 Cu-Nt alloy contatnmg mobtum and
exposed to a 3% NaCI aerated solunon ( a ) In a qutescent condition ( b ) After 8 h of rotanon at 5000 rpm ( c )
In a qutescent condmon 16 h after the rotation period
lng to the 70-30 with Cr, and (2) the high capacitance values (Cdl) calculated for the 70-30 with
Cr (220-450 #F cm -2) compared to those calculated for the 70-30 with Nb (106-150
#F cm -2)
By using a limited number of frequencies dunng EIS measurements and avoiding potentio-
static control it was possible to monitor both the E~o~and the R p (inversely related to t~o=)during
the partial breakdown ofpassivatlon films of these Cu-NI alloys when they are suddenly submit-
ted to erosion conditions Figures 6 to 8 illustrate some of the results obtained dunng the study of
Cu-NI alloys exposed to erosion corrosion conditions
Figure 6 illustrates the evolution of E~o~ and Rp for the Cu-Ni alloy containing Nb in an
air-saturated saline solution Immediately after starting the rotation, E~o~ goes toward more
negative values, reaching a minimum after 30 mln and a stable value after 2 h Rp also decreases
rapidly, but it levels offat its minimum value after 2 h Both Rp and free Eoo~ tend to recover
their onginal values when the rotation is stopped When the solution is partly depleted of its
oxygen, E~,~ and Rp behave very differently (Fig 7) In this case E~o~ drops slowly to more
negative values when the rotation is started and comes back slowly toward positive values when
it is stopped The changes i n Rp are also very slow during the erosion sequence, and the recovery
of the onglnal values, when the rotation is stopped, takes a very long period (24 h) The
transitory shift in E~o~ has also disappeared and E~o. now follows the Rp behavior
The results obtained with a 70-30 Cu-N1 alloy modified by the addition of 2% Cr show (Fig 8)
a relatwely similar, but less accentuated, lag between Rp and E~o,~ for ten-day prepassivated
specimens On the other hand, the surface of this alloy remained shiny with the exception of a
few tarnished spots, whereas the 70-30 Cu-NI with Nb became green as is usual with Cu-N1 alloys
exposed to saline solutions [ 12] But this apparent excellent performance is not confirmed by a
comparison of the calculated values for the two Cu-Ni alloys Rp'S The 70-30 Cu-Ni modified
with Nb recovered spontaneously from an erosion period while the 70-30 Cu-Ni with Cr did It
with more difficulty
12500,
oooo \ )t Iti
Od
m
u
.-0,,,
E 7500 0
S
w
~E 5000
I-4
I
.$ ~ .Ol Hz
00 5000 t0000 15000

FIG 5--hnpedance dtagrams made wtth a lO-day passtvated 70-30 Cu-Nt alloy contammg chromtum and
exposed to a 3% NaCI aerated solutton ( a ) In a qutescent condztton ( b ) After 8 h of rotatton at 5000 rpm (c)
In a qutescent condttton 16 h after the rotatton period
Corroston o f Carbon Steel
Figures 9 and 10 dlustrate some typical impedance patterns obtained when freshly pohshed
C-steel speomens were exposed to a deaerated (Fig 9) or aerated (Fig 10) environment The
analysis by permutation of data points contained m Curves 9a, 9b, and 9c (Table 3) confirms
the visually obvious fact that these curves are close to being part of perfect circles In the
presence of an inhibited solution (9a) the steel surface has a very high impedance that is drasti-
cally decreased by adding salt to the solution When the same steel is exposed to a deaerated
TABLE 2--Resuhs obtained by permuting tmpedance data points for two types
of 70-30 Cu-Nt alloys prepasstvated m an aerated 3% NaCI solunon
Surface Depression
Velocity Rp SR Angle Cal
Type Curve (ms -I) (kfl 9tzm2) (%) (deg) (t~F cm-2)
+0 4% Nb 4a 0 38 18 24 106
4b 31 16 6 22 130
4c 0 45 14 22 150
+2 1%Cr 5a 0 25 70 33 220
5b 31 9 6 37 450
5c 0 27 9 37 270
-250 i i i i ] i i i i
.... I ' ' ' I .... I .... Ii00
Rp ~
8o
-260
S
60
-270
i
I
.o
2O
ROTATION I
-280 .... I .... I , , , , l , I , , I , , , , I , , , , 0

0 5 I0 15 20 25 30
TIME (Hours)
FIG 6--Behavtor of E~o. and Rp wtth nine and rotatton (5000 rpm) for a lO-day passtvated 70-30 Cu-N~
alloy contatnmg 0 4% Nb tn an atr saturated 3% NaCI solutton ([ 02] = 6 3 ppm)
solution (9c) containing only 3% NaC1 Its surface is even less passwated While the absolute Rp
values are different m these three experiments, it should be noted that both the standard devia-
tion and the depression angles calculated for these curves are nearly constant (SR ~ 5% and
depression angle ~ 12 ~ The microscopic inspection of samples exposed to these conditions
revealed the uniform nature of corrosion attack in all these cases On the other hand, the
calculated capacitance values seem to indicate an increase of the available surface for specimens
exposed to saline environments (64 and 80 #F cm -2) compared to those only exposed to an
inhibited and deaerated aqueous environment (20 #F cm -2)
The presence of oxygen m the same electrolytes can drastically change the behavior of the
steel After only a brief exposure to an aerated 3% NaCI solution the unprotected steel surface
becomes rusty in th~s neutral environment The data obtained w~th steel specimens m contact
with aerated electrolytes had to be normalized m order to present them m one figure Figure 10
contains data, corresponding to three different experiments, which have been reduced to a
common relatwe scale by dividing them by their respective calculated Rp'S In the presence of an
aerated solution containing 1 2% Na-molybdate (Fig 10a), the steel remains quite passive and
corrodes umformly quite slowly Both the relative standard deviation (5%) and the depression
angle ( 13 ~ calculated by permuting data pomts of Curve 10a remain low
On the other hand, it ~s impossible to d~stmgmsh, with such a representation, curves corre-
sponding to an exposure to either an aerated solution containing 1 2% Na-molybda~te or one
containing 3% NaC1 In the latter case, corrosion has become very rapid but remains uniform
The calculated results corresponding to these experiments are presented in Table 4, where it can
be seen that, for an exposure to 3% NaC1, the steel is roughly 300 umes less passwe than when it
-250 , i u u [ r i i i i i
Rp ~ 100
.
Ecorr
BD 7O
"10
-260
P.
, i BO
"r"
Z
tO
(3
=1
L
L X
(3
O tO
LU 4O 0
-270
I 20
ROTATION l
#
-280 .... Ill, I , , , , l , }, , t I = , , , I , l l i 0
0 5 10 15 20 25 ~q0
TIME (Hours)
FIG. 7--Behavior of Eco~ and Rp with time and rotation (5000 rpm) for a lO-dar passivated 70-30 Cu-Ni
alloy containing 0.4% Nb in an air-depleted solution ([ 02] = 3.5 ppo O.
is exposed to 1.2% Na-molybdate. But it can also be observed that the calculated standard
deviation (6%) and depression angle ( 15 ~ ) for a steel surface exposed to 3% NaCI remain small.
The calculated capacitance values for both the experiment with a 3% NaCI solution (80 #F
cm -2) and with 1.2% Na-molybdate (90 #F cm -z) remain relatively small in comparison with
two other experiments simulating conditions favorable to the occurrence of localized corrosion.
By exposing the steel specimens to an aerated solution containing 1.2% Na-molybdate and 3%
NaCI it was possible to keep the metallic surface partially protected and slow down the general
corrosion processes, thus favoring the occurrence of localized pitting corrosion. The typical
shape of curves when pitting corrosion is dominant is illustrated in Fig. 10b, where a generally
depressed pattern can be observed. This is translated into a high calculated depression angle
(42 ~ but with a standard deviation still very low (8%) indicating good agreement with the
circular pattern associated with the simple RC model. Besides the high depression angle calcu-
lated in this case, one should remark the phenomenally high value also observed for the calcu-
lated capacitance (2000 #F cm-2).
In another series of experiments crevice corrosion conditions were simulated by neglecting to
apply the protecting layers of primer on the edge of the steel specimens. A typical pattern of
impedance measurements obtained in these cases is illustrated in Curve 10c, where it can be
seen that both ends of the impedance spectrum are affected. While the high frequency data
points cross over to negative resistance values, the low frequency measurements become erratic
and unreliable. The calculations made by permuting data points of Curve 10c translate these
discontinuities into a large relative standard deviation (35%) accompanied by an also large
depression angle (30 ~ and high capacitance value (600 #F cm-Z).
-210 ' ' I
Ecorr
' ' ' ' I] ' ' ' ' I '
, / , ....! 100
-220
Rp ~ 80
-230
ROTATION J 0
H
L
N
L X
8 -240
,,i 4o
-250 20
-260 . . . . t , , , , I I I I ] I , , L I , ,, I . . . . 0
0 5 10 15 20 25 30
TIME ( H o u r s )
FIG 8 - - B e h a v t o r of Er and Rp wtth ttme and rotatton (5000 rpm) for a lO-day passtvated 70-30 Cu-Nt
alloy conlammg 2 1% Cr in an atr saturated solutton
Discussion
Eroston Corroston of Cu-Nt Alloys
The kinetics of the corrosion reactions can best be explained with the help of the Evans'
&agram shown m Fig 11 [ 15 ] The catho&c reaction (Eq 5) supplying the adsorbed oxygen is
represented by hne AB
cathode 1/2[O2] + [H20] + 2e = 2 [ O H - ] (5)
The ano&c reaction (Eq 6), which would take place m absence of passwaUon, IS
anode 2Cu = 2Cu+~l + 2 e - (6)
represented by hne CD Shortly after immersion into aerated seawater, a copper-mckel alloy will
form a protectwe layer of corrosion products (Eq 7)
2CU+l + 2 [ O H - l = Cu20 + [H20] (7)
with an associated IR drop that causes the slope or resistance to mcrease from the value gwen by
hne CD to the value gwen by hnes T. The mtersecUon of hnes 7". and AB gaves the corrosion
potentml E~o,. and the corrosion current I~o,. Eventually, the IR drop wall be large enough that
200
"-r-
C3
HZ
100
[
02 HZ
l I I
O0 l J I J ] ] (
100 200 300 400
RE IZ) {KOHNS)
FIG. 9--Impedance diagrams made with 1020 C-steel specimens exposed to a deaerated solution containing
(a) 1.2% Na-molybdate, (b) 1.2% Na-molybdate + 3% NaCl, and(c) 3% NaCl.
E~o~reaches Ec~2o/c.2(on)3c~( Eq 8 ). At this point the outer corrosion product layer of Cu2 (OH)3
will form [16].
2 [Cu~o,]
+z + 3[OH-] + Cl- = Cu2(OH)3Cl (8)
The behavior of copper-nickel alloys under hydrodynamic conditions can also be explained
.5
.4
t-~
t"t-
.3
/)" >oo2 .z
I .2 -.,'~" b ~ o
.t .z \N
0.~). , I
91
, I
.2
, [
.3
, I
.4
, ]
.5
, I
.6
,
.7
1 , I
.B
i . I
.9
l
~..0
RE (Z) /np
FIG. I 0-- Impedance diagrams made with 1020 C-steel specimens exposed to an aerated solution containing
(a) 1.2% Na-molybdate, (b) 1.2% Na-molybdate + 3% NaCl, and (c) 3% NaCl.
TABLE 3--Results obtained by permutmg tmpedance data pomts for AISI 1020 steel spectmens
exposed to deaerated electrolytes
Depress=on
E~o,~ Rp SR Angle Cal
Solution (mV vs SCE) (kfl. cm2) (%) (deg) (uF cm-2)
3% NaCl -740 70 7 I1 80
l 2% Na-Molybdate -420 420 4 12 20
l 2% Na-Molybdate +3% NaCl -740 130 3 13 64
with this model Under erosion condmons the following phenomena occur At first, the film is
eroded by moving solution and dissolution of the outer porous layer [ 16] occurs, shifting Eq 5 to
the right On the Evans diagram this would correspond to a shift from point 1 to point 2 This
breakdown observed on Er and Rp at 5000 rpm is not observed at low rotation speed where
erosion is less likely to happen Dunng a second phase, the oxygen reduction reaction rate could
increase (line A'B') due to the modification of the metallic surface On the Evans diagram this
would correspond to a shift from intercept 2 to point 3
The results illustrated m Fig 6, where the evolution of Er and Rp of the Cu-NI alloy contain-
lng Nb is momtored dunng an erosion corrosion period, can be explained by using this Evans
diagram The important time lag ( ~ 2 h) observed between the increase of the rate of oxygen
reducuon, momtored by followmg the decreasing Rp, and the film breakdown Itself (Er is
md~catwe of the sohd-state nature of the changes occurnng on the metalhc surface Such an
explanauon for this unexpected behavior was recently confirmed by other soentlsts using the
sophisticated electrohydrodynamlc ( E H D ) techmque [17] dunng the study of pure copper
exposed to aerated sahne environments [ 18] The complex results obtained with the EHD
techmque could then be explained by invoking a blocking surface model to descnbe the diffi-
culty oxygen has m reaching the reaction sites on the metalhc surface covered by a sohd oxide
film The behavior observed (Fig 7) when oxygen is partly depleted (3 5 ppm) would indicate
that the concentratton of oxygen m solution has become critical for the stabd~ty of the passw-
atlon film covenng the Cu-NI alloy
When compared to the EIS results obtained with the 70-30 Cu-NI containing Nb, those
obtained with the Cr-modlfied alloy seem to possess puzzhng and fundamental differences
(slower recovery after the erosion period, high SR and depression angle) The microscopic
examination of 70-30 Cu-Nl (Cr) specimens after a few weeks' exposure to the sahne environ-
ment revealed that the addmon of 2 1% Cr to create a higher strength alloy had also created the
spontaneous suscepUbdlty to suffer from mtergranular corrosion The EIS parameters became
thus retrospectwely good indicators of localized corrosion problems The study of carbon steel
TABLE 4--Resuhs obtamed by permuting trnpedance data points for AISI 1020 steel spectrnens
exposed to aerated electrolytes
Depress|on
E~o~ Rp SR Angle Cal
SoluUon (mY vs SCE) (kft. cm2) (%) (deg) (~F cm-2)
3% NaCI (umform) -680 14 6 15 80
3% NaCI (crevtce) -730 21 35 30 600
I 2% Na-Molybdate - 100 420 8 15 90
1 2% Na-Molybdate + 3% NaCI -550 42 8 42 2000
z Cu -* Cu+(oxide) + e
ILl
89 + H20 + 2e :~ 2(OH-)
Cu ~ (CU~o l) + e
LDG (CURRENT)
FIG I l--Evans dtagram of the eroswn corroston behawor of Cu-Nt alloys as a functton of trine (trine T2
> T,) [15]
corrosion as a funcUon of water chemistry condmons was planned to verify these conclusions
with a system more easily controlled
Carbon Steel Experiments
The study of carbon steel exposure to vanous aqueous environments permitted us to venfy
that the nonadherence of the EIS measurements to a perfect RC model is a nch source of
information concerning the types of corrosion processes occumng on a metalhc surface The
depression angle or angle of tilt of the orcular arc from the real axis is an almost ommpresent
character of EIS measurements [ 19] The constant phase element (CPE) which has to be added
to the classical RC clrcmt to model the departure from ldeahty of some lnterfaclal systems has
been demonstrated experimentally to onginate from the microscopic roughness of the interface
[20-22]
In a recent pubhcatlon [ 23 ], the apphcablhty of the CPE to estimate the roughness of solid
metal electrodes was put to test for a series of freshly pohshed metalhc surfaces It was demon-
strated then that with increasing roughness the diameter of the semlorcles does not only de-
crease, due to the apparent expected decrease of Rp and parallel increase of Col (themselves
caused by an increased real surface area), but that the semicircles are progressively more de-
pressed The data given m Table 5 are the results obtained from iron speomens mechanically
pohshed with emery paper of different gram size and immersed in an acidic environment before
making the impedance measurements
Generally a CPE occurs If the material under investigation cannot be regarded as homoge-
neous The experimental demonstraUon was made, in the same paper [ 23 ], that electrodes of
TABLE 5--Results from EIS measurements on tron

electrodes m H2SO 4 solutton, pH 1. m dependence
on the pohshmg pretreatment [23]
Pohshmg Rp Dep~sslon Cdl

(Eme~) (~) Angle (~F)
280 105 19 6 16 5
500 110 15 8 12 5
600 119 11 6 10 7
800 167 92 10 0
different matenals have a constant depression angle when their metallic surface, polished to a
constant grit, is immersed in a common environment (H2504, pH l ) It is then a valid extrapola-
tion to project that the surface modifications introduced by the formation and propagation of
localized pits should be related to the calculated depression angle Work presently under pro-
gress is strongly focused on establishing correlations between pit depth measurements and the
integration of depression angles with respect to exposure time
The scatter represented by the relative standard deviation calculated for Rp's has a straightfor-
ward significance, since it represents the adherence of the real measurements to a single and ideal
arc A large standard deviation would thus indicate a far from Ideal behavior which in turn could
be attributed to the composite nature of the corrosion processes in such cases A more elaborate
model would then have to be used in order to fit the real data more closely Such a model could
become quite complex and more resemble a network of parallel and senes RC circuits [14]
Conclusion
By simplifying both the instrumental and analytical complexities involved in performing EIS
measurements, it is possible to apply the EIS technique to very practical problems where m sttu
monitonng techniques are scarce and badly needed EIS has been proven to be applicable to a
broad variety of problems, ranging from low conductivity environments, to very difficult erosion
corrosion conditions
The present paper has tried to demonstrate how the automatic and relatively simple data
analysis performed by permuting EIS data points to generate the resistance to polarization (Rp)
or ItS associated corrosion resistance can also reveal fundamental characteristics of interfaclal
behaviors While the Rp relative standard deviation seems to be related to the macroscopic
complexity of the corrosion mechanisms, the angle of tilt seems to be more closely associated to
the microscopic transformations occurnng on the metallic surface Work is under progress to
establish solid and useful correlations between the fundamental EIS parameters and specific
corrosion conditions typical of inhibitor treatment interruptions, corrosive agent ingresses, or
even simply alloy/environment systems
References
[1] Epelbom, I, Keddam. M, and Takenoutl, H. Journal ofApphedElectrochemtstry, Vol 2, 1972, pp
71-79
[2] Zeller !II. R L and Savmell. R F, Corroston Scwnce, Vol 26, No 8, 1986. pp 591-599
[3] Mansfeld, F, Ken&g, M, and Tsal, S, Corroston Sctence. Vol 22, No 5, 1982, pp 455-471
[4] Bonnel, A, Dabosl. F, Deslouls. C, Duprat, M, Keddam, M, and Tnbollet, B, Journal of the
Electrochemwal Socwty, Vol 130, No 4, April 1983, pp 753-766
[5] Duprat, M and Dabosl, F, in Proceedings, 9th International Congress on Metalhc Corrosion, Toronto,
Canada, Vol 4, 3-7 June 1984, pp 104-109
[6] Mansfeld, F, Kendlg, M W, and Lorenz, W J , Journal of the Electrochemwal Soctety. Vol 132, No
2, Feb 1985. pp 290-296
[7] Sekme, I, Ohkawa, H , and Handa, T , Corroston Sctence, Vol 22, No 12, 1982, pp 1113-1123
[8] Lorenz, W J and Mansfeld, F. Corrosion Science. Vol 21, No 9-10, 1981, pp 647-672
[9] Sllverman, D C and Carnco, J E, Corroston. Vol 44. No 5, May 1988. pp 280-287
[10] Roberge, P R and Beaudom, R , Journal ofApphedElectrochemtstry, Vol 18, 1988, pp 38-42
[11] Roberge, P R and Halhop, E m Proceedmgs. Corrosion '90, Nattonal Association of Corrosion
Engineers, Las Vegas, 23-27 April 1990, Paper No 15, pp 1-11
[12] Macdonald, D D , Syrett, B C, and Wing, S S, Corroston, Vol 34, No 9, 1978, pp 289-301
[13] Wdhams. D E and Asher, J , Corroston Sctence. Vol 24, No 3, 1984, pp 185-196
[14] Roberge, P R , Halhop, E, Asplund, M. and Sastn, V S, Journal ofApphedElectrochemtstry. Vol
20, 1990
[ 15 ] Elselstem, L E , Syrett, B C, Wing, S S, and Cahgmn, R D , Corroston Scwnce. Vol 23, No 3, 1983,
pp 223-239
[16] Kato, C, Castle, J E , Ateya, B G , and PIckenng, H W, Journal oftheElectrochemwalSocwty. Vol
127, No 9, 1980, pp 1890-1896
[17] Trlbollet, B and Newman, J , Journal of the Electrochemwal Soczety. Vol 131, No 12, 1984, pp
2780-2785
[18] Deslouls, C, Mengoh, C, Muslam, M, and Tnbollet, B, m 2t~me Forum sur les Impddances Electro-
chomques. C Gabnelh, Ed, Montrouge, France, 28-29 Oct 1987, pp 295-309
[19] Jonscher, A K, Dtelectrtc Relaxatton m Sohds. Chelsea Dielectrics Press, London, 1983, Chapter 5
[20] De Levle, R , Electrochtmwa Acta. Vol 10. 1965, pp 113-130
[21] Bottelberghs, P N and Broers, G H J , Journal ofElectroanalytlcalChemtstry, Vol 67, 1976, pp
155-162
[22 ] Bates, J B, Wang. J C, and Chu, Y T . Sohd State Ionlcs. Vol 18 & 19, No 2, 1986, pp 1045-1049
[23] Rammelt, U and Remhard. G , Electrochtmlca Acta. Vol 35, No 6, 1990. pp 1045-1049
[24] Macdonald, J R (Ed), Impedance Spectroscopy. Wdey. New York, 1987
Spatial Corrosion Modeling
R a y m o n d S. M u n n i
A Review of the Development of

Computational Corrosion Analysis for Spatial
Corrosion Modeling Through Its Maturity
in the Mid-1980s
REFERENCE: Munn, R S, "A Review of the Development of Computational Corrosion Anal-
ysis for Spatial Corrosion Modeling Through Its Maturity in the Mid-1980s," Computer Model-
mg m Corroston. ASTM STP 1154. R S Munn, Ed, American Sooety for Testing and Materials,
Phdadelphla, 1992, pp 215-228
ABSTRACT: The last decade and a half has seen the development of the dlsclphne of computa-
tional corrosion analysts Thejornmg of electrochemical theory, numerical methods, and computer
technology has facthtated rigorous quanutatwe evaluauon ofgalvamc corrosmn systems that now
obvmtes trial-and-error developments, quahtatwe rules of thumb, and full-scale system expenmen-
tatmn This paper reviews the development of this capablhty from its conceptmn m the mld-1970s
through its maturatton and essenually ns compleUon m the mld-1980s Thls review centers on the
domain (fimte element and finite difference) methods, with a bnef review of boundary methods in
corrosion analysis
KEY WORDS: corrosion analysis, galvanic corrosion, computatmnal methods, fimte element
method, fimte difference method, mathemaucal models, d~fferenual equauons, mathemaucal pre-
diction, nonhnear polanzatmn
Introduction
Interest in the quantitative prediction ofelectnc current and potentml distributions in conduc-
tive media has existed for at least five decades, with some background mathematics evident over
a century ago Attempts to quantify these predlcUons for the specific discipline of electrochemis-
try are traceable back nearly as far, the motwation for which being applications in corrosion
prediction, electrodeposltion, and battery technology The history of this problem follows a slow
development via analytical methods for thirty-five years before the more rapid advancement
using numerical methods that began in the late 1970s This paper will trace the history of the
development up through modern methods after stating the specific problem to be solved Follow-
lng will be a statement of the objective o f this research and a description o f several computa-
tional methods
Statement of the Problem

The problem under consideration m this paper is that o f n u m e n c a l prediction o f the electric
potential distribution in an electrolyte m e d m m due to the presence o f submerged dissimilar
metals a n d / o r externally-apphed ~mpressed currents From the electrochemical potential value
Engmeenng team leader, Naval Undersea Warfare Center, Code 412, New London, CT 06320
215
adjacent to a wetted metal surface may be deduced the corresponding "applied" or net current
density, using a potentiostatlc polarization curve for that particular metal/electrolyte system
Further, depending on the proximity of other reactions, the predicted potential state of the metal
surface may be indicative of the current density associated with the metal dissolution partial
reaction, from which may be calculated the metal dissolution rate, using Faraday's law A
successful computational corrosion analysis method must be capable of performing the electro-
chemical potentml prediction for a system of general geometry, involving several dissimilar
wetted metals, it must incorporate the generally nonhnear electrode kinetics (polarization behav-
ior) of the constituent metals, and it must adhere to the pnnclples of the modem mixed potential
theory of electrochemical kmetics Further, the method must be applicable to practical situations
involving galvanic corrosion, sacrificial anode and impressed current cathodic protection design,
electrodeposltlOn, and battery technology
Ltterature Revzew
A literature search was performed on background information literature through mid-1986
relating to the computational corrosion analysis problem General topics which are prerequisite
to this development include corrosion chemistry and theory, corrosion kinetics, electncal field
theory, analytical mathematics for field problems, measurement experimentation and hardware,
pnnclples of cathodic protection, and numencal methods including finite difference, finite ele-
ment and boundary element methods
A large part of the early work on electrochemical current and potential distribution make
reference to the general mathematical work of Laplace, Kelvin, Riemann, and Fourier, applying
that mathematics to the role of geometry on solutions involving known physical laws The
review of the background work described in this paper will be separated into analytical, graphi-
cal, and numencal solutions to this mathematics, introducing electrochemical theory as appro-
priate The literature of analytical and graphical solutions is presented here, and reviews of the
numerical methods will be presented
Analyttcal Methods
The earhest of references that provide a basis for modem work in the corrosion field, ironi-
cally, had no such intended application Dwight [ ! ] synopsized much of his earlier work that
dealt with the "grounding resistance" of electrical connections to the ground and arrays thereof
His work was based on the mathematical expressions for capaotance of elements in dlelectnc
media, derived as emplncal senes expansions of the basic equation He correctly drew the
analogy to resistance in conductive media, and he used symmetry rules to extend the solutions to
arrays of but'led rods and plates The (uniform) resistivity of the soil was employed, but no
accounting for local effects (polarization) at the metal/soil interface was attempted
A decade later, a book by Sunde [ 2 ] concentrated on the same subject ofgeometncal effects in
earth conduction That work was more complete in apphcation and more rigorous in basis
Sunde began by formulating a differential equation to describe the potential field due to an
lnfimteslmal current source in a conductive medium By integration of that current over the
length or surface of a particular conductor, using an assumption of uniform "leakage current"
over the conductor, the potential distribution over the conductor was derived and the "anode
resistance" was defined Sunde then considered the phenomenon of"mutual resistance", inter-
ference due to the symmetric locations of multiple electrodes, an important geometrical consider-
ation This work, however, was again hmlted to specific geometnes and nonpolanzing elec-
trodes Sunde's work, as well as Dwight's, has become classical to those in the cathodic
protection industry for prediction of current dlstnbutlon in large systems Committee T-7L-2 of
MUNN ON COMPUTATIONAL CORROSION ANALYSIS 217
the National Association of Corrosion Engineers (NACE) has included these works in a state-of-
the-art review [3] of the subject of anode resistance, in which this author has participated
Further, work today by Cochran [4] and others continued in this area, applying computer
techniques to solve the traditional equations of Dwight and Sunde Because those approaches do
not consider the polarization kinetics of the electrodes, however, they cannot be considered
complete or capable of yielding accurate results except m "macroscopic" systems where dimen-
sions are large, polanzatlon is low, and/or electrolyte conductivity Is low (These parameters
will be discussed hereinafter )
In a series of papers [5-9] in the early 1940s, Kasper used fundamental electrical theory to
calculate current distributions in electrodeposmon systems This appears to be the first such
application of theory to electrochemical problems Kasper's first paper [5 ] described the mathe-
matical theory of the potential This is not to be confused with "mixed potential theory" which
was developed later with apphcatlon only in electrochemistry Moreover, the theory of the
potenual pervades most fields of physics, not explaining the physical laws involved, but rather
describing the effect of geometry on the mamfestatlon of the particular phenomena throughout
the system The theory of the potential was described in general terms of the distribution of
potential energy between spatial boundaries which represented different levels of potential en-
ergy The theory was applied to the "electrokmetic" situation involving the conduction of poten-
tial energy as opposed to the electrostatic case The term "electrokmetlc" may be ambiguous
because of other modern usage of the word The term "electrodlc" will be used in this paper to
indicate the phenomenon of the kinetics of electrode polanzauon, following the terminology of
Bockns and Reddy [ 10] "Electroconductlon" will hereafter apply to that conduction of electri-
cal energy referred to by Kasper as "electrokmetic"
In that apphcation, Kasper observed the following restrictions ( 1) the medium (electrolyte)
exhibits a linear conduction behavior (Fourier-Ohm law of conduction ), (2) the electrolyte is
electrically homogeneous and lsotropic, (3) the current flow through the electrolyte surface does
not alter the equlpotentlal nature of the electrode, and (4) a dlscontlnmty in potential may exist
across the boundary of the electrode due to the passage of current, but the &scontmulty must be
uniform over the electrode surface Of these restrictions, only the equipotentiahty of the elec-
trode is physically unreahstic The solution of this shortcommg is one of the objectives of the
work described, as will be detailed later Kasper's introduction of the potential discontinuity at
the electrode surface was a novel consideration and is, of course, an accurate description of the
polarization phenomenon Kasper noted the general reluctance of the electrochemical commu-
nity to apply the theory of the potentml and the mathematical prowsion for potential discontinu-
ity to the phenomena of electrochemistry
Kasper [ 5 ] applied this mathematics to current flow between parallel plates, between concen-
tric cylinders, and between concentric spheres The mathematics of this scheme is presented
elsewhere In these cases, the uniform electrode potential assumption ((3) and (4), above ) was
valid because of the symmetry of these problems In subsequent papers [6-9], Kasper applied
this mathematics to a number of unsymmetrical geometries, applying the method of images and
graphical techniques to bnng the solutions into conformance with the eqmpotentml electrode
assumption, with the addmonal recognmon that polarization tends to make current distributions
(m electrodeposltlon) more uniform Kasper [7] went on to refute the common idea that
"throwing power" (in electrodeposmon, and later used in cathodic protection) was a property of
the electrolyte, independent of the material or shape of the electrode He then discussed the
problem of non-equipotential electrodes as boundaries of the medium for which the Laplace
equation descnbes the potential distribution, classifying the boundary condmon mathemati-
cally He also discussed the effect of polarization on current distribution, but the remainder of
his work m solving problems of particular geometries was based on the limiting assumption of
eqmpotential electrodes
Kasper's senes of papers [5-9] was clearly the most rigorous application of mathematics to
electrochemical phenomena to that date, and for several decades to come Wagner and Waber
and others to following picked up on Kasper's lead, but directed it toward a more pracUcal
apphcaUons approach
Wagner [11] apphed the mathemaUcs used by Kasper to several geometric cases, gleanmg
from these certain trends of geometry, polarization, and size effects That and subsequent work
[12] pursued the slgmficance of a "polanzaUon parameter", defined as the product of the
electrolyte conductwlty and the slope of the cathodic polanzatlon curve (kr = ~hc), earher
ldenUfied by Kasper [7] and Hoar and Agar [13] m describing the geometrical influence
("throwing power") of a particular system He apphed the "polarization parameter" to simple
system geometries with hnear polarizing boundary metals, companng the polanzaUon parameter
(kc) with a characteristic dimension of the system (L. f ) Wagner tabulated the characteristic
dimensions of several geometrical condmons, wntmg expressions for current density m the
system These relations were actually alternatwe forms of the expressions derived by Dwight [ 1]
and Sunde [2], but accounting for electrode polarization
Waber and his colleagues [14-18] apphed the pragmatic aspects of the preceding work to
(mathematically) simple geometries The senes of papers considered the various geometries with
increasingly complex combmaUons of electrode polanzaUon The last of this series [ 17] empha-
sized the size effect m potentml and current distributions m galvanic cells, concluding that a
galvamc cell could be characterized as "microscopic" or "macroscopic" (irrespective of absolute
size), depending on whether a characteristic dimension of the cell is small or large compared to
the polarization parameter In "m~croscop~c" systems, the effect of polarization is dominant
(over the spatial separations, which appear "small") and the current distributions are relatwely
uniform over the electrode surfaces Whde Waber's work apphed the mathematics to physical
cases of practical importance, it must be remembered that it was hmlted to rather simple geome-
try and hnear polanzauon behavior
A textbook m conduction heat transfer by Carslaw and Yeager [ 19] gwes solutions to dozens
of particular geometrical and boundary condmon cases revolving the Laplace equation The
straightforward analogy between the application of the Laplace equation to the phenomena of
conduction heat transfer and the electrical conduction revolved m electrochemical systems ~s
described elsewhere The mathematics of Carslaw and Yeager's soluUons is rigorous and vahd
for the particular cases No attempt was made, of course, to treat the nonhnear boundary condi-
tions of electrochemical processes, because these have no analogous form m heat transfer Fur-
ther, the solutions were limited to cases of particular, although increasingly complex, geometries
Two papers by Parnsh and Newmann [20,21] extended earlier soluUons of simple geometry
to include both hnear and Tafel polarization behawor and dlffuslon-hmlted current density
Current d~stnbut~ons for the particular geometries were calculated, noting the relatwe indepen-
dence of electrodes (referred to by Waber as macroscopic behavior) for particular hmlts of
nondlmens~onal cell sizes A further result was a secondary calculation of the concentration
gradients within the cell Th~s latter aspect was investigated further by Newmann and colleagues
[22,23], consldenng the transients aspect of ~on migration The kinetics aspects of d~ffUSlOn
were apphed to predict the current density reqmred to maintain a given electrode potentml
(polanzaUon) as a function of t~me, with the conclusion that t ~ 1 / ~ Th~s was sub-
sequently extended to predict the potentml d~stnbuuon m the (nonuniform) electrolyte and to
address the magmtude ofth~s phenomenon when the electrolyte and the electrode surface experi-
ence a relatwe velocity Correlation between prediction and experiment was good, indicating a
"stagnant" condmon (lower current density at increasing Umes) at small relatwe velocity, and
ummpeded condmons (t ~ tL) at h~gh velocity Th~s correlauon indicates that the analyUcal
representation of polarization was vahd, captunng both the Tafel and d~ffus~on-hm~ted portions
of the polanzaUon curve and the change m the adjacent electrolyte w~th t~me
A review paper [24] on the Soviet literature of the 1950s and 1960s indicated a significant
amount of work directed toward calculation of the potential and current distributions dunng
corrosion and electrodeposltion of metals The review cites work analogous to, but postdating,
that of Kasper, Wagner, and Waber, and then goes on to indicate a predominance of superposi-
tion, approximation, and graphical methods used to solve these problems and superpositions of
time These methods were limited to simple geometnes, or combinations thereofifsuperposltion
approximations were tolerable A book on cathodic protection by Iossell, Kochanov, and Strans-
kiy [ 25 ] exploits these approximations to make cathodic protection recommendations for ships
It appears that Soviet work lagged that of others by at least a decade Even as late as 1980,
highly-referenced work [26] uses "separation resistances" and hnear circuitry to simulate the
electrochemical systems of ships' structures
Alkire and colleagues [27-29 ] contributed to the developing science of current and potential
distribution predlctton by extending it for simple geometries to include (collectively) diffusion,
and Tafel and active/passive electrode kinetics The method was to derive the governing differ-
entml equation from the principle of conservation of charge in the electrolyte, impose the analyti-
cal form of the boundary conditions, and solve the boundary value problem numerically using
computers This work extended the prediction capability to systems for which closed-form differ-
ential equations could be written but not solved exactly
The equation describing the general theory of the potential, the Laplace equation, has been
the subject of many efforts of analytical (closed-form) solution A textbook by Myers [30] deals
primarily with this effort, under the realm of the analogous discipline of conduction heat
transfer The analogy ends, however, when the boundary conditions of electrochemical phenom-
ena are introduced Gal-Or, Raz, and Yahalom [31] used the classical separation of vanables
technique to treat circular corrosion systems, evaluating the total current conducted in these
systems McCafferty [32] extended this to predict the actual distribution of potential and current
within those systems McCafferty [33] continued this work for orcular systems ofhnear corro-
sion kinetics on electrodes with unequal polarization parameters This work used Wagner's/
Waber's polanzatlon parameter (.E) to formulate the problem and descnbe the results The
results of this analytical (closed-form) solution will be compared with a numerical analysis using
the techniques derived in this current research
The rewew of hterature to this point m the field of electrochemical potential and current
prediction indicates the shortcomings of analytical solutions to these problems ( 1 ) the cases of
geometncal configuration of the electrodes is finite, restricted to classical (simple) arrangement
that do not begin to approach general geometries, and (2) the electrode kinetics that may be
represented by mathematical boundary condmons have been limited to being linear in polanza-
tion behavior, vahd within only a few tens of mllhvolts of the corrosion potential for most
corroding metals These limitations define the challenge for the current research Further review
of the background hterature in the particular theoretical area to follow will be incorporated
therein
Research Objecnve
The objective of this research was to develop a method for a priori quantitative prediction of
electrochemical potential distributions and galvamc currents m a system of dissimilar metals
submerged in an electrolyte, with the motwatlon being mitigation of corrosion effects by mate-
nal selection, geometric configuration, and cathodic protection system design Specifically, the
method used existing numencal techniques for solving the Laplace equation and applied them in
developing an electrochemical analysis technique for a system of any specified geometry of
electrodes with known electrodic polarization properties The research placed particular empha-
sis on the quantitative characterization of electrode kinetics behavior using analytical expres-
slons that are amenable to the boundary conditions and have physical significance m the electro-
chemical problem Other intended contnbutions of this work were the imposition of conserva-
tion of electrical charge within the developed method and a facilitation of the method for
enhanced convergence and ease of use
This research investigated the modern numencal methods of finite difference, finite element,
and boundary integral element methods The application of each of these methods to the model-
ing of electrochemical phenomena is presented with the particular advantages of each The
background literature m each of these areas is presented
Numerical Methods for Solving the Boundary Value Problem

Discussion of "Approxtmate Methods"
The experience ofearher investigators in attempting to provide solutions to the electrochemi-
cal problem pointed out the limitations of geometry and polanzation description tmposed by
analytical (closed form) solutions The partial differential equation governing electrochemical
conduction may be solved analytically for only certain simple geometries and boundary condi-
tions, only a very limited number of real problems may be described by these geometnes, and
virtually no real metal ] electrolyte system obeys the simple behavior of the mathematical bound-
ary conditions for which the differential equation may be solved
While analytical solutions are important to evaluate limiting cases of asymptotic solutions for
bounding real problems, approximate numerical solutions are required to solve realistic prob-
lems From a pragmatic point of view, this is clearly more desirable than finding exact closed-
form soluUons to academic problems
Approximate methods nghtfully include graphical, experimental, and analog methods that
have been used in field theory disciplines for many years However, such methods are difficult to
apply to electrochemical modeling because of the failure of graphical and analog methods to
accurately simulate the electrochemical boundary conditions and because of the labonous na-
ture of experimental methods This paper addresses only numerical methods of solving the
electrochemical problem
The approximate solution methods which will be discussed herein should not be considered
crude estimates to the solutions Rather, they offer plecewise approximations by representing
exact derivatives at a point by difference quotients or integrals over an interval The degree of
approxtmation is dependent on the degree of spatml and temporal dlscretizatlon and the order of
the difference or interpolation functions used These factors will be described later, but suffice it
to say at this point that an "approximate" solution may be rendered as accurate as desired, or as
accurate as the input data and computational accuracy, upon which analytical solutions are also
dependent The limits on the accuracy of approximate solutions are imposed only by the model-
lng time and computational time expended
Htstory of the Apphcanon of the Fmtte Difference Method to Galvamc Analysts

By way of apphcatlon, Smyrl and Newmann [34] and Dolg and Flewltt [35] independently
performed finite difference solutions for the potential distributions in particular galvanic cells
The details of their solution schemes were not made available, but limitations to exponential
(Tafel) polanzatlon behavior were pointed out A colleague of Dolg and Flewitt's, Elson [ 36]
described a computer program designed to perform their analysis, still limited in polarization
description
Strommen and Rodland [ 37] performed another attempt at a finite difference solution to the
galvanic corrosion problem Even cruder boundary conditions were used, however, assuming
constant and uniform current densmes on the cathode components and current sources ofhnear
potential vanation on the anodic surfaces
One finite difference galvanic analysis scheme [ 38 ] incorporates the formulation described by
the differential equation with boundary condmon representation m terms of the common polar-
lzation parameters, fully accounting for activation- and diffusion-controlled polanzaUon, sec-
ondary cathodic reactions, metal dissolution, and passivation/transpasslvatlon behawors The
development of this analytical expression is descnbed therein This scheme also employed an
iteration order that alternated spatial direction with each iteration, improving the propagation of
nodal potential changes
Despite the validity of this latter development, all finite difference applications are deficient in
handling nonuniform meshes, curved or oblique boundanes, and nonuniform electrolyte proper-
ties Although some of these difficulties were later surmounted [39], there was still sufficient
impetus for investigating other numerical methods Two other methods will be described in the
following sections, with a companson of the three methods following thereafter
History of the Apphcatton of the Fmtte Element Methods to Galvamc Analysts

The history of the apphcatlon of the finite element method to the solution of the general
electrochemical problem is now about twelve years old However, the foundations upon which it
is bmlt are due to fifty years of development of the kinetics background m electrochemistry by
Wagner and Traud, Bockrls et al, Vetter, Stern et al, and others and thirty-five years' mathemat-
ics background of the finite element method by several mathematicians, physicist, and engineers
such as Clough, Argyns, Courant, Melosh, and others and especially as applied by Zienklewlcz
and others to field problems in continua
An early attempt [ 40] at applying mixed potential theory to realistic problems was made by
recalling the relative area effects on the mixed potentials and current densmes of galvanic
couples, and then conceptualizing a circuit model of a galvanic system for a simple planar
geometry That approach ran into difficulty when a nonlinear current density Op) at an electrode
surface was considered a function of potentml (not determinant by geometnc IR drops alone)
and consideration of nonslmple geometnes rendered the integration unwieldy or impossible
Further hypothesis m that work made the first known mention of applying a heat conduction
analogy and therefore computational methods designed for heat conduction problems to the
electrochemical problem The heat conduction/electrochemical analogy was tabulated [ 40] m
the context of the equation solved by the NASTRAN computer program [ 41] for heat conduc-
tion problems That work left unmentioned the problem of introducing the electrodic current
densities as boundary conditions of the fourth kind nonhnearly dependent upon local potential
Alkire, Bergh, and Sani [ 42 ] made a large advancement in applymg finite element techniques
to the electrochemical problem by writing a specialized form of the Laplace equation m terms of
a nondimensional potential An electrochemical boundary condition was incorporated for the
cathode surface only and consldenng only activation polarization there The anode was consid-
ered to be of uniform constant potential The coupling of this specialized Laplace equation with
Faraday's law for electrodeposmon at the cathode allowed calculation of a transient growth rate
at the cathode for this limited example of boundary condition That research indicated the
potentml advantages of applying the finite element method to electrochemical analyses
Following the analogy drawn by Kasper [ 43 ] between electromagnetic and elasticity equa-
tions in order to apply known numerical methods to the former, Brauer [ 44], under contract to
Kasper, performed an application of the finite element program to electrostatic and electrocon-
ductive examples and later [ 45 ] to an electrochemical problem using an analogy to heat convec-
tion for the linear approximation to polarization boundary condmons
A compilation of the developments in numencal electrochemical modeling was made [ 46 ] in
1979 and later formally reported [ 47] with unhmlted &stnbutlon That work summarized the
development mentioned earher, and then explored the feaslbdlty of representing polarizing
electrodes by a hnear expression Finding this to be inadequate for general polarization behavior,
an analytical expression was derived to represent (as current density (iv) as a nonhnear function
of potenUal (4~)) the actwaUon-controlled portion of the anodlc and cathodic polarization
curves and the &ffuslon-hmlted catho&c region This initial development allowed the represen-
taUon of nonhnear current density boundary condmons of the fourth kind
DeCarlo pubhshed several papers [48-51] In the &rectlon of corrosion analysis by fimte
element methods using a mo&ficatlon of the method used by Brauer [44,45] with the hnear
program Although the details of the analyses were not pubhshed, It appears that polarization
resistances were used for catho&c boundary condmons (wa convection CHBDY finite ele-
ments) and fixed-potential constraints were used for the anodes Although the latter assumption
can be vahd for certain anode materials under certain ranges of service, the catho&c behavior
cannot adequately be represented by constant-resistance convectwe elements, as shown earher
[46] These convectwe elements have more recently been employed by Kasper and Apnl [52]
to represent, plecewlse hnearly, nonhnear polarization behavior by using a double layer of them
at all electrode elements However, the mcorporatlon of these adds to the size of the numerical
problem, over that of the method developed by this author [53] Further, using this fimte
element program this method is apparently limited to a maximum of two &fferent metals
By this time, efforts m electrochemical modehng had "polarized" to follow one of two differ-
ent modehng schemes Following the development of Frye [54], the majority of researchers had
(and are to date) exphcltly modeled the polarization layer, and m some cases the base metal, at
electrode boundaries These works included film elements (e g , CHBDY elements) on the
boundaries, using an analogy to heat convection Conversely, the research described [53] ig-
nores the detads and degrees of freedom involved with the polarization double layer and the base
metal and considers only the electrolyte as a conductwe medmm, the effects of the electrode are
included lmphcltly as current density fluxes into and out of the electrolyte This reduces the
numerical size of the problem and the modehng complexity It further deals with experimentally
measurable variables This method was first proposed by this author [40] and continued
throughout this research ( A film flux approach was investigated [55] to evaluate its effect on
convergence rate, but lack of benefit deemed the approach to be of no value) Each of the
hterature citations hereto wdl, ff appropriate, ldenufy the above classification of the research
Forrest, Fu, and Blclcchl [56] redeveloped the fimte element formulation for the particular
case of cyhndncal coordinates m order to compare closed-form, numerical, and experimental
results for a similar example The particular example used employed a simple constant-current
anode and an ~mphc~t representation of the polarization layer as a single polarization resistance
(Rp) in the variational statement, "adjusted to match the experimental data as reqmred" If the
polarization resistance could have been incorporated as an a prtort funcUon of potentml, this
work would have been a significant contnbuuon to corrosion analysis Without that, it did not
enhance the capabdlty to pre&ct the electrochemical potentml field, the goal of this research
Fu [57] later used the fimte element method advantageously to calculate the IR drops of
particular corrosion cells, this was done by accurately modehng the cell and &d not reqmre the
incorporation of polarizing boundary con&tlons
Forrest and Blclcchl [58] used the same formulation as their earher work w~th Fu [56] to
investigate acceptance methods for catho&c protection systems for propeller blades That work
employed the ANSYS fimte element computer program [59], apparently the heat conduction
mode Because of the particular potentml range of the mvest~gauon and the polarization behav-
ior of the bronze propeller alloy, the use of a constant polanzaUon resistance (rp), apparently
lmpllclty as m the earher work, was justified for th~s study
Another apphcaUon of numerical methods to the electrochemical problem was described by
Helle, Beek, and Llgtehjn [60] as two different methods The discrete source-sink method fol-
lowed that practiced in hydrodynamics, m this case employing a large number of potential
sources (sinks), calculating the potential decay from each, and superposmg the decays of all the
sources They allude to using iteration of nonhnear current-potential relationships at the
sources This source-smk concept in simdar to the basis of the boundary integral equation
method, to be discussed later hereto Their employment of the finite element method, using a
variational pnnclple derived by others, again followed that for hydrodynamics and again referred
to an lteratwe approach to account for "non-constant" boundary condmons implicitly, follow-
mg that of Waber Their analysis was further constramed by requmng some fixed-potential
(Dmchlet) boundary condmon somewhere on the model, to avoid a singular conductwlty ma-
trix and thus to allow a solution
Kasper and April [ 52 ] used the explicit modehng of the polanzauon layer on the cathode with
double convection film (CHBDY) elements using the hnear finite element program [ 41] The
anode was assumed to be of constant uniform potentml, and the base metals were assumed to
have uniform potential, although unknown m magnitude This assumption is vahd throughout
any one metal, as the base metal conductivity is very much higher than that of the electrolyte and
therefore will exhibit a correspondingly lower potential gradient The emf potentml between
base metals at their interface outside of the electrolyte will introduce discontmmtles in potential
between the metals, but these are not mfluentml to the electrochemical potentials measured w~th
a reference cell in the electrolyte Their apphcatlon involved a galvanic couple for which the
cathode was nearly covered with a paint system of high resistivity (although not lnsulatlve), with
a small unprotected area (e g , chipped paint) at the center of the cathode This explicit method
revolves the addition of two layers of film elements being assigned tangent "resistance" proper-
ties as a function of potentml using a table of pmrs of potentml and resistance values The
analysis predicted potentml and normal current density distnbutions along the cathode, no
experimental values were presented for correlation This method used the variational formula-
tion and solution sequence employed by the program, and is therefore hmlted to cases hawng a
fixed-potential (Dmchlet) boundary condmon somewhere m the system This method is pres-
ently also limited to systems with no more than two surfaces with nonhnear polarization
behawors
An introduction to the work behind the present paper was made [ 61] with a companson of
measured and numerical results of a laboratory-scale experiment revolving two d~sslmllar metals
m an electrolyte An improvement of the method was published [ 62] with an improved analyti-
cal expression for descrlbmg electrodlc polarization behavior, the first known openly-pubhshed
treatment of electrodics as boundary conditions for corrosion analysis
Fu [63] made a new approach to the concentric circular corrosion cell analysis performed
earher [56], this time using the Wesnnghouse WECAN computer program [ 64 ], heat transfer
option, in a convection analogy which followed that of Kasper and April [52] Fu and Chan
[ 65 ] later performed a similar analysis on a particular corrosion cell with the added complexity
of tracking the change in electrolyte composition with time This added a significant capabihty to
their electrochemical analysis for closed systems, although it did not purport to have updated the
metals' electrodic behaviors along with composition and conductwlty, an effect that must be
included for completeness
The convectwe film analogy (with no additional elements for the film) was investigated
[66,67] m an effort to include a fixed-potential (Dmchlet) boundary condition that did not
artificmlly affect the solution of the problem It was hypothesized that ffthe "ambient" potential
were given a fixed value (e g , the corrosion potential of the metal) and the boundary current
density were a function of it (the polarization curve function), then this would provide a solu-
tion to the problem Th~s was not the case, because the ambient potential was not assocmted with
any node m the medium, therefore it afforded no fixed-potential boundary condition to the
problem
To overcome this inadequacy, a pseudo-transient scheme was introduced [55] wherein mass
and specific capacitance ("capacltlVity") properties were assigned to the electrolyte elements,
thereby rendenng the operator matrix in the governing equauon nonslngular and allowing the
solution to proceed An expression for optimum value of capacity has been denved
Further work m the literature [ 68-70 ] has been application of the methods cited earlier, with
no new developments in the technology
History of the Apphcatton of the Boundary Element Method to Galvamc Analysts

An early application of boundary methods to solve the Laplace equation was made by Redser
and Appl [ 71] In that application to heat conduction problems, a singular integral was devel-
oped to describe steady-state sources and sinks of variable intensity over the boundary of the
domain These sources were hmlted to being linear (simulating convection boundary condi-
tions) The results were distnbutlons of temperature (potential) within and on the boundary,
with a secondary set of calculations yielding the gradients, and thus fluxes Bolteus and Tullberg
[ 72 ] later made another application to heat conduction, with the added capabdlty for handhng
lnhomogeneous media That analysis still dealt with, at most, linearly-varying boundary
conditions
Fu and Chow [73] also used a boundary integral techmque in an apphcatlon to galvanic
corrosion problems, claiming that lntenor potentials are extraneous results in the electrochemi-
cal problem, and the surface potentials yielded by boundary methods were sufficient results In
that work, reference was made to nonlinear boundary conditions as potential gradients as a
function of potential, but the method of including ~t for the integral was not developed
Telles, Mansur, and Wrobel [ 74 ] applied the boundary element method to external problems,
the geometric inverse of those dealt with previously In these cases, the "boundary" IS the surface
of a body imbedded in the medium, the medium being lnfimte in outer dimension The obwous
newly-exercised capability there was the ability to treat infinite domains That apphcatlon,
though, dealt only with the Dmchlet problem, specified potentmls over the (internal) boundary
surface Therefore the lack of consideration of higher order boundary condmons renders the
advancement inapplicable (directly, anyway) to the electrochemical problem
An improved analysis with the boundary element method was developed by Bardal, Johnsen,
and Gartland [7.5] This was applied to an internal problem, so no infinite boundaries were
involved The analysis descnptlon recognized the nonlinear nature of electrochemical boundary
conditions, but then slmphfied those to activation-controlled polanzatlon (anodlcally) for the
anode and to a position-dependent function of the diffusion-limited current density for the
cathode Because of the particular system chosen for an example, good correlation was realized
between prediction and expenment except near anode/cathode boundanes This deficiency
would be expected, because of those points the polanzatlon simplifications would not be valid
A recent contnbutlon to this method has been made by Cherry, Foo, and Slauw [ 76 ] That
development followed the standard one described hereto earlier, wnting an integral equation
from the Laplace differential equation In the evaluation of the element boundary integrals, the
authors incorporated the several forms of boundary conditions up to the most general nonhnear
fourth kind [53] for the most general Their application to examples of fairly simple geometry
yielded good results between prediction and experiment Unfortunately, the details of incorpo-
rating general polanzatlon behavior were not published, and no apphcatlon was made involving
infinite boundaries
This section has given a brief descnption of the boundary element method and a review of its
application in the hterature to complete the coverage of numencal methods which may be
Copyright
appliedbytoASTM Int'l (all rights
electrochemical reserved); Tue Feb 10 09:33:27 EST 2015
problems
Comparison of the Numertcal Methods
Most of the attnbutes and requirements of the three numerical methods apphcable to electro-
chemical analysis have been described hereto Their relative capablhUes and limitations should
be considered w~thm the context of the particular type of problem to be solved and the computa-
tional capabilities available
The finite difference method ( F D M ) was the first of the three methods developed, and it is at
the same time the most elementary and the most exercised Relatwe to other methods, the FDM
would usually require less computer storage space than the others but would usually require a
longer solution time for the same problem size Its prime disadvantage is its difficulty m model-
mg curved or obhque boundaries and geometries which require nonuniform mesh
descretlzatlon
While the FDM yields a "pomtwlse" approximation to the governing differential equations
represented by difference equations, the finite element method ( F E M ) yields a "plecewlse"
approximation to the differential equations in the region which is built up of many small subre-
glons (elements) Because of the flexlblhty of element shapes and orientation, the FEM is much
better suited for handling problems revolving complex geometries and regions with lnhomo-
geneous a n d / o r amsotroplc (not common for electrochemical problems) material properties
The stzes of the elements may be vaned between small elements to accommodate geometric
complexities where warranted and large elements to allow modehng economy There are several
both general purpose and specialized heat conduction computer programs now m use that may
be candidates to employ with the analogy described hereto, many of these avadable programs
have particular routines to design the finite element model and to graphically display the results,
in addition to performing the solution One pnnclpal disadvantage of the FEM is the mabdlty to
represent infinite domains, such as a large expanse of ocean or earth However, progressive
dlscretlzatlon has been shown [53] to mitigate this deficiency The inference therein indicates
that a practical modehng ofmfimte domains may be successful with model sizes far smaller than
lnfimte
The boundary element method (BEM) offers some aid to the deficiencies in the FEM Infinite
domains may be modeled, and calculations need not be performed for potential solutions at
points in the electrolyte remote from any electrode, usually not of interest in an electrochemical
analys~s (However, the potential distribution within the medmm may be of interest in some
cases, for example ( 1 ) when the effects of an induced field are important considerations for
other aspects of the design, (2) when mampulatmg geometric configuration in the design stage,
and ( 3 ) when use of one (or a few) remote measurement pomt(s) wall be used to momtor the
status of a system, as in buried pipeline cathodic protection ) Although there are thus fewer
equations to solve with the BEM, the equations are generally more complex and lengthy to
solve The equation number advantage of the BEM diminishes as the internal complexity m-
creases, the FEM has a distinct advantage in modeling these cases By 1986, there were no
known general-purpose BEM programs that may be analogously employed for electrochemical
analyses Each of the hterature references noted refer to one particular geometry modeling,
programmed, and solved
Today, the finite difference method has been all but completely abandoned by practicing
corroslonlsts because of the hmltatlon described, except in cases where computing power is
hmlted A number of general-purpose and corrosion-specific fimte element and boundary ele-
ment codes are used throughout the industry, the BEM being the method of choice for those
having problems revolving lnfimte domains, geometric simplicity, and homogeneous electro-
lytes, and FEM being chosen more for contained problems, geometric complexity, and mhomo-
geneous electrolytes Because the finite element method offers several advantages over and
Copyright
suffers by ASTM
httle fromInt'ldisadvantages
(all rights reserved);
to theTue Feb numerical
other 10 09:33:27 methods,
EST 2015 it has been chosen by this
226 COMPUTER MODEUNG IN CORROSION
a u t h o r as the m e t h o d most suitable for a larger spectrum electrochemical analysis problems, a n d

thus the m e t h o d exploited by this a u t h o r
References
[l] Dwight, H B, "Calculations of Resistances to Ground," Electrical Engmeermg, Vol 55, 1936, p
1319
[2 ] Sunde, E D , Earth Conduction Effects m Transmtsston Systems, Chapter III, Van Nostrand, New York,
1949
[3 ] Benedict, R L, Ed, Anode Reststance A State of the Art Revtew, National Association of Corroston
Engineers Committee T-7L-2, Houston, forthcoming
[4] Cochran, J C , "Offshore Platform Catho&c Protection OpUmlzatlon via Computer Use of Classical
Equations," CORROSION/84 Paper No 252, New Orleans, 1984
[5] Kasper, C , "The Theory of the Potential and the Techmcal Practice of ElectrodeposlUon I--The
General Problem and the Cases of Uniform Flow," Transacttons of the Electrochemical Society, Vol 77,
1940. p 353
[6 ] Kasper, C , "The Theory of the Potential and the Techmcal Pracuce of Electrodeposmon II--Polnt-
Plane and Line-Plane Systems," Transactions of the Electrochemtcal SocletV, Vol 77, 1940, p 365
[7] Kasper, C , "The Theory of the Potential and the Techmcal Practice ofElectrodeposmon III--Lmear
Polarization on Some Line-Plane Systems," Transactions of the Electrochemtcal Soctety, Vol 78, 1940,
p 131
[8] Kasper, C , "The Theory of the Potential and the Techmcal Practice of Electrodeposltlon IV--The
Flow Between and To Circular Cyhnders," Transactions of the Electrochemical Society, Vol 78, 1942,
p 147
[9] Kasper, C , "The Theory of the Potenual and the Technical Practice of Electrodeposluon V--The
Two-Dimensional Rectangular Enclosure," TransacttonsoftheElectrochemtcalSoctety, Vol 82, 1942,
p 153
[10] Bockns, J O'M and Reddy, A K N , Modern Electrochemtstry, Chapter 8, Plenum Press, New York,
1970
[11] Wagner, C , "Theoreucal Analysis of the Current Density Distribution m Electrolytic Cells," Journal
of the Electrochemical Soctety, Vol 98, No 3, 1951, p 116
[12] Wagner. C , "Contnbuuon to the Theory of Cathodic Protection," Journal of the Electrochemtcal
Society, Vol 99, No 1, 1952. p 1
[13] Hoar, T P and Agar, J N , Dtscusstons of the Faraday Society, Vol 1, 1947, p 162
[14] Waber, J T , "Mathematical Stu&es on Galvamc Corrosion II--Coplanar Electrodes with One Elec-
trode Infinitely Large and with Equal PolanzaUon Parameters," Journal of the Electrochemical Soctety.
Vol 102, No 6, 1955, p 344
[15] Waber, J T , "Mathematical Studies on Galvamc Corros|on IV--Influence of Electrolyte Thickness
on the Potentml and Current DlstnbuUons over Coplanar Electrodes Using Polanzatxon Parameters,"
Journal of the Electrochemtcal Society, Vol 103. No 1, 1956, p 64
[16] Waber, J T,"MathematlcalStudlesonGalvamcCorroslon VI--LlmltlngCaseofVeryThmFdms,"
Journal of the Electrochemtcal Soctety, Vol 103, No 10, 1956, p 567
[17] Waber, J T , "Study of a Size Effect m Galvamc Corrosion," Corrosion, Vol 13, No 2, 1957, p 25
[18] Kennard. E and Waber, J T , "Mathematical Study of Galvamc Corrosion Equal Coplanar Anode
and Cathode with Unequal PolanzaUon Parameters," Journal of the Electrochemtcal Soctety, Vol 117,
No 7, 1970. p 880
[19] Carslaw, H S and Yeager, J C . Conduction of Heat m Sohds, 2nd ed. Oxford Umverslty Press,
Oxford, 1959
[20] Parnsh, W R and Newman, J , "Current Distribution on a Plane Electrode below the Llmmng
Current," Journal of the Electrochemtcal Soctety, Vol 116, No 2, 1969, p 169
[21] Parnsh, W R and Newman, J , "Current Distributions on Plane, Parallel Electrodes m Channel
Flow," Journal of the Electrochemwal Soctety, Vol 117, No 1, 1970, p 43
[22 ] Hsueh, L and Newman, J . "The Approach to Llmmng Current m a Stagnant Diffusion Cell," Journal
of the Electrochemical Socwty, Vol 117, No 10, 1940, p 1242
[23] Plennl, P, Appel, P, and Newman, J , "Current Dlstnbutlon on a Disk Electrode for Redox Reac-
tions," Journal of the Electrochemtcal Soctely, Vol 123, No 3, 1976, p 366
[24] lossel, U Y and Klenov, G E , "Methods of Calculatmg the Potentxal and Current Distribution m
Electrochemical and Corrosion Systems (A Review)," Zashchlta Metallov, Vol 9, No 6, 1972, p 635
[25 ] lossel, U U , Kochanov, E S, and Stranskly, M G , Questtons Concerned with the Destgn and Modehng
ofElectrochenncal Anttcorroston Protecttonfor Ships, Shlpbuddmg Publtshmg House, Lenmgrad, | 965
[26] lossel, Y Y, Klenov, G E , and Pavlovskly, R A , "Method of Computing Electrical Separation

Resistance of Ship Structures," Sudostroyemye, No 1, 1980, p 27
[27] Alkire, R , "A Theoretical Study ofBlpolar Porous Electrodes," Journal of the ElectrochemwaISocwty.
Vol 120, No 7, 1973, p 7
[28] Alklre, R and Nlcolaides, G , "The Existence of Multiple Steady States Dunng Differential Aeration
Corrosion," Journal of the ElectrochemwalSociety. Vol 122. No 1, 1975, p 25
[29] Alktre, R and Mtrarefi, A A , "Current Distribution m a Tubular Electrode under Laminar Flow Two
Electrode Reactions." Journal of the ElectrochemicalSociety. Vol 124, No 8, 1977, p 1214
[30] Myers, G E, Analytical Methods m Conduction Heat Transfer, McGraw-Hall, New York, 1971
[31 ] Gal-or, L, Raz, Y. and Yahalom, J , "Mathematical Characterization of Corrosion Currents in Local
Electrolytic Cells," Journal of the Electrochemical Socwty. Vol 120, No 5, 1973, p 598
[32] McCafferty, E , Corrosion Science, Vol 16, 1976, p 183
[33] McCafferty. E , "Mathematical Analysts of Circular Corrosion Cells Have Unequal Polarization Param-
eters," Naval Research Laboratory Report No 8107, 1977
[34] Smyrl, W H and Newman, J , "Current and Potential Distributions in Plating Corrosion Systems,"
Journal of the EleetrochemwalSociety. Vol 123, No 1, 1976. p 1423
[35] Dolg, P and Flewltt. P E J , "A Fimte Difference Numerical Analysts of Galvanic Corrosion for
Seml-lnfimte Linear Coplanar Electrodes," Journal of the Electrochemical Society. Vol 125, No 12,
1979. p 2057
[36] Elson, G D , "GALVAN - A Program to Numerically Solve the Equations Pertaining to a Galvamc
Corrosion Model," Central Electnclty Generating Board Report No CC/P556, London, 1978
[37] Strommen, R and Rodland, A , "Computerized Numerical Techmques Apphed in Design of Offshore
Cathodic Protection Systems," Materials Performance. Vol 20, No 5, 1981, p 15
[38] Munn, R S and Clark, J H , "Simple Method for Prediction of Galvamc Corrosion Rates on Real
Structures m Seawater Using Numerical Techniques on a Microcomputer," CORROSION/83 Paper
No 74, Anaheim, Cahf, 1983
[39] Munn, R S, "Numerical Corrosion Rate Prediction on Structures Immersed m Inhomogeneous Me-
dia," CORROSION/84 Paper No 49. National Association of Corrosion Engineers, New Orleans.
1984
[40] Munn, R S, "A General Apphcatlon of Electrochemical Pnnclples to Three-Dimensional, Multi-
Metalhc, Underwater Structures." U S Naval Underwater Systems Center Technical Memorandum
No 771183, New London, Conn, 1977
[41] NASTRAN TheoreticalManual National Aeronautics and Space Administration. Washington, D C ,
1976
[42] Alklre, R and Bergh, T , "Predicting Electrode Shape Change with the use of Fimte Element Meth-
ods," Journal of the ElectrochemwalSociety. Vol 125, No 12, 1978, p 1981
[43] Kasper, R G , "Equivalent ElectromagneUc/Acoustlc Formulations Developed from the Theory of
Elasticity," U S Naval Underwater Systems Center Technical Report No 5593, New London, Conn,
1976
[44] Brauer, J R , "Finite Element Analysis of Electnc Fields using MSC/NASTRAN," m Proceedmgs,
Conference on Computer Techniques Apphcable to Three-Dimensional Electrostatic Field Analysis,
Santa Barbara, Cahf, 1978
[45] Brauer, J R , "MSC/NASTRAN Analysis of Electric Currents m Cathodic Protection Systems," in
Proceedmgs. MSC/NASTRAN Users' Conference, Pasadena, Cahf, 1979
[46] Munn, R S, "Electrochemical Modehng," U S Naval Underwater Systems Center Technical Memo-
randum No 801018, New London, Corm, 1979
[47] Munn. R S, "'Electrochemical Modehng," U S Naval Underwater Systems Center Technical Report
No 6415A, New London, Corm, 1981
[48] DeCarlo, E A , "Computerized Current Density Program," Lockheed Manne Service Technical Bulle-
tin No 79-2, 1979
[49] DeCarlo, E A , "Computer Techmques for Offshore Corrosion Protection," Sea Technology. Vol 22,
No 9, 1981, p 25
[50] DeCarlo, E A . "Computer Aided Cathodic Protection Design Techmque for Complex Offshore
Structures," CORROSION / 82 Paper No 165, National Association ofCorroston Engmeers, Houston,
1982
[51] DeCarlo, E A , '*Computer Aided Cathodic Protection Design Technique for Complex Offshore
Structures," Materials Performance. Vol 22, No 7. 1983, p 38
[52] Kasper, R G and April, M G , "Electrogalvamc Finite Element Analysts of Partially Protected
Manne Structures," CORROSION/82 Paper No 168, National Association of Corrosion Engineers.
Houston, 1982
[53] Munn, R S, The Modeling of Galvame Corrosion Systems using Numerical Methods with Parttcular
Attention to Boundary Condmons of Nonhnear Polarization, University Microfilm International
(~8622913), Ann Arbor, Mlch, 1986
[54] Frye, J W , "Electrogalvanlc Finite Element Formulauons," U S Naval Underwater Systems Center
Technical Memorandum No 801103, New London, Conn, 1980
[55] Munn, R S, "Modeling of Electrochemical Phenomena for Finite Element Analysls of Galvamc
Systems II--Pseudotranslent Solutions Using Applied Current Boundary Conditions," U S Naval
Underwater Systems Center Technical Memorandum No 831158, New London, Corm, 1983
[56] Forrest, A W , Fu, J W , and BlClCChl,R T , "Validation of Finite Element Technique for Modeling
Cathodic Protection Systems," CORROSION/80 Paper No 150, National Association of Corrosion
Engineers, Chicago, 1980
[57] Fu, J W , "IR Voltage Correction in Electrochemical Atmospheric Corrosion Probes Using a Flmte
Element Calculatlon,"CORROSION/81PaperNo 115, NatlonalAssoclatlonofCorroslonEnglneer,
Toronto, 1981
[58] Forrest, A W and BlclCChl, R T , "Cathodic Protection of Bronze Propellers for Copper Nickel
Surfaced Ships," Corrosion, Vol 37, No 6, 1981, p 349
[59] ANSYS Ftmte Element Computer Program, Swanson Analysis Associates, Durham, N H , 1974
[60] Helle, H P E, Beek, G H M , and Llgtehjn, J T , "Numerical Determination of Potential Distribu-
tions and Current Densities in Multi-Electrode Systems," Corrosion, Vol 37, No 9, 1981, p 522
[61] Munn, R S, "Numerical Analysis of Galvanic Systems for Manne Cathodic Protection System De-
sign," CORROSION/82 Paper No 171, National Association of Corrosion Engmeers, Houston,
1982
[62] Munn, R S, "A Mathematical Model for a Galvanic Anode Cathodic Protection System," Materials
Perforniance, Vol 21, No 8, 1982, p 29
[63] Fu, J W , "A Finite Element Analysis of Corrosion Cells," Corrosion Technical Note, Vol 38, No 5,
1982. p 295
[64] WECAN The System for Structural Analysts, Westinghouse Research and Development Center, Pitts-
burgh, 1978
[65] Fu, J W and Chan, S K, "A Finite Element Method for Modehng Localized Corrosion Cells,"
Corrosion, Vol 40, No 10, 1984, p 540
[66 ] Munn, R S, "Modeling of Electrochemical Phenomena for Finite Element Analysis of Galvanic
Systems I--Use of Applied Current (Conduction) Boundary Conditions," U S Naval Underwater
Systems Center Technical Memorandum No 811109. New London, Conn, 1983
[67] Munn, R S, "Using the MARC Finite Element Computer Program for Numerical Analysis of Gal-
vanic Systems for Manne Cathodic Protection System Design," in Proceedmgs, MARC Users' Sympo-
sium, Palo Alto, Callf, 1982
[68] Crowe, C R and Kasper, R G , "Calculated and Measured lomc Current Densmes in the Nearfield of
a Corroding Iron-Copper Galvanic Couple," submitted to Corrosion (1984)
[69] Kasper, R G , "Theoretical and Experimental Comparisons ofNearfield Electrogalvanlc Fields due to
Nonlinear Polarization Layers," U S Naval Underwater Systems Center Technical Report No 7299,
New London, Conn, 1985
[70] Munn, R S, "Analysis of Current and Potential Distribution in an Internal Shipboard Seawater
Tank," CORROSION/86 Paper No 46, National Association of Corrosion Engineers, Houston,
1986
[71] Relser, M J and Appl, F J , "A Numerical Method for Conduction Heat Problems," Journal of Heat
Transfer, Vol 96, No 8, 1974, p 307
[72] Bolteus, L and Tullberg, O , "Boundary Element Method Applied to Two-Dimensional Heat Conduc-
tion in Non-Homogeneous Media," Advances m Engmeermg Software, Vol 2, No 3, 1980, p 131
[73] Fu, J W and Chow, J S K , "Cathodic Protection Designs Using an Integral Equation Numerical
Method," CORROSION/82 Paper No 163, National Association of Corrosion Engineers, Houston,
1982
[74] Telles, J C F, Mansur, W J , and Wnbel, L C , "On Boundary Elements for External Potential
Problems," Mechamcs Research Comtnumeattons, Vol I 1, No 6, 1984, p 373
[75] Bardal, E , Johnsen, R , and Gartland, P O, "Prediction of Galvanic Corrosion Rates and Distribu-
tion by Means of Calculation and Experiment Models," Corrosion, Vol 40, No 12, 1984, p 628
[76] Cherry, B W , Foo, M , and Slauw, T H , "Boundary Element Method Analysis of the Potential Field
Associated with a Corroding Electrode," to be published in Corrosion (1985)
Roe D. Strommen
Computer Modeling of Offshore Cathodic

Protection Systems: Method and Experience
REFERENCE: Str~mmen, R D, "Computer Modeling of Offshore Cathodic Protection Sys-
tems: Method and Experience," Computer Modeling lrl Corroston,ASTM STP 1154, R S Munn,
Ed, Amencan Sooety for Testing and Matenals, Phdadelphm, 1992, pp 229-247
ABSTRACT: Th,s paper offers a brief review of methods that are used and presents &fferent
apphcatlons and experience from computer modehng of offshore catho&c protection systems Thxs
compnses state-of-the-art software based on the Flmte Difference Method (FDM), Finite Element
Method (FEM), and Boundary Element Method (BEM) adapted for the calculation of current
and potentml distributions on complex, cathodlcally protected steel structures m seawater
The numerical dlscretlzatlon procedures referred to above are combined with a data base and
procedures for handhng the electrochem,cal boundary condmons In addmon, software modules
are included that handle the mmahzatlon of the computer models, definmon of geometry, the
numerical soluuon of the nonhnear dlscretized equations, and presentauon of results
In particular, this paper presents the principles and procedures used to handle boundary con&-
t,ons The procedures are based on bas,c corrosion theory and general experience as well as on
laboratory and field tests The author and his company have made use of extensive amounts of data
obtained by m sttu measurements of current densmes and potentials on offshore platforms using
proprietary electrical field gra&ent/current dens,ty systems Thus the modehng results and predic-
tions have been verified by field data
KEY WORDS: offshore cathodxc protection systems, computer modehng, software
The apphcatlon of computers in design evaluation o f offshore cathodic protection systems

began in the mid to late 1970's [1-3] This followed some early work o f Finite Difference
Method ( F D M ) analysis of electrochemical systems o f simple geometry [4,5] The background
and motivation for developing these more sophisticated methods for cathodic protection ( C P )
analysis relate to increased activity m exploration and production ofoll and gas in the North Sea
Large and complex structures in deep waters combined with hostile weather conditions resulted
in the need for review and revision of CP design requirements and procedures [ 6-8] A number
of research projects and studws were initiated in this period in the United Kingdom, Norway,
The Netherlands, and France, among others While the United States has had activity in this
area for many years, it probably increased dunng this penod, resulting in a number of publica-
tions m the early 1980's, several of which referred to computerized techmques for CP design
evaluation The interest and activity in the development and adaptation o f numerical modeling
was intensified, and a number of research groups were active in this area [ 9-15 ] The majotaty o f
the papers presented through this last decade have referred to applications in offshore cathodic
protection However, other electrochemical systems and processes have also been treated (e g ,
as reported m Refs 16 to 20)
A mam goal in developing software for computer analysis of offshore CP systems has been to
optimize CP designs As in other fields ofengmeenng, the main objectives have been to improve
CorrOcean a s, Teglgfirden, Hornebergvn 7, Trondhelm, Norway
229
the accuracy in the calculations and thereby reduce safety margins and to allow for reductions in
weight and costs Secondly, the more sophisticated computer systems aim at improving the
efficiency (i e , reducing the time and effort required in the preparatory work) in in-putting data
and in analysis and review of the output This has been obtained using pre-processors for auto-
matlc generation of gnds representing the structural geometry of complex structures (for defin-
ing anode shapes and locations) and post-processors (including software) for color graphics
presentations of potential and current density distnbuuons
Background
Corrosion of steel in seawater occurs by a mechanism that involves at least two reactions The
anodic reaction, which is dissolution of iron, is written as
Fe = Fe ++ + 2e (1)
The rate of reaction and, therefore, the corrosion rate can be expressed as a current density, s~o,~
( m A / m 2 ) , and is determined by the cathodic reaction that normally is oxygen reduction
1/202 + H20 + 2e = 2OH- (2)
For corroding steel in seawater (l e , at the corrosion potential (E~or~)), these two reactions
balance each other (Possible hydrogen evolution has been neglected ) All electrons produced
by the anodic reaction are consumed by the cathodic reaction, i e ,
ftdA=ft,dA+f,~dA=O
s & &
where
ta = anodlc current density,
tc = cathodic current density, and
Sa/Sr = anodlc and cathodic surfaces
Corrosion and reaction rates depend on the electrochemical potential of steel in seawater If the
potential is reduced to a level called the reversible potential, E 0 (steel), or lower, the reaction is
stopped Such reduction in the potential is achieved in practice using CP either by sacrificial
anodes or by an impressed current system
Figure 1 shows in pnnclple the reaction rates on the steel and on the sacnficial anodes versus
potential The potential of the steel becomes more negative and the potentials of the sacnficial
anodes become more positive, balancing somewhere between the open circuit potentials of the
two different metals Provided an adequate CP design, a high quality anode will polarize only a
few milhvolts while the steel surface can polanze several hundred mllhvolts
Traditional design procedures for CP systems involve the calculation of anode current output
applying Ohm's law
AE
I ..... (4)
R
where
AE = "the driving force",
R = ohmic resistance, and
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursu
STROMMEN ON OFFSHORE CATHODIC PROTECTION SYSTEMS 231
E(mV)J
E os . . . . . . . . . . .
Ecs ~ ~ ) c
Eca ..... 'I

I
'
Z~E-R Ig
1
Ig log [
FIG l--Polarization diagram for protected steel structure wtth sacrtfictal anodes
I = current output from anode

The driving force for a sacrificial anode design, AE, is equal to the total IR drop m the
seawater between the anode and the protected structure, normally defined as the difference
between the protection potential of steel, Eprot, and the closed-circuit potential of the anode,
E~no~ (Fig 1)
Ideally the ohmic resistance, R, includes the following elements
R=Ra+,%+R. (5)
where
Ra = anode-to-electrolyte resistance, or simply "anode resistance",
Re = cathode (or steel structure)-to-electrolyte resistance, and
Rm = any metalhc resistance(s) m the structure (1 e , cables) between anode and cathode
Field measurements offshore have proven that the Re element often is considerable (e g , at
complex nodes, at pile grades and conductor guides on the structures) Errors ofth]s nature have
added to errors and maccuractes m anode resistance formulae This has been compensated for by
using sohd safety factors Thus the anode current output ]s calculated as
AE
la = aR-- (6)
where
la = anode current, and
= Ep~t - Ea.oae
The anode resistance ]s obtained here using a formula that includes the seawater/electrolyte
reslstwlty and parameters defining the anode geometry
Boundary Element Method (BEM) Modeling

The electrostatic potential reflecting the flow ofelectnc current m the seawater from anodlc to
cathodic sites obeys the Laplace's equation
V2E = 0 (7)
where E 1s referred to a known reference electrode

Calculation of the potential and current density distributions over the surfaces of a protected
structure involves the solution of this equatmn for adequate boundary condmons In addition to
definmons of the geometry, such boundary condlhons must compnse equatmns or data descnb-
mg the relationship between potentml and current denmty for the anodlc and cathodic surfaces
The current denmty must furthermore satisfy the relattonshlp
+'I.+ (8)
where
t = current density,
K = conductivity of electrolyte (seawater),
n = normal to the surface area in question,
and Eq 3 must be satisfied
Equation 8 takes different forms depending on location, t~me, and characteristics of the sur-
face, and the environmental conditions in the sea This is particularly Important for the cathode
(1 e, the protected steel)
t r = f ( E , T, V 02, temperature, salinity, blo-foullng, surface location, morphology) (9)

where
tc = local cathodm current density,
E = potential,
T= time, and
V= flowrate (and local turbulence)
For an insulated surface (t e , a well-coated surface)
6E
lo = - K - i f =0 (10)
For a sacnfioal anode a similar funcUon is applicable However, the dominating parameters may
be
I a = f ( E , T metallurgy/surface morphology) (11)
Pamcularly for local models, recent expenence has indicated that it may be an oversimplifica-
tion to assume E a = constant, as has been suggested by many authors For example, the time
dependence of Eq 11 has proved important
The rather complex relationship between the parameters ofEqs 9 and I l adds to the complex-
lty of the geometry of a typical offshore structure There are therefore very demanding require-
ments to methods and procedures for the numencal solution of the resulting equations
Methods for Numerical Solutions

As indicated above, methods for numencal solutions compnse the FDM, FEM, and BEM All
these techniques are based on dlscretlZatlon of the electrolyte a n d / o r the cathode and anode
STRE~MMEN ON OFFSHORE CATHODIC PROTECTION SYSTEMS 233
Potential
~E
H10 H 9 . . . . -.,-- H2 H1
Current dens,ty ,
FIG 2--The Baste Data Ftle contains polartzatton curves reflecting changes m the quahty of the calcareous
coatmgs wtth "'growth" m a parameter H, reflecting the prevtous charging h/story (current denstty and
potenttal)
surfaces into small elements that in turn are represented by linear, quadratic, or other forms of
equation that satisfy Laplace's equation and the relevant boundary conditions The resultant set
of equations is solved simultaneously using various numencal techniques and powerful high-
speed computers
The FDM was an early technique that, despite quite acceptable numerical efficiency, has a
major drawback in its inability to fit complex geometry While this problem was partly overcome
with introduction of the FEM, both these methods require dlscretizatlon of a large volume of
electrolyte surrounding the structure, resulting in a very large number of equations As the BEM
requires dlscretlzation of the anode and cathode surfaces only, the size of the numencal problem
can be reduced by an order of magnitude Accordingly the BEM has through the 1980's become
the most commonly used technique, at least for software packages developed for handling large
problems
A number of review articles descnbe in detail the mathematical techniques for solution of the
equations and the procedures used [ 16,17,21-25 ]
Procedures for Handling Boundary Conditions

Early programs for modeling CP offered simple procedures for handling the boundary condi-
tions This comprised specificatioqs of constant potential or constant current density or specify-
ing a selected distribution Alternatively these early programs allowed for specification of a
theoretical polanzation curve [ 1-5] Software packages presented dunng the 1980's aimed at
more versatile procedures for modeling potential and current density distributions and redistri-
butions, also following variations in environmental conditions
Modeling or prediction of calcareous coating formation presented as a dynamic polarization
curve was suggested in 1961 by Gngorev [ 26 ] (see Fig 2) He made certain assumptions as to
maintaining the shape of the cathodic polanzatlon curves as these are shifted towards lower
current density values following the formation of the calcareous coating A similar approach has
been used by several authors, including the present author [ 11,14,15,27-29]
Nlsancloglu [23,28,29] has presented excellent review papers in this field In his work it has
been suggested to make use ofgalvanostatlc polarization measurements and, based on regression
analysis of the measured data, a function for the time-dependent decay has been obtained
E
(mY)
static
polarization
curve
\ \\\\
\ \ J~/ ~ instantaneous
t ~ ~ ~\ curves
" \ ~ \
log i (mA/m 2 )
FIG. 3--1nstantaneous (potentiodynamic) polarization curves that represent small surface elements of a
structure, and static polarization curve representing an average for a large structure at a given moment of time.
Our work has followed a somewhat different approach. In our developmental activity of
software procedures for CP modeling we had two major requirements:
9 Organization of the data base must follow a procedure making it possible to utilize the large
amount of current density versus potential data obtained in situ from real-life CP perfor-
mance. Our data base included readings from sacrificial systems where the potential and
current density had a simultaneous and often irregular decay. However, it also included
galvanostatic and potentiostatic data.
9 It required flexibility in the software procedure for handling the polarization data to allow
for future modifications, if necessary, as a result of any new findings and new understanding
of the calcareous coating formation process.
In describing this procedure we have differentiated between what we call instantaneous (dy-
namic) polarization curves and static polarization. This is illustrated in Fig. 3, where the dashed
lines represent the instantaneous polarization curves which have the same meaning as the curves
in Fig. 2 and as represented by other authors.
It is obvious that the various dashed curves have been shifted towards lower current densities
following the calcareous coating growth and, accordingly, represent different coating qualities.
STRE}MMEN ON OFFSHORE CATHODIC PROTECTION SYSTEMS 235
I,LI
n-
Or)
E
LU
-750
istan tan, ous
- 800
t~ instanta ~eous
X \
- 850
,- st,~tiol ta ry
instantaneo JS .-b~l
-900
-950 ,\
20 40 60 80 100 m A i m 2
FIG. 4--Measured polarization curves of the static and instantaneous types obtained from isolated steel
specimens on an offshore platform [ 1].
The solid line in Fig. 3 (i.e., the static polarization curve with its S-shape) accordingly reflects a
variation in calcareous coating quality over the entire surface of the structure. This variation in
calcareous coating quality furthermore reflects local differences in the "charging history". Proce-
dures and results from measuring instantaneous polarization curves have been presented else-
where [ 1]. S-shaped static polarization curves have been measured using proprietary electric
field gradient systems for large offshore structures ] 30,31]. This effect has also been documented
by Fischer and AI [32]. Figure 4 shows such a static polarization curve and three instantaneous
polarization curves for the same panels obtained by measurements [ 1 ].
In the computer models this has been accounted for by relating the calcareous coating quality,
defined by the location of the instantaneous curve in Fig. 4, to a parameter H, the history
parameter, and calculated from:
(a) The integral i c • time for short time increments and calculated for each single surface
element.
(b) Next apply a correction of the integral (a) above for very negatwe or very posmve
electrochemical potentials for the same time mcrement, I e ,
H=f, (,r215 for E<-E, (12)

for E>--E2
The resultant value of the H parameter defines at any t~me the relatwe location of the mstanta-
neous polanzat~on curve for each surface element This instantaneous curve ~sobtained from the
data base, by lnterpolaUon in a diagram of the type shown m Fig 2, vahd for the specified
enwronmental con&tlons m terms of seawater temperature, sahmty, flowrate and 02
concentration
This procedure gwes the flexibility reqmred to analyze and uUhze data from &fferent sources
as outhned above Tests have proven its capability to regenerate performance data m terms of E
(mV) versus t c ( m A / m 2) for large platforms as measured m offshore mspecuons
The procedure descnbed above was designed for and proved satisfactory for handhng the
slow, long-term changes following growth of calcareous coatings at steady-state environmental
condmons However, at an instantaneous change m the enwronmental condmons, this is fol-
lowed by an instantaneous change m the catho&c current density This means that an interpola-
tion is reqmred from a data set of the format shown in h g 2 vahd for (vl, tempi, sahmtyl (O2)1)
to a new set of data on the same format but vahd for (v2, temp~, sallmty~ (O2)~) The procedure
for such mterpolauon has been described briefly below for two of these parameters, namely for
the flowrate and the temperature
FlowrateEffects
In an earher study [ 1 ] of flow-reduced effects on the current density m catho&c polanzatlon
of steel m seawater, it was shown that the following relaUonshlp was vahd
Sh = K • Re x • Sc y (13)
where
Sh = Sherwoud number,
Re = Reynolds number,
Sc = Schmldt number,
K= 0 070 - 0 678 depending on type of flow (laminar, turbulent rotating cyhnder),
x= 0 5 - 0 67 (depending on type of flow), and
y = 0 33 (vahd for &fferent relevant flow patterns)
By combining th~s equauon with the equauon for &ffuslon controlled O2-reducUon it was
shown that the cathodic current density could be expressed as a function of the flowrate, all other
parameters remaining constant
Ir ~" (14)
where
C = constant, and
m = 0 5 - 0 67 (typically for surfaces without scale)
A model was also developed and tested for the dependency of It on V ~ in the case that scale
was formed on the surface According to this model there are two important parameters defining
the quality of the scale m terms of influencing lr These are the thickness, t, of the scale and the
porosity, K It was demonstrated that the catho&c current density would be approximated by the
STRCtMMEN ON OFFSHORE CATHODIC PROTECTION SYSTEMS 237
mA/m 2
2500
2000
0 67
" 7O V
1500
1000
500
l r l i i l
04 08 1 2
m/s
FIG 5--1c as a funcnon of v for surface wtthout scale
same equation (14) also in the case that calcareous coatings were formed on the polarized steel
surface The theoretical model as well as numerous tests showed that Eq 14 was vahd with the
following comments
9 For a high quahty scale of high thickness and/or low porosity the constant C and the
constant m both are very low C may be less than 50 and m = 0 01 to 0 05 (when i c is
expressed m m A / m 2)
9 For lower quahty scale the constants C and m both increase C may be on the order of 100
to several hundreds and the exponent rn increase to 0 10 to 0 30 for poor quahty/hlgh
porosity and low thickness scales See Figs 5 to 8
For offshore polanzatlon tests conducted on isolated steel specimens and reported elsewhere,
cathodic current density variations were measured during a period of strong variations in wave
heights and sea current [1,23] see Fig 9 The C and m values of Eq 14 were calculated for
specimens polanzed to different potential levels and located at various depths, dunng a penod of
initial polanzaUon, for two of the same sensors (1 e, dunng formation and growth of calcareous
deposits) For one of these located at 40 m depth, C dropped from 800 to 362 and m from 0 60
(as for a surface with no coating) to 0 14 dunng a period of 5 days (Table 1) For three other
specimens located at the seabed (95 m waterdepth) the low C and m values confirm that a high
quahty calcareous coating exists
A similar analysis with slmdar results has been done by Fischer et al [ 32 ] See also the work of
Gartland and AI [33] and Wolfson and Hartt [34]
238 COMPUTER
MODELING
INCORROSION
I
mA/m2
t:lmm r
250
i=C 9 v m
K=06
K= 05
150 / 04
/
, 0.3
100
K = 02
50
K= 0.1
K: 0 05
1 l I l
04 08 1 2
m/s
FIG 6-- b as a functton o f v for surface wtth calcareous deposits of I mm thwkness and dtfferent porostty
values (theoretwal model) K = 0 6 htgh porostty and K = 005 dense layer, low porostty
Using Eq 14, interpolation can be done between different sets of curves of the data base on the
format of Fig 2
Temperature Effects
S~mdar interpolation is possible for instantaneous changes m the seawater temperature Again
this will result in an instantaneous change m the current density for a gwen quality of the
calcareous coating As for flowrate effects, this instantaneous change is in addmon to the long-
term effects of a temperature change on the growth and future quahty of the calcareous coating
In a model developed it was demonstrated that the catho&c current density at one tempera-
ture could be expressed as a function of the current dens]ty at a higher or lower temperature by
an equation of the form [ 1]
tc = to X e kt (15)
It was shown that the model was vahd also m the case that scale was present on the steel
surface Typ]cal results from tests conducted over a period of approximately 12 h are shown m
Fig 10 Due to the short test period it was assumed that the quahty of the calcareous scale was
essentially unchanged Typical test results showed that the instantaneous change m tc was on the
order of 3 to 6% per degree centigrade
I
mA/m2 t : 0.1mm
250
200
K = 0 05
150
K : 0 03
100
50
K : 0 01
0 4 0 8 I 2 m/s
FIG 7--As Fig 6 except that the thickness of the scale lS much lower
tc = t 0 X ( 1 0 p ) t (16)
where
p = 3-6 typical, and
t = Instantaneous change in temperature, ~
Other Effects
A number of other parameters were hsted m Eqs 9 and 10 that influence the current density
and potential distributions Despite all the work conducted m this field there is not yet a full
understanding of all relevant effects Need exists for further study on the process of formation
and growth on calcareous coatings, the effects of marine orgamsms, the possible effects related to
water depth for deeper waters, etc
Computer Modeling Procedures and Applications

A system known as the SEACORR/CP Program, developed by th]s author and co-workers
described previously [25], includes the following software modules and procedures
1 A pre-processor for corros]on and CP parameters

mAim
300
250 = 233 v~176
200
f , = 206 V0043
f I I I I I
04 08 1 ?- mls
o -920 mV SRE
9 -8110 mV SRE
ta - 7 5 0 mV SRE
FIG 8--Measured current densittes for cathodically protected steel in seawater at varlous flowrates for a
situation with "medmm quahtf'" calcareous coatings [1]
2 A pre-processor for generation of geometry, an mteractwe mesh-generator ( F E M G E N ) 2

3 A boundary element analysis module (BEASY) 3 plus especially developed addmonal
procedures for handhng the electrochemical boundary condmons
4 A comprehenswe data base with data obtained in situ on offshore structures using proprie-
tary electrical field gradient systems for collecting simultaneous potential and current
denstty data
5 A corroston/CP post-processor
6 A post-processor for color graphics data presentation (FEMVIEW) 2
The system was developed to handle large and complex offshore structures and at the same
time to enable detailed calculations for local sections of such structures This was obtained by
designing the software to be run m two modes
9 M o d e 1--Handhng of global models (1 e , models of entire structures, often large and

complex offshore structures utdlzmg tubular elements)
9 M o d e 2 - - " L o c a l box" model where a section or "box" of the global model ~s cut out and
the boundary conditions transferred lfreqmred to th~s local model (e g , of a complex node
comer using quadnlateral surface elements) See also Figs 11 to 13
2 FEMGEN and FEMVIEW are developed and supphed by Fegs Ltd, London, U K
3 BEASY is developed by Computational Mechamcs Ltd, Southampton, U K
u~-930 $2 (-66m)
" ' - 940 . . . . . . . .
130
125
E $1 ( - 4 0 m )
E 120
o
115
750
~3 ( - 4 0 m )
500
E " ~' "~, 10
E
m
o .r
250
0w
5 Ill
"!"
UJ
>
1 2 3 4 5 6 DAYS
FIG 9 - - V a r l a t t o n tn p o t e n t t a l d u r i n g g a l v a n o s t a t w m e a s u r e m e n t (top) a n d current denszty variations
during potenttostatw measurements ( two middle curves ) and vartattons of wave hetghts(bottom) [ 1,33 ]
The system was furthermore designed to carry out a time-step analysis This means that the
gradual change with time m potential and current density distributions is calculated and pre-
sented for selected time intervals It takes care of local redlstnbutions of potentials and current
densiues reflecting the former charging history ( H parameter value) and previous variations in
environmental c o n d m o n s for any local section or element of the structure Sacnficlal anode
depletion is also calculated
The software allows for halts in the program execution to change the environmental condi-
tions (e g , to simulate seasonal variations over the hfe span of the structure, to simulate storms,
etc ) This restart capablhty also allows for making changes in the structure itself. This may
include the addition ofplpehne risers, conductors, etc If the user wants to remove the pllegulde
of a structure to improve the protection locally and to reduce the rate of depletion of the anodes
locally, this can be simulated as well [25]
TABLE l--Change in C and m m Eq 14 dunng a pertod of polartzatton (see Ftg 9)
Specimen Sensor Depth,

No m C m E (mV SCE) Date
SI -40 159 0 19 -920 8 Dec 1977

130 0 12 -920 1 Jan 1978
120 0 07 -920 3-4 Jan 1978
113 0 05 -920 5 Jan 1978
91 0 035 -920 5 Feb 1978
$3 -40 800 0 60 -750 1 Jan 1978
640 0 36 -750 3-4 Jan 1978
570 0 26 -750 5 Jan 1978
362 0 14 -750 5 Feb 1978
SI -95 65 0 029 -920 30 Dec 1977
$2 -95 61 0 023 -800 30 Dec 1977
$3 -95 58 0 027 -750 30 Dec 1977
Naturally this faclhty allows for adding anodes at any time m the hfe span o f a structure (] e ,
m the m o d e h n g s e q u e n c e ) a n d thereby to simulate a n d test alternatwe CP retrofit programs
In a d d m o n , the system can h a n d l e current sources hke impressed current anodes a n d current
sinks hke the reside o f o p e n pale sleeves In the latter case success obviously depends o n proper
m a p p i n g o f the existing structure m terms o f condition o f the sacrificial anodes a n d not least o n
the current density a n d potential d l s t n b u t l o n s o n the structure This can be done using a m o d e r n
current density system [30,31,35]
mAim 2
350
i "
300
250
200
. 101
150
9 No 4 0.8 mls
1 i I i I l I
4 6 8 10 12 14 16 18 ~
FIG lO--Instantaneous change m ic on short-term change m temperature The quahty of the calcareous
coating remamed vtrtually unchanged during the test
FIG. 1 l--Showing the principle of using global and local models," the first gives the general solution to the
problem, the latter shows the detailed distribution locally.
FIG. 12--Global model of offshore platform in 145 m water depth.
Although the conductivity has to be constant throughout the regime that is modeled, it is
possible to handle layers of different conductivity. This is done by splitting the problem into
different zones, solving the problem within each such regime separately, and matching the
solutions at the boundaries.
Applications
Computer modeling techniques for offshore cathodic protection systems have been developed
by several research groups over the last decade. The primary objective has normally been to
develop and use such programs for new CP designs. Considerable savings have been obtained
from optimized but still safe and reliable CP designs of reduced weights and reduced costs
compared with more traditional designs that normally have to include solid safety factors. Re-
duced weight is especially important with today's single jacket lift technology.
Practical use of these new techniques has shown, however, that there may be great advantages
using computer modeling also for other purposes such as inspection, trouble-shooting, and
maintenance of offshore CP systems. The main areas of computer modeling application may
comprise the following:
1. Cathodic Protection Design Analysis of New Structures--Optimization of anode size, num-

ber, and distribution by modeling over the life of the structure. Included in the design
analysis is the study of possible shadow effects in geometrically complex sections of the
platforms and possible interference effects between platform, risers, and pipelines.
FIG. 13--Local model of pile sleeve with anodes.
Application of the program may be particularly useful for structures of new design or
increased size or complexity compared with previous projects, for which no data are avail-
able to the design engineer based on previous experience. The same applies when going
into a new geographical area for which the environmental conditions may vary compared
to previous experience.
2. Troubleshooting by Analysis and Redesign of CP Systems for Existing Under-ProtectedStruc-
tures-Modeling an existing CP design and matching the results with measured potentials,
a proposed redesign is checked by adding the suggested type and number of anodes in the
model. It will be demonstrated whether this is a satisfactory method of solving the problem.
By an interative process the modeling will demonstrate the optimal number and positions
of anodes to bring back the required value.
3. Processing of Potential and Field Gradient Readings Obtained In Situ on the Structure, to
disclose performance data (current density versus potential) for the CP systems and
thereby also causes of possible problems. Such applications have previously demonstrated
needs for revision of design methods and criteria for offshore cathodic protection.
4. Study of Cathodic Protection and Training of CP Engineers by Using the Program as a
Training Simulator--Training simulation programs typically may include the study of the
aging process ofcathodically protected steel and the dynamics in distribution of potentials
and current densities.
The models may furthermore be used for comparison of alternative systems and CP
designs, including the development of new anode types and geometries. In this context it is
also used to calculate anode resistance values as used in the more basic analysis procedures
described above.
Acknowledgments
The author is indebted to his colleagues, Mssrs Terje Blakset and Harald Osvoll, for useful
suggestions and comments
References
[1] Stremmen, R D, "Aspects Related to the Cathodic Protection of Offshore Facdltles," Thesis for the
Dr lng Degree at NTH-Norweglan Institute of Technology, Dec 1978
[2] Strommen, R D , paper presented to 2nd Israel-Norwegian Symposium, Electrochemistry-Corrosion,
NTH-Trondhelm, Norway, June 1978
[3] Strommen, R D, Tram I Mar E, Vol 91, 1979 (NCS Conference, 1978, Edinburgh, Scotland)
[4] Khngert, J A , Lynn, S and Tobisa, C W, ElectrochlmActa, Vol 9, 1964, p 297
[5] Sale, J P, "The Evaluation of Anode Configurations for the Internal Protection of Pipes," EFC
Conference, London, June 1968
[6] Ellassen, S and Steensland, O in Proceedings, 8th OTC, Dallas, Tex, 1977, pp 429-436
[7] Wyatt, B S, Bnttain, R and Jones, G R , Materials Performance, Vol 19, 1980, pp 16-23
[8] Smart, J , Trans I Mar E, Vol 91, 1979, (NSC Conference, 1978, Edinburgh, Scotland)
[9] Str~mmen, R D and Rodland, A , Paper No 241, NACE Corrosion-80, Chicago, Ill, March 1980
[10] Munn, R S, Materials Performance, Vol 21, No 8, 1982, p 29
[11] Warne, M A in Proceedings, 1st International Conference on CP Theory and Practice, 1 CorrSt,
U K, 1982
[12] DeCarlo, E A , Materials Performance, Vol 22, No 7, 1983, p 38
[13] Ju, J W and Chow, J S K, Materials Performance, Vol 21, No 10, 1982, p 9
[14] Strommen, R D , Kelm. W, Fmnegan, J and Mehdlsadeh, P, NACE Corrosion-86, Paper No 45
[15] Gartland, P O and Johnsen, R , NACE Corrosion-85, Paper No 319, Houston, Tex, 1985
[16] Zamani, N G , Chuang, J M and Porter, J F, Internatzonal Journal for Numerical Methods m
Engmeermg, Vol 24, 1987, pp 605-620
[ 17] Telles, J C F et al Corrosion Journal (NACE), Vol 46, No 6, 1990, pp 513-518
[18] Prentice et al, Corrosion Journal (NACE), Vol 46, No 1, 1990, pp 75-83
[19] Zamam, N G , Chuang, J M and Hsiung, C C, International Journal for Numerical Methods m
Engineering. Vol 24, 1987, pp 1479-1497
[20] Munn, R S, NACE Corrosion-84, Paper No 49, 1984
[21] Brebbla, C A and Walker, S, Boundary Element Techmques m Engineering, Butterworth, London,
1980
[22] Danson, D J , "BEASY A Boundary Element Analysis System," paper presented to 4th InternaUonal
Conference on BEM, Southampton, England, 1982
[23] Nlsancloglu, K, "Design Techmques in Cathodic Protection Engineenng," to be published In Modern
Aspects of Electrochemistry
[24] Zamam, N G , Porter, J F and Mufti, A A, InternattonaIJournalforNumerwalEnglneermg, Vol 23,
1986, pp 1295-1311
[25] Strommen, R D, Kelm, W, Finnegan, J and Mehdlzadeh P, Paper No 45, NACE Corrosion-86,
Houston, Tex, 1986
[26] Gngorev, V P, JournalofApphedChemtstry, (USSR). Vol 34, No 1, 1969, p 169
[27] Sander, K F, Paper No 2, Conference on CP Theory and Practice, Coventry England. 28-30 Apnl
1982, I Corr St, U K, 1982
[28] Nisancloglu, K, Materials Performance, Vol 23, No 12, 1984, p 36
[29] Nisancloglu, K, "Modehng for CP," Conference on CP Theory and Practice, O K, 1988, I Corr St
[30] Levings, K, Fmnegan, J , MclOe, W and Strommen, R , OTC Paper No 4565, OTC, Houston, Tex,
May 1982
[31] Strommen, R , Osvoll, H and Kelm, W, Paper No 297, NACE Corrosion 1986, Houston. Tex,
March 1986
[32] Fischer, K P, Sydberger, T and Lye, R, Matertals Performance~Vol 27. No 1, 1988, p 49
[33] Gartland, P O, Strommen, R D and Bardal, E, MaterlalsPerformance, Vol 22, No 6, 1983. p 40
[34] Wolfson, S L and Hartt, W H , Corroston, Vol 37, 1981, p 70
[35 ] Cochran. W, Bonner. M, Strommen, R , Keim, W and Morton, D. Paper No 375, NACE Corrosion
1990, Las Vegas, Nev, April 1990
DISCUSSION ON OFFSHORE CATHODIC PROTECTION SYSTEMS 247
DISCUSSION
R S Munn i (wrmen dlscusston)--You mentioned computing separate "zones" of a system

(e g , seawater and mud) as separate problems coupled at the interface, because the BEM does
not allow for mhomogeneous media How is the couphng accomphshed--mathematlcally9
R D Strgmmen (author's closure)--It is correct that by separating and computing separate
"zones" of d~fferent conductwlty, it is possible to analyze problems comprtsmg an mhomo-
geneous electrolyte (e g , one zone of seawater and another zone of mud having a different
electrical res~stwlty) The solution ~s achieved by solving the equations for each zone separately,
usmg special mterphase elements on the boundary between the zones Having solved the equa-
tions for one zone, the gradients for the mterphase elements are used as input for the next zone
i U S Naval Underwater Systems Center, New London, ~ 06320
R. A. A d e y 1 a n d S M. N i k u 1
Computer Modeling of Corrosion Using the

Boundary Element Method
REFERENCE: Adey, R A and Nlku, S M, "Computer Modeling of Corrosion Using the
Boundary Element Method," Computer Modehng m Corroston, ASTM STP 1154, R S Munn,
Ed, American Society for Testing and Materials, Phdadelphm, 1992, pp 248-264
ABSTRACT: The development of computational systems for the sxmulatlon ofgalvamc corrosion
is discussed Techmques are described for the representation of the physics and chemistry of
corrosion in mathemaUcal form and their computaUonal implementation Apphcatmns of the
system to manne and offshore englneenng problems are described
KEY WORDS: corrosion, computer simulation, boundary element method, computer modehng,
cathodic protection
In recent years there has been a growing interest in the predlcnon of the behavior ofengmeer-
mg problems revolving galvanic effects This class of problem includes galvamc corrosion, cath-
odic protection methods, and the reverse problem of electrodeposmon commonly used in
manufactunng
The initial impetus for the development of computational systems to analyze galvamc corro-
sion problems came very much from the od and gas industry The discovery of slgmficant
offshore fields In deep water entailed a significant shift m production facdmes from land to the
ocean
The cost of corrosion to the oll and gas industries is extremely large This is apparent when the
amount of capital tied up in offshore structures ~s considered However, corrosion reduces the
service life of not only offshore structures but deteriorates the performance of sea-going ships
and boats and industrial plant and machinery To combat this, cathodic protection (CP) systems
and other devices and systems are fitted m an effort to reduce corrosion
If these systems are not performing to the reqmred extent, ~t can prove far more expenswe to
alter the system after commission of the structure or vessel than the lnltml cost of the CP system
Ifa vessel has to be laid up m order to perform this work, a loss of revenue is also recurred With
offshore structures the retrofit ~s carned out m an extreme environment Th~s makes the work far
more difficult and costly
Furthermore, the reqmrements of offshore structures wdl vary from those of sh~ps, and the
restncnons placed on the design of the CP system may vary from design to design For offshore
structures there may be a hmstanon on the amount of power avadable for the CP system and, ff
too much power is used, detrimental side effects may occur Ann-fouhng coatings can be dam-
aged, causing less efficient performance and leading to more frequent wslts to dry dock Hence
excessive ~mpressed current may be as harmful as too httle
This leads to the conclusion that m many cases the abdlty to model CP systems is desirable
and in other cases it is absolutely necessary
i Computational Mechanics Inc, Billenca, MA 01821
248
ADEY AND NIKU ON BOUNDARY ELEMENT METHOD 249
The majonty of designs of CP systems have in the past rehed upon the skill and expenence of
the engineer However, the installation of high value manne structures in deeper and more
hostde environments bnngs with it more scientific methods of design
Evaluation of CP systems normally takes place after commissioning, but this is expensive and
clearly post-design Until recently laboratory tests have been impracticable Either the cases
examined have been too simple to be indicative of the real world or the structures have been too
large and comphcated to be brought within a test facihty Recently however [ 1 ], it has been
shown that scale models may accurately be used when assessing CP system performance, the
properties of seawater being scaled by appropnate dilutions Although useful for ship systems,
this technique is still expensive, requinng models of 5 ft or more m length with an equivalent test
facihty A further problem is encountered when considenng offshore structures where the bound-
ary condmons are now nonlinear The dimension of the problem and seawater properties may be
scaled, but the polarization effects cannot However, scaled modehng can stall be seen as a major
advance and may prove useful for validation of a computational CP analysis system
Although much of the lmtml demand for computer modehng occurred in the oil and gas
industry, many new interesting apphcations have been found in the design of boats, ships, and
industrial plants In the manufactunng industry the "inverse problem" of designing systems to
deposit material has also generated research into mathematical modeling
The equations describing the galvanic system can be dwided into two classes The first, de-
scribing the potential distnbutlon in the electrolyte, can be represented by the Laplace equation
Thin is a fairly simple equation to solve and from a numerical sense is well behaved The second
class descnbes the electrochemical reactions which take place on the anodlc and cathodic sur-
faces These equations are nonlinear and time dependent
For experimental setups and many lndustnal problems the geometry of the system is enclosed
(I e , the electrolyte is contained in a vessel or container) However, In many apphcations the
electrolyte is the sea and from the practical point of view is an infinite domain This is another
significant factor which influences the choice of numencal techmque
Prediction Techniques
Early predictions of corrosion rate and estimates of adequate cathodic protection (CP) have
traditionally been based on rules of thumb derived from trial-and-error case studies and sample
exposure tests Applying these techniques to real structures usually involve gross extrapolations,
use of large safety factors, and on-going corrections and maintenance of the system
In the late 1960's the fimte difference ( F D ) method was applied to the problem [2] This
method requires the &scretizatlon of the seawater with a mesh The solution is found at the
intersection points, or nodes, of the mesh The solution is numerical because the vanation of the
solution from one node to adjacent nodes is governed by an approximate form of Laplace's
equation FD methods, although supplying accurate results m many situations, have major
disadvantages These early programs mainly considered two-&mensional problems However,
the majority of offshore structures do not lend themselves to two-dimensional analysis Many
joints are three-dimensional Nearly all are made from tubes with relatively large diameters
where shadow effects are important Moreover, the accuracy achieved is dependent upon the
number and d~stnbutlon of nodes Hence, for large three-&mensional volumes to be modeled as
is the need with CP systems, the number of nodes can become prohibitively large For this
reason, the use of FD methods becomes more feasible only with an increase in power of the large
computers However, a further problem IS that FD methods do not lend themselves to systematic
assembly of the equations Hence they are difficult to program for general geometries and it IS
&fficult for users to describe the geometry
Further fimte difference results were by Sale [3], Strommen [4], and Doig et al [5]
In the 1970's solutions were sought using finite element ( F E ) methods [6-11] As with FD
methods the volume to be analyzed (the seawater) has to be dlscretlzed with a mesh The mesh
this time divides the volume into small elements of finite size, each of which is of simple enough
shape for the equations to be solved simply numencally over the volume of the element For
each element a set of equations IS obtained The final system equations are obtained by assem-
bling the equations for all the elements to form a consistent set (l e , a set with a unique
solution) The advantage of FE methods over FD methods is that they are algorithmic and easy
to program to cope with general problems However, creating finite element meshes is an ex-
tremely tedious and time consuming process This can be made far easier by automatic mesh
generators To date. these are very efficient for two dimensions but require a large amount of
manual checking and amending by hand when used for three dimensions Comphcated models
can take weeks, or months, to construct This problem is heightened by the need to analyze the
"Infinite" domain of the seawater Again, the accuracy achieved is dependent upon the number
and size of the elements used Hence for CP models the models can become prohibitively large
In the late 1970's another form of numerical technique, boundary element (BE) methods,
became available [ 12] As the name Implies, the method requires elements to be created, but
now only on the boundary (or surfaces) of the problem geometry The advantages of boundary
elements for CP analysis are many fold
9 The meshes are now only on the surface, hence only (equivalently) two-dimensional ele-
ments are required Mesh generators can be used with confidence, and models can be
constructed extremely quickly and inexpensively
9 BE gives the solutions on the boundary and, only if required, at specified internal points
Since for CP analysis the solution is only required on the surfaces, it IS far easier to analyze
the results than for FE analysis which automatically gives results for all nodes (internal or
boundary)
9 BE methods are very effective and accurate for modehng infinite domains as is the case for
CP analysis
J
The first paper describing the application of boundary element techniques to corrosion engt-
neenng problems was published by Danson and Warne [ 13] They described the application of
Boundary Elements to the Conoco Hutton Tension Leg Platform installed in the North Sea The
system they described used constant boundary elements (l e , the potential and current density
were assumed to be constant over each element) and a simple Tafel slope relationship to repre-
sent the polarization Subsequent developments at Computational Mechanics following this
initial work are descnbed by Adey, Brebbla and Nlku [ 14-21 ] and application using the software
by Strommen [22.23]. Other work in this area has also been carried out by Gartland [24], Aokl
[25], Munn [26], and Telles [27] Fu [29,30] was also one of the first to pubhsh work on the
application of the boundary element technique to galvanic cells and corrosion
Theoretical Foundations of Cathodic Protection and Galvanic Corrosion

A cathodic protection system consists of three parts The structure to be protected (cathode),
the anode with provides the protection, and the electrolyte (e g . seawater) [31 ] There are two
general types of anodes in normal use Sacnficlal anodes are usually made of zinc, aluminum
alloys, or similar materials which are more active in the galvanic series than iron or steel The
sacrificial anode, therefore, corrodes In place of the protected structure Impressed current an-
odes apply a potential difference by means of an external power supply
Dunng the electrochemical corrosion process, several anodlc (oxidation) and cathodic (re-
ducuon) reactions occur The pnnopal anodlc reaction in the corrosion of an offshore structure
IS
Fe --~ Fe +2 + 2e- ( 1)
and the pnnclpal cathodic reaction is
02 + 2H20 + 4e- --~ 4OH- (2)
When the structure 1s placed under the control of a suitable cathodic protection system, the
anodlc (corrosion) reactions are transferred from the structure to the sacrificial or impressed
current anodes The flow of current IS reversed by this electrochemical process and the structure
surface becomes the cathode upon which reaction (2) occurs In the case of sacrificial anodes
(i e , zinc), the anode metal simply &ssolves due to the inherent potential difference between
the anodes and the structure However, using "inert", impressed current anodes causes a gas
evolution reaction (i e , hydrogen) to occur on the anode (without loss of material) and the
familiar protective, cathodic reaction occurs on the structure
A further important concept m cathodic protection ~s that there is a minimum potentml
(thermodynamically reversible potential) E which must be exceeded before any reaction occurs
(and consequently before any current can flow)
To describe a cathodic protection system mathematically, not only must the equations which
represent the flow of current through the medium (e g , seawater) be developed but also the
equations which represent the electrode reactions
Mathematical Aspects
For a uniform, lsotroplc medium, the flow of current can be shown to obey the Laplace
equation
kV2E = 0 (3)
where
E = potential,
k = conductivity,
together with
1 OF.
Ix, = ~ Ox--~, (4)
where Ix, = current density flowing in x, direcUon.

Therefore the Laplace equation can be used to represent the electrolyte
The boundary element formulation can be developed as follows Let us assume that the
boundary conditions over (the boundary enclosing the volume)
E = E on I' 1 / (5)
I= [ F2 J
where/~ and [ a r e given, and P t and F 2 are parts of the boundary such that F, UP2 = F (the
complete boundary) (In reahty a complex relationship between the current density and poten-
tim has to be specified to represent the polanzatlon of the metal surfaces This will be descnbed
later )
We wtsh to solve Eq 3 numencally We wish to mimmize the error and this can be done by
starting from the weighted residual statement
fn V2E(x)E*(y'x)dfl(x) = ~ 2 [/(X) -- [(x)]E*(y,x)dP(x)
- drfl [ E ( x ) - ff~(x)]I*(y,x)dF(x) (6)
Following standard procedure (l e , taking the weight function E as the fundamental solution
to •2E = 0 and integrating by parts twice), the integral equation can be reduced to the boundary
integral expression
c(y)E(y) + f~ E(x)l*(y,x)dr(x) = f~ l(x)E*(y,x)dr(x) (7)
where E* and I* are the fundamental solutions

For example, in three-dimensional geometry the fundamental solutions are
4
E*(x,y)- 4rkR
l*(x,y) - e," n
47rR 2 (8)
where
R = distance in the space,
e = unit distance vector, and
n = unit normal vector
Numerical Solution
Equation 7 can be seen to contam only integrals over the boundary No volume integrals exist,
hence the ability to use elements on the boundary only
For particular geometries and boundary con&tions this can be solved analytically for each
point y on the boundary However, for general problems, geometnes, and boundary conditions,
we required a numencal solution Note, firstly, that E and I are known at all points Secondly,
either E or I is known at every point on the boundary, the other being the unknown to be solved
for Hence, provided enough equations can be formed, they may be solved simultaneously to
obtain the solution
The boundary is divided into elements Hence the boundary is approximated by elements
which are non-overlapping and cover the whole of the boundary (Fig 1 )
From Eq 7 one can write
FIG I--Boundary element model showing elements only on the boundary
Since r has been approximated by N elements, this becomes
c'E' + ~ f r j E I * d I ' = j=l

~ (10)
where f r ) denotes integration over elementj

The elements used may be denoted as constant, linear, or quadratic This denotes the vana-
tlon that functions (the solutions) are allowed to take over the elements This is the point at
which the procedure becomes "numerical"
The node points are the points at which the solution will be found The mesh points are used
to define the shape of the elements The solution is assumed to be constant over a constant
element with the value being defined at the single node points For linear elements the solution
is assumed to vary linearly along the element The solution is assumed to vary quadratically
across quadratic elements
The boundary element equations can now be assembled into a system of linear simultaneous
equations
Expressing the complete set of equations in matnx form gives
HE = GI (11)
where
H and G = problem influence matnces, and
E and I = potential and current density vectors
For each node there is one equation and as seen in Eq I l one value of potential and one
current density unknown However, when applying the technique to real-problem geometry
additional information will be known which will enable us to solve the system of equations
For example, the potential may be known on the anode but the current density unknown
Alternatively the current density may be known on some nodes but the potential unknown
By rearranging to get all knowns on the right-hand side, and all unknowns on the left-hand
side, we obtain
AX = B Y (12)
The right-hand side is multiplied out to obtain
AX = F (13)
The simple situation descnbed above does not occur frequently, since the boundaries conditions
to the model are descnbed by complex electrode kinetics but the general approach applies
Electrode Kinetics
The previous discussion has been restricted to the case where the electropotentlal or flux
density is known on the surface of the electrolyte in contact with the anod,c or cathodic surfaces
However, polanzatlon on the metal surface can be considered to introduce an impedance or
resistance between the electrolyte and the metal
For simplicity this can be written as
I a .= f a ( E a )
'c = f~(E~) (14)

where
to = current density on the anodic surface,
Ea = electropotentlal on the anodic surface,
f~ = a function which represents the electrode kinetics and polarization on the anodic sur-
face, and
to, E~ and f, describe the conditions on the cathodic surfaces
In practice f~ and f, are functions of many factors, both chemical and environmental, which will
be dtscussed later
Coupling of the System

From the analysis of the anode and cathode electrode kinetics and the boundary element
model of the medmm, sufficient equations are available to couple the system
The boundary element equation ( I 1) relates to the flow of current between the anode and the
cathode and models the potenual drop in the medium due to its resistivity Rewriting Eq I l
using electropotential terminology
HE = GI (15)
It IS convenient at this stage to partition the E and I vectors into those nodes which form the
anode and those which form the cathode
hca h~JLEcJ &o g,~JLicJ (16)
where the subscript a refers to anode surface and c refers to cathode surface
From Eq 14
,~ = f o ( E , )
t, = f ( E ~ ) (17)
Substituting into Eq 16"
h,~JLEcJ I ~ g,~ J[. f ( E c ) J (18)
The resulting Eq 18 is now solved by iteration to obtain the current density, and electropoten-
tial E at all nodes on the anode and cathode
~ f
FIG. 2--Special tube element developedfor the representation of anodes and offshore platforms.
Polarization
In the derivation of the governing equation the electrode kinetics on the anode and cathode
have been assumed to be represented by an equation of the form
i=f(E) (19)
The function f ( E ) is known as the polarization curve which describes the relationship be-
tween the current density and electropotential E for the electrode reaction.
In practice this equation does not sufficiently describe the electrode reaction, since other
factors are involved. The most important of those factors is the buildup of a calcareous deposit
on the cathode (if steel is polarized sufficiently in seawater). This deposit is in addition to any
organic film and marine growths being formed. The scale alters the polarization behavior and
reduces the effective surface area, introducing an additional physical resistance and conse-
quently introduces a time dependent factor.
The polarization algorithm used in the program allows for both steady-state and transient
analysis of a cathodic protection system. The user can supply a family of polarization curves that
vary with the quality of scale.
The system can therefore predict the current density and potential, including the temporal
effects of calcareous scale and the environmental factors of water resistivity, salinity, oxygen
content, temperature, and velocity.
Systems Approach
Many engineers will be familiar with the systems approach to the analysis of engineering
problems. General purpose finite element systems have proved extremely successful, enabling
engineers to solve a wide range of stress analysis problems with widely varying geometry and
loading. The approach can also be adopted for galvanic corrosion type problems.
The following section describes some of the features of such a system, BEASY-CP, based on
the BEASY general purpose boundary element analysis system. The system can be used for the
analysis, design, and parametric study of galvanic corrosion, cathodic protection, and
electrodeposition.
The procedure to perform an analysis essentially requires three stages: (i) model preparation
(description of the problem geometry and collection of suitable polarization data), (ii) simula-
tion (basically a computational process which requires no interaction from the user); and (iii)
post-processing.
Model Preparation
The first stage involves the definition of the geometry and the environmental conditions.
The geometry is described by subdividing the boundary of the problem (the surface of the
FIG. 3--Tubular joint on marine offshore structure with sacrificial anodes.
structure and anodes in the case of CP) into a number of elements interconnected at nodes. The
nodal coordinates and element connectivities are defined. The size and type of elements are
chosen according to the complexity of the problem and the order of approximation required to
describe the variation of voltage or current density over the surface of the elements.
The system also allows one to study the potential field inside the corrosive electrolyte. If this is
required, the area of interest should be defined by a pattern of internal points whose coordinates
are specified.
The geometry model can be set up manually or generated interactively by the use of a wide
range of compatible pre processors such as BEASY-IMS, PATRAN, or SUPERTAB.
E l e m e n t s - - S t a n d a r d boundary elements can adequately define most geometries but in the
case of cathodic protection systems involving sacrificial anodes, considerable improvements in
1100 !
L .30 D~ys
1050 [ ~ . - . > / . . . . . . . . . . .o
o
< 950
.~_ 800 ' 7
~ 700
650
600 i i i
0 20 80 1;0 120' 1<0'
Current density ( M A PT l)
FIG. 4--Polarization curves for mild steel held at 215 mA / m for various periods.
FIG. 5--Structure element model.
modeling can be achieved if special elements are developed. Figure 2 shows a rod-shaped ele-
ment developed within for the representation of anodes. This element assumes the potential and
current density is constant around the circumference and along its length. Other forms of this
element are available which assume linear and quadratic variation along the length.
This element has proved to be extremely effective in representing sacrificial anodes on jacket
type offshore prodfiction platforms (Fig. 3). In these cases it is not unusual to have 1000 to 3000
anodes on the structure.
Jacket-type offshore platforms have also spurred the development of tubular elements to
represent the members of the structure. These are similar to the anode elements described in Fig.
2 and can be used to model large-scale frame-type structures.
In general, any geometry can be represented either as two-dimensional axisymmetric or three-
dimensional using the wide variety of element types available.
Some types of problems particularly with impressed anodes require the ability to specify a
source of current at a point or along a line. Special elements can be developed to represent these
point and line sources, and they can be located anywhere within the electrolyte.
These type of elements can be effectively used to represent wire anodes and impressed anodes
on boats and ships. However, as with any element type the user is free to use them to represent
any feature of his problem.
Polarization D a t a - - T h e polarization behavior on the surface of cathodic and anodic surfaces
is described by the definition of boundary conditions.
Depending upon the degree of complexity involved, the polarization conditions can take the
FIG. 6-- Potential distribution on structure.
form of either constant voltage or current density, or a steady or time dependent nonlinear
relationship between the voltage and the current density. The latter can be used to simulate real
polarization, taking into account the effect of environmental conditions.
The generation of the time dependent nonlinear boundary condition is more complex, since it
may involve experimental data readings. Each curve describes a potential current density rela-
tionship for a specified condition of calcareous deposit or other environmental parameters.
Because the polarization and environmental data can take varying forms from simple coeffi-
cients representing linear polarization to numerous data points representing experimentally
derived polarization data, these data are best separated from the geometric data. For example, in
BEASY the user simply specifies on the geometric model the name of the material and the
system automatically picks the appropriate polarization data from a file. In this way, a library of
polarization data can be easily built.
Figure 4 shows a typical cathodic polarization graph obtained from a potentiostatic test.
Environmental D a t a - - T h e final data required to complete the model is the resistivity (conduc-
tivity) of the electrolyte.
Simulation
The computational scheme assembles the boundary element equations representing the elec-
trolyte and couples them with the equations derived from the polarization data. If time-
FIG. 7--Potential prediction near a joint.
dependent polarization data are defined, the conditions at the nodes is predicted at different
times as requested by the user.
An important point to note is that the solution itself determines which surfaces are cathodic or
anodic, based on the polarization data. This is particularly useful in general galvanic corrosion
problems.
Post-Processing
The results from the calculation describe the condition of the surfaces in terms of the electro-
potential and current density. From these results the following information can be determined:
(a) The degree of protection provided by a CP system.

(b) The rate of corrosion,
(c) The anode consumption rate.
(d) The total current demand and how it changes with time.
(e) The life expectancy of anodes.
(f) The rate of deposition of material in an electrodeposition problem.
(g) The optimum location for anodes.
(h) The optimum location of reference electrodes.
These data can be viewed graphically using post-processing software.

FIG. 8--Joint tube model showing overlap of elements.
Applications
Analysis of a Jacket-Type Offshore Platform
The use of tube elements makes large-scale analysis of jacket type offshore structures possible.
These structures typically consist of hundreds of tubular structural members and many thou-
sands of anodes. Defining this type of structure using surface elements would result in extremely
large models which would require supercomputer-like performance to solve.
This example shows a structure protected by sacrificial anodes. The anodes are represented by
special elements which can represent the anodic electrode kinetics. The structural members are
described using the tube elements which represent a variation in the potential (and flux) along
the variation around the circumference is constant. Figure 5 shows the model of the structure
with the anode elements.
This type of model can represent global type behavior as it accurately describes the structure
surface area and the geometric configuration. Therefore given the material polarization parame-
ters conductivity and details of the anodes a prediction can be made. This includes the current
density and potential distribution on the structure surface and its variation with time (Fig. 6).
The global analysis provided by the tube elements does not, however, give accurate predic-
tions in the area of the joints because the geometric model does not model the complex intersec-
tion of the tube members. This can be seen in Fig. 7 and more clearly in Fig. 8 where the tubes
can be seen overlapping.
FIG. 9--Local analysis ofjoint using boundary conditionsfrom global analysis.
The simulation of the electropotential distribution near the joints requires a model which can
accurately represent the geometry.
This is particularly important in order to reproduce the shadowing effects which the various
structural members have on each other.
In order to model the complex potential fiekt near a joint a model can be created using surface
elements. This type of model can produce a very detailed picture of the potential and current
density fields, and it is possible with this type of model to reveal small underprotected regions
near the intersection of the members. This type of local analyses can include the more global
effects by application of the global field on the surface of a box surrounding the joint. This box is
constructed using elements and can be conveniently placed as it does not have to be part of the
physical structure (Fig. 9).
Conclusions
Computer simulation of galvanic corrosion and cathodic protection systems can now be under-
taken with confidence with systems like BEASY.
The boundary element technique has been found to be very suitable for modeling corrosion
problems as only the surface has to be defined and values of potential and current density are
computed with high accuracy on the metal surfaces.
The adoption of a general scheme for representation of polarization is essential as polarization
data is available in a wide variety o f forms and levels of detail.
Finally the technology descnbed here can be equally well used for any electro-chemistry
problem including electro-deposition and electro-forming
Acknowledgments
The authors wish to acknowledge the contributions of IMI Marstons. Conoco. Norway. and
the Department of Energy. U K . to this work
References
[1 ] McGrath. J N. Ttghe-Ford. D J . and Hodgklss. L. "Modehng Impressed Current Catho&c Protec-
tion System by Dimension and Conduct,vlty Scahng"
[2] Fleck. R N. "Numencal Evaluation of Current Dlstnbutton m Electrical Systems." M Sc thesis.
Umverslty of Cahforma. Berkeley. Sept 1964
[3] Sale. J P. "The Evaluation of Anode Configuratton for the Internal Cathodic Protection of Pipes."
Conference on Corrosion and Protectton of Pipes and Plpehnes
[4] Strommen. R D. "Computer Modehng of Cathodic Protection Systems Utlhzed m CP Monltonng."
OTC 4357. Houston. Tex. 1982
[5] Dolg. P and Flewm. P E J . "A Finite Difference Numencal Analysis of Galvanic Corros,on."
Journal of the Electrochemtcal Soctety. Vol 126. No 12. Dec 1979. pp 2057-2063
[6] Fu. J W. Paper No 115. NACE Corrosion Conference. Toronto. Canada. 1981
[7] Helle. H P E. Beek. G H M. and Ltgtehjn. J T H. "Numencal Determmat,on of Potential
Distnbutlons and Current Densities m Mulu-Electrode Systems." Corroslon/NACE. Vol 37. No 9.
Sept 1981. pp 522-530
[8] Fu. J W. "A Finite Element Analysis of Corrosion Cells." Corroslon/NACE. Vol 38. No 5. 1982.
pp 9-12
[9] Kasper. R G and Apnl. M G . "Electrogalvanlc Ftmte Element Analysis of Partially Protected
Manne Structures." Vol 39. No 5. May 1983. pp 181-188
[10] De Carlo. E A . "Computer Techmques for Offshore Corrosion Protection." Lockheed Horizons.
Winter 1980 / 81
[11] De Carlo. E A . "Computer Aided Cathodic Protection Design Techmque for Complex Offshore
Structures." Paper No 165. Corrosion/82. March 1982
[12] Brebbm. C A . Boundary Element Methodfor Engmeers. Pentech Press. 1980
[13] Danson. D J and Warne. M A . "Current Denstty/Voltage Calculations Using Boundary Element
Techniques." NACE Conference. Los Angeles. 1983
[ 14 ] Adey. R A. Modelhng CP Systems. Odman. June 1985
[15] Adey. R A . N,ku. S M. Brebbla. C A . and Fmnegan. J . "Computer A,ded Des,gn of Cathodic
Protect,on Systems." paper presented at the International Conference on Boundary Element Methods
m Engineering. Villa Olmo. Lake Como. Italy. 24-27 Sept 1985
[16] NIku. S M and Adey. R A . "A CAD System for the Analysis and Des,gn of Cathodic Protection
Systems." Plant Corros,on Prediction of Materials Performance. Cranfield Institute of Technology.
Cranfield. U K. Feb 1985
[17] Adey. R A and Nlku. S M. "Comparison Between Boundary Elements and Fm,te Elements for CAD
of Cathodic Protect,on Systems." BETECH Conference. South Austrahan Institute of Technology.
Adelaide. Austraha. Nov 1985. Computational Mechamcs Pubhcatlons. Southampton. 1985
[18] Nlku. S M. Brebbla. C A . and Adey. R A . "BEASY-CP A CAD System for Mathematical Model-
hng of Galvamc Corrosion and Cathodic Protection Problems." CADMO '86. Washington. D C.
Sept 1986: Computauonal Mechamcs Pubhcatlons. Southampton and Spnnger-Verlag. Berhn and
NY. 1986
[19] Adey. R A and Nlku. S M. "Computer Modelhng of Galvamc Corrosion." ASTM Conference.
Phoemx. Anz. Nov 1986
[20] Brebbm. C A and N,ku. S M. "Computational Apphcatlons of Boundary Element Methods for
Cathodic Protection of Offshore Structures." OMAE Conference. Houston. Tex. 1988
[21] Nlku. S M and Adey. R A . "Computer Prediction of Cathodic Protecuon Expenments." unpub-
hshed report for the Department of Energy by Computattonal Mechamcs Consultants. Ashurst. South-
ampton. U K. 1986
[22] Strommen. R et al. "Advances m Offshore Cathodic Protection Modelhng Using the Boundary
Element Method." Matertals Performance. NACE. Feb 1987. pp 23-28
[23] Str#mmen, R and Rodland, A, "Computensed Techmques Apphed m Design of Offshore Cathodic
Protection Systems," Matertals Performane, NACE, April 1981, pp 15-20
[24] Gartland, P O and Johnsen, R, "COMCAPS Computer Modelhng of Catho&c Protection Systems,"
Corrosion/85, Boston, Mass, March 1985
[25 ] Aokl,S, Klshtmoto,K, and Sakata, M, "Boundary Element Analysisof Galvamc Corrosion," Bound-
ary Elements VII, Villa Olmo, Lake Como, Italy, Computational Mechamcs Pubhcatlons, 1985
[26] Munn, R S, "A Mathematical Model for a Galvamc Anode Cathodic Protection System," Matertals
Performance, NACE, Aug 1982, pp 29-32
[27] Telles, J C F, Wrobel, L C, Mansur, W J, and Azevedo, J P S, "Boundary Elements for Cathodic
Protectton Problems," Boundary Elements VII, Villa Olmo, Lake Como, Italy, Computattonal Me-
chamcs Pubhcatlons, 1985
[28] Brebbla, C A and Dommguez, J, Boundary Elements An Introductory Course, 1988
[29] Fu, W J and Chen, S K, "Finite Element Determination of Galvamc Corrosion Dunng Chemical
Cleaning of Steam Generator," Matertal Performance, March 1986, pp 33-40
[30] Fu, J W and Chow, S K, "Catho&c Protection Designs Using an Integral Equation Numerical
Method," Corrosion/82, Paper No 163, 1982
[31] Jacob, W R, "Pnnctples of Catho&c Protection," paper presented at Design of Offshore Cathodic
Protection Systems, Computauonal Mechanics Centre, Southampton, 11 Sept 1984
DISCUSSION
J Fahey I (wrttten dtscusswn)--Do any of your results Influence the mechanical destgn of
these structures9
R A Adey and S M Ntku (authors" closure)--If the model predicts significant corrosion
problems, then the design of the structure may be changed to increase the level of cathodic
protection or the design geometry mo&fied to remove problem areas The choice of materials
can also be mfluenced by the results
For large floating or deep water structures, the design of the cathodic protection system can
add slgmficantly to the weight of the structure and hence its mechanical behavior Numerical
models of the type described in the paper can be used to mvestlgate various design options and to
provide the reformation necessary to make informed decisions
R S Munn 2 (wrttten dlscusswn)--How can a BEM computer program account for the vary-
ing electrolyte conductivity (e g varymg mudhne, etc )9
R A Adey and S M Ntku (authors' closure)--There are two ways m which the variation m
conductivity can be represented
For the case where a structure is partially submerged in mud (e g , plpehne on the sea bed) the
model can be simply split into two zones Each zone can have a different conductivity (e g, for
the seawater and the mud) .The interface between the seawater and mud will be described with
elements
For the case where the conducttvlty varies w~th depth, for example, there are numerical
techmques to represent this m the computer model However, although we know how to do this
It has not been currently implemented m the BEASY CP software because there has not been
sufficient demand from users
S Smith 3 ( written dlscusston)--Although BEM analysis has not been used to effect anything
Teledyne Wah Chang, Albany OR 97321

2 U S Naval Underwater Systems Center, New London, CT
3 Exxon Products Research, Houston, TX 77001
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreemen
more than the placement of anodes to date, future platforms may see mechanical changes The
future of the conventional piled steel platform is hmlted and as oll is produced in deeper waters,
new platforms are being designed and the use of BEM systems to design CP for these platforms
will increase
R A Adey and S M NIku (authors'closure)--This IS a key point and one which the authors
very much agree with One of the greatest benefits of computer simulation systems is that they
enable the engineer to predict in the computer the performance of any new ideas and designs
which exist only on paper Conventional designs have a considerable body of data and experi-
ence to support and justify their use The computer model provides a powerful tool to the
engineer to investigate new concepts, conduct "what if" studies, and determine the critical
factors (i e , sensitivity studies)
The computer model enables the engineer to gain a greater understanding of the physical
processes which impact a design and it can also provide an excellent educational tool
V. Genshetmer De Giorgt, i E. Dail Thomas 11, 1 and Alexts I. Kaznoff I
Numerical Simulation of Impressed Current

Cathodic Protection (ICPP) Systems Using
Boundary Element Methods
REFERENCE: De Glorgi, V G, Thomas II, E D, and Kaznoff, A I, "Numerical Simulation
of Impressed Current Cathodic Protection (ICPP) Systems Using Boundary Element Meth-
otis," Computer Modehng m Corrosion, ASTM STP 1154, R S Munn, Ed, American Society for
Testing and Materials, Philadelphia, 1992, pp 265-276
ABSTRACT: The numerical simulation of a prototypic ship and impressed current cathodic
protection (ICCP) system to determine the required current for adequate cathodic protection is
documented in this paper The prototypic ship is modeled using a commercial boundary element
code The propellor assembly and rudder are included in the boundary element model as separate
detached geometric features Nonlinear polarization data are used to define the material response
Electrolyte static (low flow) conditions are examined The current required for cathodic protection
for a bare steel hull is compared with an estimated value based on matenal polarization data
KEY WORDS: cathodic protection, boundary element, simulation, impressedcurrent, corrosion

analysis
The ablhty of impressed current cathodic protection (ICCP) systems to reduce the effects of
corrosion on structures is well estabhshed The mathematical and electrochemical pnnciples for
analytical determination of system characteristics have existed for several decades [ 1 ] However,
many systems are still designed and implemented based largely on designer "expertise" The
ever increasing avadabihty and decreasing cost of computer resources has generated a new
interest in the development of computational methods which can be used for ICCP system
design and evaluation Of Interest to the designer are numerical simulation techniques which can
be readily applied to geometrically complex structures
The three major numerical approaches used for cathodic protection analyses are the finite
difference, finite element, and boundary element methods [2] Each of these methods has
advantages and disadvantages The finite difference method is limited to relatwely simple ge-
ometries The numerical simulation techniques amenable for use on geometrically complex
structures are the finite element and boundary element methods
The finite element method is a versatile analysis procedure which can be applied to almost any
structure Cathodic protection analyses of various components have been performed using finite
element methods [ 3-5 ] In a finite element analysis, as in any cathodic protection analysis, the
region which must be dlscrettzed ts the electrolyte surrounding the structure Complex structures
often reqmre large numbers of three-dimensional elements to accurately model the structural
details and the surrounding electrolyte Three-dimensional finite element simulations reqmre
significant computer and financial resources While many finite element packages have been
used for the design of cathodic protections systems [ 3 ], the cost can easily become prohibitive
t Naval Research Laboratory, Washington, DC 20375
265
The boundary element method is based on the solution of boundary integral equations [ 6 ]
Therefore only the boundary of the structure has to be included m the numencal simulations In
boundary element catho&c protectmn analyses the boundary of the electrolyte must be dlscre-
Uzed, not the entare volume as m fimte element samulatmns The boundary of the electrolyte
consists of a structure-electrolyte anterface and an outer boundary In the case of a structure
surrounded by a nearly mfinate medmm such as seawater, the outer boundary as an artlficml
boundary placed a sagmficant &stance away from the structure The volume of electrolyte to be
modeled can be very large wathout sagmficantly affecting the number of elements and nodes
reqmred for the &scretlzataon A boundary element model of a structure surrounded by an
electrolyte wall, m general, be much simpler than the corresponding fimte element model The
boundary element method allows for the evaluation of larger and more complex geometries for a
gaven level of financaal and computatmnal resources Thas is a tremendous advantage m the
design process where numerous anode configuraUons along with a complex geometry may re-
qmre evaluauon before a final ICCP desagn as determined
Extremely complex geometries as well as mfimte electrolyte volumes can be readily modeled
using boundary elements The level of catho&c protecUon developed on a gaven geometry by a
particular cathodic protectaon system can be determined from a computatmnal analysas
Changes an eather geometry or cathodic protectmn system design can be readily evaluated Use
of numerical samulatmns m the desagn process allow for the rataonal determmaUon of the better
catho&c protecUon system design
Recent work by Adey and Naku [ 7] has examined the capabdaty of the boundary element
method to accurately assess galvamc corrosion system behavior Adey and Nlku used the com-
mercaal boundary element code BEASY-CP In other recent work Zamam [8] used boundary
elements to samulate the catho&c protecUon system of a prototypac shap Zamana modeled the
propeller as a catho&c area on the hull The rudder was not included m the model The re-
mainder of the hull was insulated to model a painted condmon Zamam used a boundary
element code developed at the Techmcal Umversaty of Nova Scotm Pre&cted protection levels
for a prescribed anode configurataon and prescnbed anode current levels were wathm 15% of
values measured from a full scale ship
The purpose of thas work as to determine the capability of the boundary element method to
accurately assess ICCP system operatmn for a multaple part model The commercml boundary
element code BEASY-CP as used to evaluate an ICCP system desagned for a prototypac shap The
ship model consists of three components the hull, the propellor, and the rudder The propellor
and rudder of the shap are modeled as separategeometnc features The surface of all components
as bare steel Use of bare steel as the matenal for all three components wall result m extreme
con&taon Much higher levels of current wall be required to maintain protectmn for the bare steel
structure than for a painted hull The pnmary purpose of the test, including the propellor and
rudder as geometric separate features, is to demonstrate the numencal stmulatmn capabflmes
wath regards to multaple part models Use of bare steel for the propellor and rudder wall result an
hagh current reqmrements Again, the use of bare steel wall result m an extreme condltmn The
results obtmned wall not be an&catave of a full scale ship system but wall allow for comparison
with current reqmrements based on sample analytacal calculauons It is felt that if the computer
modehng techmques perform accurately for extreme condmons, normal operating condmons
can be accurately modeled using the same techmques
Nonlinear catho&c polanzaUon data are used to characterize the matenal behavaor In the
computatmnal samulataon all envaronmental factors and chemacal lamatataons of the corrosmn
process must be incorporated into the polarization data The polanzauon data are representatave
of bare steel m a low flow seawater envaronment Since the present work as exammang the
numerical stabahty and samulataon capabflaty for extreme condmons, not all hmmng factors of
the catho&c polanzatmn data have been incorporated into the material polanzatmn response
In thebypresent
Copyright ASTM analysas,
Int'l (all the number
rights and placement
reserved); Tue Feb 10of09:33:27
anodes are
ESTfixed
2015Daelectnc shaeldmg of
DE GIORGI ET AL ON IMPRESSED CURRENT CATHODIC PROTECTION 267
Fc
r A
FIG l - - D o m a i n for use m solunon of LaPlace equatton
fixed dimensions is included for each anode in the computer model An accurate computational
simulation of a fixed number of anodes with fixed locations Is the first stage of a procedure which
would allow for the movement and addmon of anodes
Theoretical Basis for ICCP Evaluation
The conservation of charge w~thln an electrolyte 1s the basis of the mathematical formulation
used in cathodic protection analysis The governing equlhbnum equation reduces to the Laplace
equation for certain ldeahzed condmons The Laplace equauon is written in terms of the electn-
cal potential
v2r = 0 (1)
Reqmred for Eq 1 are steady-state condmons, a umform homogeneous electrolyte, and no

charge sources or sinks in the domain
Numerical solutions for Eq 1 have been developed for finite element and boundary element
methods primarily for the solution of heat transfer problems Program developers Interested in
cathodic protection problems have adapted the heat transfer solutions by appropriate changes in
boundary condmons and variable defimtlons A detailed denvatlon of the Laplace equation and
boundary conditions for cathodic protection analysis can be found in Ref 6 A brief descnpuon
of the boundary condmons required for the solution ofEq l in two dimensions is presented here
The domain, t2, for the solution of the Laplace equation is shown in Fig 1 The domain is
bounded by the surface, I', such that
F=FA+Fc+F~ (2)
where FA is the anode surface, Fc is the cathode surface, and F~ is the insulated surface
For an ICCP system the flux along the anode surface, FA, has a constant value qA
~e~(x,y )
); Tue =
C o p y r i g h t b y A S T M I n t ' l ( a l l r i g h t s r e s e r v e d~n(x,y) F e qA
b 10 09:33:27 EST 2015 (3)
where O(x,y) is the electnc potential, ( x , y ) is the point being evaluated, and n ( x , y ) is the
outward normal to the boundary at the point ( x , y )
As an alternative to defining the flux at an anode, the potential at an anode can be defined as a
constant
4a(x,y) = 4~A (4)

The ICCP system is evaluated at steady-state conditions The anode is not treated as a charge
source but as a fixed boundary condition In this analysis approach the current level of an anode
is fixed and no variation is allowed The current level at an anode will vary with time and
operating conditions dunng the life of an ICCP system Therefore separate solutions must be
performed for various times during the life of the system when this approach is taken
The flux at a point on the cathodic surface, I'c, is
~,(x,y) _ fc[ , ( x , y ) ] (5)

6n(x,y)
whereJ~ is the cathodic polarization function An accurate representation of the cathodic polar-
ization function is required for an accurate solution While numerical solutions are possible
using linear representations for the cathodic polarization function, this approach has been recog-
nized as an over-simphcation [ 1 ] The current-polarization relationship is often nonlinear The
cathodic polanzation function included all effects of surface condition and treatment, tempera-
ture, and other environmental factors
At insulated surfaces, Pi, such as dielectnc shields or well painted surfaces, the flux is zero
~r _ 0 (6)
tSn t,,,y )
Equations 1 to 6 are combined to solve for the electncal potential and current, or flux, density
at all points along the boundary Additional boundary conditions based on conditions at infinity
and along the surface of the structure may be required for a particular problem
Commercial boundary element codes have been developed to solve the Laplace equation in
the domain defined by the boundary elements These codes are specifically designed for cathodic
protection system analysis Of the codes available, BEASY-CP was chosen for the current analy-
sis [10] Other boundary element codes should perform in a similar manner
The commercial code used allows for nonlinear polarization boundary conditions The code
uses an iterating solution procedure when nonlinear polarization boundary conditions are used
to describe material behavior A valid solution must satisfy three independent criteria
9 The potential satisfies the Laplace equation throughout the electrolyte domain
9 The flux balance is satisfied (the current entering the electrolyte is equal to the current
leaving the electrolyte)
9 The potential and current density results fall on the given polarization curve for each
nonlinear matenal type for each element
As part of the iterating solution procedure, the differences in solution vanables between two
solutions is determined for the entire model A valid solution occurs when solution vanables at
all points for two lterative solutions are within defined limits The solution tolerance, or allowed
range in variables at a point, is defined in terms of percentage of the current value of solution
DE GIORGI ET AL. ON IMPRESSED CURRENT CATHODIC PROTECTION 269
FIG. 2--Boundary element model of prototypic ship.
variables. The smaller the tolerance criterion, the more accurate the converged solution. Sug-
gested tolerances are 0.1 to 0.5% for the commercial code used [ 10]. Smaller tolerances may be
required to satisfy all three solution criteria simultaneously for particular problems.
In the case of a structure in seawater the electrolyte domain can be considered to be infinity
large. In the numerical simulation the domain must be limited to a finite volume to ensure that
no current is lost between the structure and the anodes. The finite domain of the computational
simulation can be of any size or shape. Domain boundaries must be placed sufficiently far away
from the structure so that any effects on the potential field of the structure are negligible. There is
no flow of current in or out of the seawater domain at an infinite distance away from the ship. In
addition, there is no change in potential at an infinite distance from the ship. These conditions
must be modeled in the defined boundary conditions of the computational model finite domain.
Boundary Element Analysis

Boundary Element Model
The prototypic ship modeled is a U.S. Navy CG-47. Symmetry conditions allow for half of the
ship to be modeled and, of course, only the portion of the ship below the water line is required.
The boundary element model used is shown in Fig. 2. The propellor and rudder are modeled as
distinct features separated from the full. The propellor and rudder models are shown in detail in
Fig. 3.
The boundary element model was created using the interactive graphics program PATRAN
[ 11 ]. The boundary element model consists of 312 constant value elements and 389 nodes. The
elements used are constant value quadrilaterals. These are four-noded elements which represent
a straight sided surface and have no variation in the variables across the element. The curved hull
of the ship is approximated by a faceted surface.
FIG. 3--Details of boundary element model of prototypic ship.
The impressed current anodes and dielectric shielding are explicitly included in the boundary
element model. They have finite areas and fixed locations. Each current source is represented by
an element with a prescribed boundary condition. The anodes and their relative positions are
shown in Fig. 2. Elements which make up the dielectric shields were assigned zero current
density and given no capability to maintain a current density in order to mathematically model
this behavior.
The hull, rudder, and propellor of the surface ship are assumed to be made of bare steel. This
results in an extreme condition. Computational results will not be indicative of current levels
required for adequate corrosion protection on actual ships but will allow for evaluation of
computational modeling accuracy. Nonlinear polarization response approximated by piecewise
linear representation is used in the analysis as shown in Fig. 4. The material polarization behav-
ior is shown with respect to a Silver-Silver Chloride reference electrode for static (low flow)
conditions. The polarization data are for initial conditions. The effects of the formation of
calcareous coatings and film coatings are not included in the material response. There are no age
or seasonal effects incorporated into the analysis. A complete service history analysis of the
current required to maintain adequate cathodic protection would require additional material
response data that incorporate time-dependent effects in addition to the initial wetting response.
The infinite seawater domain is approximated by a box of constant-value quadrilateral ele-
ments used to enclose the ship model. The edges of the box are a large distance away, 20 times
the ship's length, so that the boundary conditions do not affect the potential fields developed
along the hull or other components. Box elements are defined with a current density of zero to
approximate the correct boundary conditions at infinity.
-0 65
\
-0 70
-0 75
oZ
-0 80
\
-0 85
-0 90
-i
0 1 08 2 15 3 23 x 10 A/n 2
-2
0 1 0 2 0 3 0 X i0 A/ft 2
Current Denslty
FIG 4--Polartzatton response curve for steel m low flow condtttons
Program and Model Ltmltanons
Three program and model hmltatlons were encountered dunng the current analyms The first
two limitations deal with the numerical solution techmque incorporated into the code The third
limitation is problem size onented and is common to both boundary element and finite element
codes In general, the larger the structure modeled, the lower the order of elements which may be
used based on computational resources available
The nonlinear polarization response option m the program was exercised m the present analy-
sis The nonhnear polanzauon data are prepared as series of data pairs These data pairs are then
used to construct a pmce-wme linear representation of the nonhnear polanzanon curve There
are numerical limitations on the range of slope changes and the absolute relative slope allowed
These limitations must be stnctly adhered to when prepanng data for entry When the slope of
the polarization curve used is such that slope and changes m slope values are near these limits,
great care must be taken in the construction of the pmce-wise linear representation of the polar-
izauon curve Constructed polanzaUon curves which do not meet these limits result m divergent
solutions Therefore, when the polanzatlon curve representation slope parameters are near the
defined hmlts [ 10], sample analyses must be performed to verify the polarization curve represen-
tation Generally, nonlinear polarization response can be readdy and successfully modeled if
sufficient care is taken
Impressed current anodes may be included in the boundary element model by defining either
the current density or potential at an element If current density is defined, the potential will be
determined as part of the solution In a simdar manner, if the potential is defined, the current
density wdl be determined for those elements A mixture of current density and potentml bound-
ary conditions is permitted in the boundary element solution procedure However, xt was found
that the choice of boundary conditions used for this particular problem affected the solution
convergence capablhty for the prototyplc ship and ICCP system modeled When the current
density was specified for the impressed current anodes, the computational simulation would not
converge for current levels required for cathodic protection When potential was used to define
the impressed current anodes, convergence solutions at the current levels required were possible
The ICCP system modeled uses small powerful anodes to achieve cathodic protection The
current density required to achieve cathodic protection is much greater than the current density
of the bulk of the hull When there is a large difference in the magmtude of coefficients within a
set of equations, numerical instabilities can occur These are due to the inherent error of manipu-
lating relatively very large and very small numbers m the same process [ 12] This is why conver-
gent solutions can not be obtained when current densities are used to define the anode current
level for the prototyplc ship This numerical procedure hmltation will vary in severity depending
on the combination of material characterization, input parameter magnitude, and geometry
Each numencal simulation must be designed with a specific question in mind The pnmary
goal of the current analysis is the determination of the total current requirement necessary to
achieve cathodic protection for the entire surface ship The choice of elements was based on
modehng the overall response of the ship structure Detads of features which are small relative to
the hull were not included in the model Nodal and element hmlts are defined by the program
and may be vaned in accordance with the available computer memory Limitations ofavadable
memory, as defined by either machine hmlts or prehmlnary job control language allocation of
memory hmits, will determine the allowable problem size Model size and element choice will
therefore be dependent on the computer resources available The constant value elements cho-
sen with the present mesh configuration do not provide sufficient refinement to accommodate
the potential gradient between the anode and ship's surface m the immediate VlClnlty of the
anodes and dielectric shielding There is some over-estimation of potential in the region immedi-
ately adjacent to the anodes and dielectric shielding The over-estimation is due to use of con-
stant value elements in this region of large variations in potential and current values [ 13]
Boundary Element Analysts Results

The boundary element analys~s uses input current values and material polanzatlon character-
lzatlons to determine the potential of all portions of the surface ship The target potential is 0 80
V with respect to a Sliver-Sliver Chloride electrode This level of voltage is considered adequate
corrosion protection [ 14] A solution is obtained when the potential on all portions of the
surface ship, including the rudder and propellor assembly, have reached a minimum of 0 80 V
The current levels of the anodes are the driving function of the ICCP system Each of the
current source anodes is assigned a potential in the numerical simulation Potentials were de-
fined for the anode elements instead of current density boundary conditions because of solution
convergence characteristics Material characteristics for bare steel, dielectric shielding, and sea-
water at mfimty are defined as described in the previous sections A solution tolerance, as
previously defined, of 0 01% was used for the numerical simulations This tolerance level was
determined from prehmlnary solutions to be necessary for the simultaneous satisfaction of the
three Independent solution criterion used m the numerical procedure
An iterating approach is used to determine the current required for cathodic protection
Potential levels are assigned to each of the three input current anodes The resulting level of
current density at each anode is determined as part of the solution procedure The resulting
degree of cathodic protection is determined by examination of potential contour plots If insuffi-
cient protection results, the potential levels of one or more anodes are Increased and the solution
procedure is repeated A final solution is obtained when the required level of protection is
reached for all portions of the model
Unacceptable solutions (1 e , those solutions which do not meet all three of the validity
requirements) can occur Useful information can be obtained from these divergent soluttons A
review of the potential and current density contours may indicate specific anodes which require
changes in input variables
A valid solution, one which meets the three independent solution criterion discussed previ-
ously, which results in a potential level of 0 80 V (Sliver-Sliver Chloride reference electrode) is
the solution of interest The numerical simulation can supply the designer with current input
requirements for the impressed current anodes In impressed current systems the anodes are
designed so that current enters the electrolyte, in this case seawater, at a prescribed level The
impressed current required to maintain a potential of 0 80 V (Silver-Sliver Chloride reference
electrode) on the prototyplc ship is
I1 = 1 1 6 8 A
I2 = 196 1 A
I3 = 33 6 A
with a resulting total current required for cathodic protection of an entire ship of 693 0 A
Current requirements are determined from the current density as calculated by the boundary
element solution and the modeled anode surface area Anode locations are as defined in Fig 2
Potential levels for the given current input values are shown in Fig 5 Voltage levels of the
anodes are based on seawater resistivity and are 25 7 V for I1, 42 4 V for 12, and 11 8 V for I3
Once again, it should be noted that these values are based on a bare steel surface and will not be
indicative of values used for protection of ships' with painted surfaces
The current required for cathodic protection of bare steel in low flow conditions can be
estimated from the polarization data presented in Fig 4 The value of current density required
for adequate protection as determined by Fig 4 (2 15 • l0 -4 A / m 2) is consistent with values
from other sources [ 14,15] The current required is for initial wetting conditions and does not
take into account any changes in polarization response due to the buildup of calcareous coatings
or film coatings The required current will reduce over time due to these factors The estimated
current reqmrement based on ship surface area, bare steel conditions, and the polarization data
shown in Fig 4 is 756 8 A The boundary element predicted current requirements is within 8 4%
of the estimated value The numerical simulation is only valid for initial wetting conditions
Time effects have not been incorporated into the numerical simulation It should also be noted
that the boundary element calculated value is for the extreme condition of hull, propellor, and
rudder of bare steel and should not be compared with current levels required for protection of
actual ships The effects of painted surfaces will result in a considerable reduction in current
requirements
Significant over-protection is observed in the numencal simulation for regions surrounding
the anodes A portion of this over-protection is an over-estimation resulting from the boundary
element type used Use of a higher order element or additional element refinement in this region
would determine the actual amount of over-protecuon and possible need for increased sizing of
dielectric shields to meet over-protection limits
Summary
The purpose of this work was to determine the capability of the boundary element method to
accurately assess ICCP system operation for a multiple part model A commercial boundary
FIG. 5--Potential contour values for prototypic ship.
element code was used to evaluate an ICCP system designed for a prototypic ship. The propellor
and rudder of the ship were modeled as separate geometric features, The ship's surface was
assumed to be of bare steel to model extreme conditions. A nonlinear cathodic polarization
relationship is used to characterize the material behavior, Steady state (low flow) conditions
were examined. The results obtained are consistent with simple analytical predictions. There
is a 8,4% difference in boundary element predicted and estimated current requirements. Addi-
tional analysis using higher order elements is indicated to accurately assess the amount of over-
protection around the anodes.
The boundary element method was found to be relatively easy to use once an initial learning
phase was completed. Geometric modeling of the structure is aided by the ability to use solid
modeling software. Knowledge of numerical solution techniques and convergence criteria is
required for assessing convergence problems. Convergence problems appear to be structure and
model specific, Based on the analysis results and the analysts' experiences, the boundary element
method and commercial boundary element codes are a viable method for ICCP system design
and evaluation for complex structures,
Numerical simulation and evaluation of ICCP systems during the design stage can result in
enhanced and more efficient systems. The location and number of anodes in an ICCP system can
be changed by simply changing the boundary conditions associated with a group of elements.
Boundary element simulations can be used to determine optimum ICCP system design.
More important to the designer is the ability to incorporate geometric design changes in an
existing model. Materials can also be changed with little effort. Use of the boundary element
method allows the designer to incorporate minor or radical geometric changes in the numencal
simulation model m a timely m a n n e r The effects of changes m material speoficaUons could be
readdy evaluated With the ever increasing pressures to reduce budgets but not compromise
structural rehablhty or performance, the ability to evaluate the impact of design changes qmckly
wdl become increasingly important Computer-assisted designs of ICCP systems using numerical
simulation wdl become essentml m the design of m a n n e structures Use of boundary element
methods wdl allow for relatwely qmck and accurate analyses of ICCP systems
Acknowledgments
The authors wish to acknowledge the assistance of Dr Peter Matlc of the Naval Research
Laboratory and Dr Shan Nageswaren of Computational Mechamcs for their assistance m the
development of the boundary element model used m this analysis
References
[1 ] Peterson, M H, "Physical and Mathematical Modehng of Current D~stnbution and Cathodic Protec-
tions," The 8th Inter-Naval Corrosion Conference Proceedings, Plymouth, England, 1988
[2] Zamam, N G , Porter, J F, and Mufti, A A, "A Survey of Computational Efforts m the Field of
Corrosion Engmeenng," Journal of lnternatwnal Numertcal Methods m Engmeermg, Vol 23, 1986, pp
1295-1311
[3] Kasper, R G and Crowe, C R, "Comparisons of Localized lonlc Currents as Measured from 1-D and
3-D Vibrating Probes with Finite Element Predictions for an Iron-Copper Galvanic Couple," m Gal-
vamc Corroston, ASTM STP 978, Philadelphia, 1988, pp 118-135
[4] Scully, J R and Hack, H P, "Prediction of Tube-Tubesheet Galvanic Corrosion Using Finite Ele-
ment and Wagner Number Analysis," in Galvamc Corrosion, ASTM STP 978, Philadelphia, 1988, pp
136-157
[5] Kasper, R G and April, M G , "Electrogalvanlc Finite Element Analysis of Parhally Protected
Manne Structures," Corroston, Vol 39, No 5, 1983, pp 181-188
[6] Brebbia, C A and Dommquez, J, Boundary Elements - An Introductory Course, McGraw-Hill, New
York, 1989
[7] Adey, R A and Nlku, S M, "Computer Modeling of Galvanic Corrosion," In Galvamc Corroston,
ASTM STP 978. Phdadelphla, 1988, pp 96-117
[8] Zamam, N G , "Boundary Element Simulatton of the Cathodic Protectton System m a Prototyplc
Sh~p," Apphed Mathemattcs and Computatton, Vol 26, 1988, pp 119-134
[9] Computational Mechanics, BEASY-CP User's Manual, Computational Mechanics Internauonal, Bd-
lerica, Mass, 1987
[10] Computational Mechamcs, Introduction to the BEASY-CP System, Computational Mechamcs Interna-
tional, Bdlenca, Mass, 1987
[11] PDA Engmeenng, PATRAN User's Manual, PDA Engmeenng, Santa Ana, Cahf, 1987
[12] Maron, M J, Numerwal Analysts- A Practtcal Approach, Macmillan, New York, 1982
[13] Fu, J W, "Galvamc Corrosion Predlcuon and Experiments Assisted by Numerical Analysis," m
Galvamc Corroston, ASTM STP 978, Philadelphia, 1988, pp 78-85
[14] Peabody, A W, "Pnnoples of Corrosion," BASIC Corrosion Course, NACE, Houston, Tex, 1970,
pp 5-1--5-37
[15] Laque, F L, Marine Corroston Causes and Preventton, Wiley, New York, 1975
DISCUSSION
R A d e y I (written d t s c u s s t o n ) - - I n your presentauon you stated that you have a problem m

representing the anode by an element upon which the reqmred current has been speofied
Computational Mechamcs, Bdlenca, MA 01821

because of numerical stability problems Have you considered the alternative possibilities avail-
able in BEASY of using pint or line sources of currents located at the position of the anode9 This
should illuminate the problem you describe and enable you to specify the current output on the
impressed anodes
In order to ensure that the point or line source behaves in the same way as a real anode a small
model of the anode dielectric shield and some of the surrounding metal surfaces could be created
and the element configuration and location of the source/sources adjusted to achieve the desired
results This configuration could be then used in the full ship model
V G De Giorgz et al (authors' closure)--There are two methods which one can use to define
the characteristics of an element so that the element is representative of an impressed current
anode One method is to define the current density The program then calculates the potential of
the element as part of the solution process The other method is to define the voltage level of the
element and the program will calculate the current density as part of the solution Since the
program used allows for mixed boundary condition problems, both methods result in valid
solutions Initial analysis attempts were made by defining current density boundary conditions
for the impressed current anode elements When this resulted in divergent solutions, the results
obtained were examined in detail to determine, if possible, the cause of non-convergence As a
result, the alternative method of defining the voltage as a prescribed boundary condition was
used on a trial basis and convergent solutions were obtained
The use of point and hne sources were considered However, once convergent solutions were
obtained by changing the boundary condition applied, it was decided that no additional model~
ing was necessary The ablhty to use mixed boundary conditions is an important aspect of the
solution capablhty of the program The analyst has multiple options when convergence is not
obtained, and an understanding of numerical procedures is required to determine if additional
modehng is necessary or if changes in the existing problem definition, either in convergence
hmlts or boundary condition definitions, are required
Slmone Louise Delarue Carvalho, l Jos~ Claudlo de Farla Telles, 1
and Lulz Roberto Martins de Miranda 1
On the Effect of Some Critical Parameters

in Cathodic Protection Systems:
A Numerical/Experimental Study
REFERENCE: Carvalho, S L D, Telles, J C F, and de Miranda, L R M, "On the Effect of
Some Critical Parameters in Cathodic Protection Systems: A Numerical/Experimental
Study," Computer Modehng m Corroswn, ASTM STP 1154, R S Munn, Ed, American Sooety for
Testing and Materials, Phdadelphm, 1992, pp 277-291
ABSTRACT: The potential dlstnbutmn over the surface of underwater structures depends on a
series of enwronmental parameters m addmon to the matenal properties of the surfaces Among
others, the water velooty, reslstwlty, temperature, sahmty, and &ssolved oxygen affect the etii-
oency of cathodic protectmn systems The present work d~scusses the influence of some of these
parameters St,rnng, res~stwlty of the medmm, and geometrical &stnbutmn of anodes are particu-
larly considered
Three electrolytes of distract conductwmes were stu&ed, and for each system analyzed two
stlrnng speeds were used The systems of cathodic protectmn were analyzed for three different
geometrical configurat,ons between ,mpressed current anodes and cathodes To assess the influ-
ence of the aforementioned parameters, the computer program PROCAT has been used to s,mu-
late the expenments This program ,s a general apphcatlon boundary element computer system It
is capable of analyzing three-&menslonal, two-dlmensmnal, and axlsymmetnc corrosion cells,
including nonhnear and possibly time-dependent polanzatlon curves In the present computer
s~mulatlon, the nonhnear polanzatmn curves were obtained experimentally under &fferent env,-
ronmental con&tlons The experiments were ~mplemented m a rectangular reservoir that was
represented as a two-&mensmnal problem
KEY WORDS: cathod,c protection, boundary element method, numerical techmques, numerical
simulation
Cathodic protection is the usual technique employed to avoid corrosion problems in buried or
submerged steel structures The increasing number of structures such as gas or oil pipehnes and
offshore platforms plainly justify design optimization of this technique based on an accurate
assessment of its performance
Traditional design procedures have been mostly based on simple empirical relations that
allow for the calculation of a key current density value Such current density is then applied to
guarantee protection of the complete structure Traditional methods, however, have proved to
be too conservative and expensive and not surprisingly are being substituted for by more sophis-
ticated numerical techniques Such modern procedures consider the actual problem geometry
and steel surface conditions in the current distribution evaluation
In this work a comparison between expenmental and numencal results for a simple under-
water structure is presented The test problem includes the effect of water stlmng, resistivity, and
geometrical anode configuration In each case, the potential distribution obtained through exper-
COPPE - Federal Umverslty of Rio de Janelro, Rio de Janelro, R J , Brazil
277
111 ~13 I151 1161 I I I 1171 Is

~oI ~! I ] I
,: T I I I
iI ioi
I I
"o,,
I I I I
!o!',,,
I [ r 15
i J I I J J2l fat t t I14 t t I t
FIG l--Dtscrettzanon employedfor FDM (lateral wew)
lmental measurements is compared with its corresponding numerical values predicted by a

boundary element simulation
The boundary element results were calculated employing the computer system PROCAT
developed at COPPE/Federal University of Rio de Janeiro for Petrobras, the Brazihan state oil
company
Numerical Techniques
In general there are three main numerical techniques which can be applied to simulated
cathodic protection systems
9 Finite Difference Method (FDM)

9 Finite Element Method (FEM)
9 Boundary Element Method (BEM)
The three methods can be used to solve, in an approximate way, the governing equation of the
problem [ 1-3], 1 e,
V2E = 0
where
E = electrochemical potential, and
02 O2
To use these methods, the first step is to generate a representative model of the system This
modeling is made by subdividing the domain and/or its surface in elements that have different
shapes and sizes (dlscretlzatlon), according to the geometry and the method selected These
elements are linked by geometnc nodes that determine the connectwlty of the mesh
The potential and in some methods the current density are determined at certain points that
are known as funcnonal nodes These nodes can be located at the centrold of each element
(constant element) or may coincide with the geometncal nodes (e g, lsoparametnc hnear,
quadratic or cubic elements)
/ / / J / / / / / /,/ / J
// /////// //
////////////
/////////////
FIG 2-- Dlscrettzanon employedfor FEM
CARVALHO ET AL ON CATHODIC PROTECTION SYSTEMS 279
I I I I I I I I I I I
IzI ~ Oo o~176
0 0 0 0
I I i I I I i I I I I
FIG 3--Discrettzatton employed for BEM
The kind of structure to be analyzed will help to determine the geometry of the element The
potenUal distribution follows the Laplace equation and the respecuve boundary condmons
These boundary conditions may be
9 Prescribed potentml
9 Prescribed current density
9 A hnear relation between potential and current density
9
cathode anodes
9
anodes cathode anodes
anodes
9
cathode anodes
%
anodes
FIG 4--Corroswn cells analyzed

10 I 9 I 8 I 7 I 6 I 5 I 4
11
12
=
13
I I I I I I
FIG 5--Numertcal dlscrettzatton for the PROCAT program
9 A nonlinear relation between potential and current density (polarization curve)
Once the boundary conditions at each surface point are apphed, a system of equations that
will give potential and possibly current density values at each node is generated The three
numerical methods are now more closely examined
Ftmte Difference Method ( F D M )
In the finite difference method the domain is usually divided in elements of equal size Conse-
quently, this method is restricted to the analysis of regular geometries
For a two-dimensional system, the potential of a given point is obtained by means of the
following expression
0" OUII[ICENT
~ - IIODrim
-0.1~ 13" ImOr~*
- 0 701
~ -0~
v -I00
IU
- I I0
- 120
ol.30 , 9 9 9 illi, | , , | ,Jl.J . . . . liiil i 9 . . . . . . . . . . . . . . . .
Kf I i0-) i0 o iOI iO l I ( mA / cm2)

FIG 6--Seawater (p = 20 $2. cm) polarlgallon curvesfor sleel
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No furth
0 " OVIESCENT
- 06 0 ~
.o,o
.o,o
- I 20 "~'~
-I 50 ........................... .................
,
x~"3 Io"2 )6 ' ~o x~' Io ~ I ( .~/~ )

FIG 7--Polartzatton curvesfor steel (o = 200 9. cm)
E,+l,j + E,-Lj + E,,j+l + E,,j-1

E,,j = 4
The potential m each point will be determined by the average potenttal of the four surround-
ing points
Thts method has been used in several corrosion problems such as optimization of anode
distnbutlon of offshore platforms [ 4,5 ] and current dlstnbution analysis ofbuned pipelines with
impressed current systems [ 6]
If the FDM is used, not only should the structure interface be discreuzed but also the complete
electrolyte This ends up by increasing the input preparation and computational time, which
may raise the total cost of the design
Finite Element Method (FEM)
The finite element method enables us to dlscretize the region in elements of variable shapes
and sizes according to the geometry of the structure/electrolyte interface or the need to obtain
more accurate current density and potential values
This method, like the previous one, presents restnctlons in the study of infinite regions The
structure surface under analysis can only be inserted within a limited region, therefore the
boundary condmons of the problem should approximately simulate the mfimte domain By
using this method, the potential value in each element is obtained through the potential values in
the funct]onal nodes The expression used is [ 7]
E=ZN, E,
1=1
0 - QUZZ'SCE~rT
-43443.
~ - lOO r m
13- ImO rpe,
-.o5c ~ ~ " " ' x :
.oro; 2
0 '. t., r
9.o eo,- 0 ,4 e
>
9.o.,,o: e
L~
-, .oo L r
-I.201 t i,..B . . . . . . . . . . . . . .
I0"~ ........ IO"Z ~ ~ ~ ~ I0 I0~ tOJ
I (mA/cm ~ )
FIG. 8--Polarization curvesfor steel (p = 4500 s cm).
where
n = number of nodes of each element,

E~ = nodal potential value, and
N~ = interpolation function.
These interpolation functions, which are usually polynomial, can be linear, quadratic, cubic,
etc.
In order to simulate FEM to cathodic protection problems, the Galerkin method can be used.
For two-dimensional problems, the starting expression is
f f . ( a~E O~E\
where Ae = area of each element.
By applying integration by parts, a system of equations is obtained that can be written in a
matrix form as
K~E,-p ~
where:
ff ON,,ONJ]dA (i,j= 1 ton)

~K['J = J J A= ~ Ox Ox + Oy Oy ]
e= e nx+~ny N~dS (i= 1 ton)
The element matrices K" are assembled in an overall matrix K which yields the global system
TABLE 1--Potenttal values (volts)for the burredsystem (hnear analysis)

Node Expenment FDM FEM BEM
1 -54 -43 -44 -41
2 -45 -36 -36 -38
3 -29 -25 -25 -25
4 -15 -15 -14 -13
5 -10 -10 -10 -07
6 -09 -09 -10 -10
7 -10 -09 -10 -08
8 -24 -21 -20 -16
9 -41 -34 -33 -30
l0 -56 -44 -44 -49
11 -57 -44 -45 -47
12 -56 -43 -44 -49
13 -58 -45 -45 -46
14 -46 -38 -37 -39
15 -29 -25 -25 -27
16 -18 -17 -17 -17
17 -09 -08 -10 -08
18 -35 -27 -27 -28
19 -29 -25 -25 -25
20 -17 -17 -17 -14
21 -55 -43 -44 -47
22 -45 -37 -36 -40
23 -30 -25 -25 -29
24 -19 -18 -17 -19
25 -11 -10 -10 -09
of equations Like finite differences, the use of FEM requires the dlscretlzatlon of complete
electrolyte
Several corrosion problems have been solved by this technique, such as submerged plpehnes
[8] and offshore platforms [9]
Boundary Element Method (BEM)

In general, when the boundary element method is used, Green's third identity of the problem
is apphed If the potential distribution over the surface fits this ldenUty, the Laplace equation will
automaUcally be satisfied The third Green ~dentlty is
C(v)E,v) = fs (E~v~) OE(,>

On(s)
_ OF.* \
On(,)E(,)) dS
where C(e) depends on the surface geometry at the boundary point p, and E~p~) is the free space
fundamental solution to the Laplace equation
The solution to the problem is obtained by applying this equation to all boundary nodes
Since there are only surface integrals revolved, the method requires element dlscretlzatlon over
the boundary without domain approximations This unique feature of the techmque makes it
very attractive, especially the reduced input data preparation and the possxbdlty of accurately
simulating infinite or seml-mfimte electrolytes without difficulty [ 10]
The results at any internal point (domain point) can be computed afterwards, as a function of
the boundary solution, with a post-processor umt that employs the same equation wntten for
points within the electrolyte
POTENTIAL (mVsce)
- 800
- 900
- 1000
4-4-4-4-4-4-4-4-4-4-4-4-
~8~~eeeoooooooooooo
-1100
I I I I I I I I I I I I I I I I I I I I I I I I !
-12 0 0
234 5 6 7 8 9 10111213141516171819202122232425
ELEMENT
4- EXPERIMENTAL n NUMERICAL
FIG 9--p = 2 0 f~ 9 c m , o n e anode, quiescent condition
Despite its recent development, the BEM efficiency has been demonstrated m several engi-
neenng fields In the case of corrosion problems, its use has been mainly in potential and current
density dlstnbutlon analysis of offshore platforms [11-13]
Problems Analyzed
This work can be divided In three parts
(a) Verification of reliability of the three methods in cathodic protection systems

(b) Experimental analysis of the influence of stlmng, resistivity, and anode geometncal
configuration
(c) Use of the boundary element method by means of the program to determine the potential
distribution of the problems analyzed and further comparison with experimental results
As a first test, a buned system is explored It consists of a box (length = 39 cm, width = 12 cm)
and two steel bars (q~ = 3 cm), one is the cathode and the other is the anode
This system was considered two-dimensional for the numencal analysis By using the FDM,
the electrolyte was discretized in 208 square elements and 243 nodes (Fig 1) Twenty-five
nodal values were selected for comparing results with the other methods
In the FEM analysis, the system was divided in 100 linear triangular elements and 70 nodes
(F~g 2)
For the BEM analysis, only the boundary is dlscretlzed, this decreases the number of elements
to be generated Several internal points were considered for comparative purposes with the FDM
and FEM results This system can be seen in Fig 3
The fabricated boundary conditions are
POTENTIAL ( m V s c e )
- 800
- 1000
4- 04-4-4-
0 0 0 0 0
0
- 1200
I I I I I I I I I I I I I I I l I I I l I I I I I
- 1400
2,54 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
ELEMENT
4- EXPERIMENTAL n NUMERICAL
FIG lO--p = 200 ft. cm, one anode, quiescent condttton
9 Box Boundary zero current density

9 Anode current density = 16 A / m 2
9 Cathode prescribed potential = - 0 9 V ~
In the second case studied, a reservoir (22 by 29 by 12 cm) was used A steel bar cathode
(length = l0 cm, ~ -- 3 cm) was located m the center of the reservoir and graphite anodes were
employed in three different dispositions These systems are presented in Fig 4
The numencal analysis was camed out by the PROCAT program (BEM) and nonlinear
polarization curves were considered as boundary conditions over the cathode Owing to the
symmetry of the systems, only half of the reservoir was dlscretlzed and 24 elements and 25 nodes
were generated
In Fig 5, one can see the system with only one pair of anodes For the numerical analysis, the
anode was considered a hne of uniform distributed current sources
For the experimental results, the potennal values were obtained through a saturated calomel
electrode In order to venfy the influence of stlrnng, three different conditions were included
quiescent condition, low snmng ( 100 rpm), and high stlmng (250 rpm)
The cathodic polarization curves, which were considered as boundary conditions, were ob-
tained first for the three stlmng speeds chosen
The total current applied was 10 mA for all analyses In order to study the influence of
electrolyte resistivity, three different media were included
9 20 ft. cm (seawater)
9 200 ft. cm (seawater + dlstdled water)
9 4500 ft. cm (fresh water)
286 COMPUTER M O D E L I N G IN C O R R O S I O N
POTENTIAL ( V s c e )
-1
4-4-4-
-2
[] [] 0
[]
[]
[] [] [] 0
-3
-4
i I I l l I i i I I I I I I I I I I I I I I ! l
-5 '
1 2 3 4 5 6 7 8 9 1011 12131415161718192021 22232425
ELEMENT
4- EXPE]RIME]qTAL o NUMERICAL
FIG 1 l--p = 4500 9 9 cm, three anodes, low stlrrmg
POTENTIAL ( m V s c e )
- 800
-900
0 0 [] O O [] O 0 0 0 O 0 0 0 0 0 0 0 O 0 O 0 [] [] O
- 1000 @ @ @ @ @ @ @ @ @ @ @ @
@ @ @ @ @ @ @ @ @ @ @ @ @
-1100
I i t i t I I I I I I I I I I I I l I I i l I l
- 1200
2 3 4 5 6 7 8 9 1011 1213141516171819202122232425
ELEMENT
4- QUIESCENT [] LOWER STIRRING 'A HIGHER STIRRING
FIG 1 2 - - 0 = 20 9 . cm. one anode
POTENTIAL (mVsce)
- 800
-900
0 0 0 0 0
~ 0 0 0 0 0
0
[] A
- 1 0 0 0 [] []
4-4-4-4-4-4-4-4-
4-4-4-4-4-4-4- 4-4-4-4-
-1100 4-
4-
4- 4-
4-
I I [ I i i i i i i i I I i i i i i i i i i i i
- 1200
2 3 4 5 6 7 8 9 1011 1 2 1 3 1 4 1 5 1 6 1718192021 22232425
ELEMENT
4- QUIESCENT [] LOWER STIRRING z~ HIGHER STIRRING
FIG 13--p = 200 9 . cm, one anode
POTENTIAL (Vsce) (Thousands)
-1
====k
o~
0 ~ 2+~+ + ~
-2
-3
4-
I I I I I I ! I I I I I I I I I I I I I I i I I I
-4
2 3 4 5 6 7 8 9 1011 1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 2 0 2 1 2 2 2 3 2 4 2 5
ELEMENT
4- QUIESGE]qT "" LOWER STIRRING [] HIGHER STIRRING
FIG 1 4 - - p = 4500 9t" cm, one anode
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursu
POTENTIAL (Vsce)
-1
0 0 6 0
66
-2 6
6
6
6
-5
6
6
-4
I I I I I I I I I I I I I I I I I I I I I I I I
-5
2 3 4 5 6 7 8 9 1011 1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 2 0 2 1 22232425
ELEMENT
4- r=20 ohrn,cm x r=200 ohrn,crn b r=4500 ohm,cm
FIG 15--One anode, quiescent condttton
POTENTIAL (Vsce)
-1
66066
-2 6 6
6
0
0
6 6
-3 6
0
0
i i i i i i I I I I I I I I I i I I I I I I I I
-4
2 5 4 5 6 7 8 9 1011 1 2 1 5 1 4 1 5 1 6 1 7 1 8 1 9 2 0 2 1 22252425
ELEMENT
4- r=20 ohm.crn x r=200 ohrn.cm 6 r=4500 ohrn,cm
FIG 16--Two anodes, qutescent condttton
POTENTIAL (Vsce)
--1
bO
--2 0 b
bb b bbb b b
--3
I I I I I I I I I I I I I I t I I I ! I 1 i I
-4 '!
1 2 3 4 ,5 6 7 8 9 1011 1215141516 171819202122232425
ELEMENT
4- r = 2 0 ohm.cm x r = 2 0 0 ohrn.crn 0 r = 4 5 0 0 ohm,crn
FIG 17--Three anodes, quwscent condttton
Results
Numerwal Methods Compartson
The experimental cathodic polarization curves are presented in Figs 6 to 8 The experimental
and numerical results at the points selected are shown m Table 1 for the buried system
Numertcal and Expertmental Results

Experimental and numerical results for some of the systems studied are presented m Figs 9 to
11 In these cases varying stlrnng and reslstwlty are considered
Influence of Stlrrmg, Reststtvtty, and Geometrical Configuratton of Anodes

Experimental results are presented m Figs 12 to 14, including the systems with only one pair
of anodes, for each reslstwlty values studied
In Figs 15 to 17, one can see experimental results obtained for each anode configuration m a
qmescent condmon
Expenmental results are shown m Fig 18 for the higher resistivity medmm (p = 4500 ft. cm)
Discussion
As can be seen m Table 1, the potential values calculated numerically and the experimental
results are m good agreement Despite the reduced number of elements reqmred by the BEM,
the results are as accurate as those obtained by the other methods The d~fference, at some
points, between numerical (all methods) and experimental results can probably be explained by
POTENTIAL (Vsce)
-1
4-4-4-4-
4- 4-
-2 0 0
O 0 ~
0
4- n
-3 []
Q
[]
[] 4-
4-
-4
-4-
I I I I I I I I I I I I I I I I I I I I I | I I
-5
234 5 6 7 8 9 1011 1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 2 0 2 1 2 2 2 3 2 4 2 5
ELEMENT
4- 1 anode n 2 anodes 6 3 anodes
FIG 18--0 = 4500 f t . cm, quiescent c o n d m o n
the lnhomogenelty of the electrolyte Therefore this method can be considered quite appropnate
to cathodic protection problems
The program was used to obtain the potential distnbution of the submerged system shown in
Fig 4 The experimental and numerical results proved that this computer program can simulate
cathodic protection problems with good precision (Figs 9 to 11 )
For stlrnng conditions, the difference between numencal and expenmental results was more
noticeable This can probably be explained by the shape variation of the polarization curves
which occurs in the stimng media Even though ideal laboratory curves were prescribed as
boundary conditions, the shape of the curves could still be quite affected by a thin rust film
formed dunng the experimental procedures
The numencal analysis of cathodic protection systems must consider the polarization curve
that actually represents the problem These curves are affected by the steel surface conditions,
stirring, and the time of metal exposition to an aggressive medium
The current density needed to protect the structure is influenced heavily by the medium
resistivity The increasing of resistivity promotes a decreasing of this current density (Figs 15
to 17)
For media with higher conductivity, the potential obtained increases In this case, it is neces-
sary to increase the current density to reach protection potential values (about - 8 5 0 mVsce)
In fresh water medium, which means high resistivity, a marked potential drop exists between
the elements that are near the anode and those far from it
The number of anodes as well as their dlstnbution are fundamental parameters in cathodic
protection design A good distribution of anodes is necessary, mainly in higher resistivity media,
to maintain the potential distnbutlon and consequently protect the structure adequately In Fig
18, one can see that the number of anodes affects the potential distribution significantly With
three pairs of anode systems, the potential values are more uniform In offshore platforms a good
dlstnbution of anodes is necessary to protect cntical areas
Conclusions
9 The fundamental parameters for cathodic protecuon systems can be found by numerical
analysis In this case, the BEM is the more adequate method
9 Stlmng is a very important parameter, since it affects directly the polarization of the
structure
9 The potential drop between points at different distances from anodes in high resistivity
media must be considered
9 The geometrical &stnbutlon of anodes must be optimized in order to guarantee a uniform
protection of the structure
References
[1] Fu, J W and Chow, J S K, "Catho&c Protection Designs Using an Integral Equation Numerical
Method." Matertals Performance. 1982, pp 9-12
[2] Danson, D J and Warne, M A , "Current Density/Voltage Calculat.ons Using Boundary Element
Techniques," m Corroston "83. Paper 211. 1983
[3] Adey, R A and Nlku, S M. "Computer Modelhng of Galvamc Corrosion," m Galvamc Corroston.
ASTM STP 978. American Society for Testing and Materials, Philadelphia, 1988
[4] Str~mmen, R and Rodland, A , "Corrosion Surveillance of Submanne P1pehnes by Electnc Field
Strength Momtorlng," Matertals Performance. Oct 1981, pp 47-53
[5] Str#mmen, R and Rodland, A , "Computerized Techniques Apphed in Design of Offshore Cathodic
Protection Systems," Matertals Performance. Vol 20, No 4, 1981, pp 15-20
[6] Munn. R S and Clark, J H, "Use of Numerical Techniques and Microcomputers to Predict Corro-
sion Rates on Underground Metalhc Structures," m Corroston "83. Paper 301, 1983
[7] Gallagher, R H. Carey, G , Oden, J T , and Zlenk.ewlcz, 0 C, FmzteElements an Fluids. Vol 6,
Wiley, London, 1985
[8] Kasper, R G and April, M G , "Electrogalvamc F.mte Element Analysas of Partially Protected
Manne Structures," m Corroston '83. Vol 39, No 5, 1983. pp 181-188
[9] DeCarlo. E A , "Computer Aided Cathohc Protection Desagn Techmque for Complex Offshore Struc-
tures," m Corrosaon "82. Paper 165, 1982
[10] Telles, J C F, Mansur. W J , and Wrobel, L C, "On Boundary Elements for External Potential
Problems," Mechanacs Research Commumcattons. Vol 6, 1984. p 373
[11] Brebbla. C A , Telles, J C F, and Wrobel, L C. Boundary Element Techmques - Theory and
Apphcatlons m Engineering. Spnnger-Verlag, Berhn, 1984
[12] Telles, J C F, Wrobel, L C. Mansur, W J , and Azevedo, J P S, "Boundary Elements for Cathodic
Protection Problems," m Boundary Elements VII. C A Brebbla and G Maler. Eds, Spnnger-Verlag,
Berlin, 1985
[13] Telles, J C F. Mannho. M G , Mansur, W J , Wrobel. L C, and Sant.ago, J A F, "Computer
Atded Design of Cathodic Protection Problems Using the PROCAT," an Brazd Offshore "87. Rio de
Janearo, 1987
Author Index
A-B N-P
Adey, R A, 248 Newman, R C , 17

Anderson, David B, 162 Nlenart, Cynthia A , 82
Attla, M Helml, 28 Nlku, S M, 248
Bertoccl, U , 143 Palus, Andrew F, 82
Pye, Earl L, 5
C R
Carvalho, Slmone Louise Delarue, 277
Rlcker, R E, 143
CottlS, R A, 17, 67 Roberge, P R , 197
de Miranda, Lmz Roberto Martins, 277 Sagues, A A, 95

De Glorgl, V Genshelmer, 265 Shlh, H , 174, 186
Devereux, Owen F, 126 Shojl, Tetsuo, 44
Sleradzkl, K , 17
Song, Q, 17
G-K Strommen, Roe D , 229
Golestaneh, Kamran, 5 T
Kaznoff, Alexis I , 265
Keenan, J S, 113 Telles, Jos6 Claudlo de Farla, 277
Kranc, S C, 95 Thomas, II, E Dall, 265
Trethewey, K R , 113
TSal, C H , 186
L-M Turgoose, S., 67
Lawson, K , 67 Y
Mansfeld, F, 174, 186
Monya, Shln-lChl,44 Yeum, Kook Sun, 126
Munn, Raymond S, 1,215 Yoshlda, Ken-lchl, 44
293
Copyright9 1992 by ASTM International
www.aslm.org
EPFL - Ecole Polytechnique Federale de Lausanne (EPFL - Ecole Polytechnique Federale de Lausanne) pursuant to License Agreement. No further re
Subject Index
A macrocell current dlstnbutlon, 95
polarization curves, 113
Alloy corrosion, 17 Corrosion analysis
Alternating current impedance, 5 impressed current cathodic protection
Atmospheric corrosion, data evaluation, 162 system, 265
spatial corrosion modeling, 215
B Corrosion monitoring, electrochemical
impedance spectroscopy, 197
BASICS, electrochemical impedance Corrosion rates, analysis, 174
spectroscopy simulation and analysis, Crack tip strain rate, 44
186 Crevice corrosion
Boundary element method, 248 data evaluation, 162
cathodic protection systems. 229, 277 thermal modeling, 28
impressed current, 265
D
C
Data analysis, polarization curves, 174
CAE/CAD software, 5 Data classification, 162
Carbon dioxide containing solutions, Diffusion, multi-reaction polarization curves,
electrode processes and surface 126
chemistry, 67
Carbon steel, electrochemical impedance
spectroscopy analysis, 197
Cathodic current density, carbon dioxide
containing solutions, 67 Electrochemical Impedance spectroscopy, 186
Cathodic current-potential-rotation speed analysis by systematic permutation of data
relationships, 67 points, 197
Cathodic protection systems, 229 Electrochemistry, 5
boundary element method, 248, 277 Electrode kinetics, 5, 143
effect of critical parameters, 277 Electrode processes, carbon dioxide
impressed current, numerical simulation, containing solutions, 67
265 Electron transfer, 126
Charge transfer control, 186 Equivalent circuits, computer generation, 5
Clnnamaldehyde, Inhibitor mechanisms, 82 Erosion corrosion, electrochemical
Concrete, reinforcing steel in, localized impedance spectroscopy analysis, 197
corrosion, 95 Evaluation, corrosion data, 162
Copper-nickel alloys, electrochemical
impedance spectroscopy analysis, 186, F
197
Corrosion, 17 Filming inhibitor mechanism interpretation,
alternating-current impedance 82
spectroscopy, 5 Finite difference method
carbon dioxide containing solutions, 67 offshore cathodic protection systems, 229
crevice, thermal modeling, 28 spatial corrosion modeling, 215
data evaluation, 162 Finite element method
impedance, 95 offshore cathodic protection systems, 229
295
spatial corrosion modeling, 215 Polarization conditions, reinforcing bar, 95

stress corrosion cracking, 44 Polarization curves, 113, 126, 143
Fretting corrosion, thermal modeling, 28 quantitative analysis, 174
Polarization resistance, analysis, 174
G POLFIT, polarization curve analysis, 174
PROCAT, 277
Galvanic corrosion
using boundary element method, 248 Q--R
spatial corrosion modeling, 215
Quantitative analysis, polanzatlon curves, 174
H--I Reactor pressure vessel steels, stress corrosion
cracking, 44
Hydrochloric acid. corrosion Inhibition, 82 Rebar, localized corrosion, 95
Impedance, 143 Redox behavior. 113
corrosion, 95 Reinforcing steel, in concrete, localized
Impedance spectroscopy, 5 corrosion, 95
Impressed current cathodic protection Resistance-capacitance model, validation,
systems, numencal simulation, 265 197
Iron-chromium alloys, corrosion, 17 Resistivity, concrete, 95
Rotating-disk studies, 67
L
Light water reactors, stress corrosion S

~-_ cracking, 44
Localized corrosion, electrochemical Seawater, offshore cathodic protection
impedance spectroscopy, 197 systems, see Cathodic protection
systems
M Slip dissolution mechanism, 44
Slow strain rate test. 44
Macrocell. current distribution, 95 Software
Mass transport control, 186 BASICS. 186
Mathematical prediction, corrosion analysis, CAE/CAD, 5
215 polarization curve analysis, 174
Monte Carlo method, alloy corrosion, 17 POLFIT, 174
Multiple crack initiation, 44 PROCAT, 277
Multi-reaction polarization curves, 126 Spatial corrosion modeling, computation
corrosion analysis, 215
N--O Steel, in hydrochloric acid, corrosion
Inhibition, 82
Nonlinear polanzat~on, corrosion analysis, Stress corrosion cracking, 44
215 Surface chemistry, carbon dioxide containing
Numerical techniques, cathodic protection solutions, 67
systems. 277 Systematic permutation of data points,
Ohmic loss, multi-reaction polanzatlon electrochemical impedance
curves, 126 spectroscopy analysis, 197
Oxygen diffusion, concrete resistivity, 95
TmU
P
Tafel slopes, analysis, 174
Passlvation, 17 Thermal contact resistance, 28
multi-reaction polarization curves, 126 Thermal modeling, crevice corrosion, 28
Pitting, data evaluation, 162 Uncompensated resistance, analysis, 174

Cathodic Protection

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Cathodic Protection

Uploaded by

Copyright:

Available Formats

STP 1154

Computer Modeling in Corrosion

Raymond S. Munn, editor

ASTM PubllcaUon Code Number (PCN)

1916 Race Street

Computer modehng m corrosion / Raymond S Munn, ed

Peer Review Policy

SURFACE PHENOMENA AND LOCALIZED CORROSION

Equivalent Electronic Circuits Computer Generated from Alternating-Current

Atomistic Computer Simulation of Alloy Corrosion--R C NEWMAN, Q. SONG,

Thermal Modeling of Crevice Corrosion and Its Interaction with Fretting in

Computer Simulation of Stress Corrosion Cracking Behavior of Reactor Pressure

Modeling of Electrode Processes and Surface Chemistry in Carbon Dioxide

The Use of Computer Modeling in the Interpretation of Filming Inhibitor

CORROSION DATA FITTING AND MODELING OF ELECTRODE KINETICS AND IMPEDANCE

Computation of Corrosion Macrocell Current Distribution and Electrochemical

Microcomputer-Based Corrosion Modeling Applied to Polarization C u r v e s - -

Modeling Electron Transfer, Diffusional Effects, Passivation, and Ohmic Loss in

Modeling Polarization Curves and Impedance Spectra for Simple Electrode

Evaluation of Corrosion Data: A RevieW--DAVID B ANDERSON 162

Software for Quantitative Analysis of Polarization Curves--H SHIH

Software for Simulation and Analysis of Electrochemical Impedance Spectroscopy

Analyzing Electrochemical Impedance Corrosion Measurements by the Systematic

SPATIAL CORROSION MODELING

A Review of the Development of Computational Corrosion Analysis for Spatial

Computer Modeling of Offshore Cathodic Protection Systems: Method and

Computer Modeling of Corrosion Using the Boundary Element Method--

Numerical Simulation of Impressed Current Cathodic Protection (ICPP) Systems

On the Effect of Some Critical Parameters in Cathodic Protection Systems: A

Author Index 293

Subject Index 295

Equivalent Electronic Circuits Computer

KEY WORDS: alternating-current impedance, alternating-current Impedance spectroscopy, im-

The use of alternating-current impedance spectroscopy (ACIS) to evaluate corrosion rates

Professor of Chemistry, Department of Chemistry, and Chemist, Technical Staff, respectwely,Cahforma

1000 1400 1800 2200 2600 3000

Z'= Zcos0 Z v-- ZslnO

wherej = ~ and 0 1S the phase angle

Equtvalent Czrcutts from Impedance Data

An eqmvalent clrcmt is viewed as two-dimensional The clrcmt elements of a real electrode

1000 1400 1800 2200 2600 3000

-OUT 0 01 +OUT +IN -IN

~t l u F == =mC1 luF =:=C2

VOIGT CIRCUIT ANALYSIS

3 The identical impedance response for a number of different equivalent clrcmts

f r~[ ge_-0 01 l z - 100 ~kHz

Atomistic Computer Simulation

FIG 4--Cr-O-Cr brtdges leading to passtvatlon

Dissolution Rate (atoms/cycle)

10000 ~ ,,.,'f 20%

U Bertoccl I (written dtscusston)--(1) I suggest putting some mlsonentatlon steps on the

National Institute for Standards and Technology, Galthersburg, MD 20899

2 Southwest Research Institute, San Antomo, TX

Thermal Modeling of Crevice Corrosion

In boding a h q m d at a gwen pressure, several regimes o f b o l h n g can be observed, d e p e n d i n g

Effect of Fretting on Thermal Contact Resistance (TCR)

l The change in surface roughness and generation of fretting wear debris

and the following dimensionless groups

the amphtude ratio (A) = a / L

lx10-q[ , , ~ , ,,L,I , ~ ...... I , , ,

obtained at t h e center of contact is presented m Fig i as a function of the frequency and

where Pe is Peclet number, Pe = a f . L / a

~ = b p m, m>0, 4><1 (6)