Libro Ruido Electroquimico

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STP 1277
Electrochemical Noise
Measurement for Corrosion
Applications
Jeffery R. Kearns, John R. Scully, Pierre R. Roberge,
David L. Reichert, and John L. Dawson, Eds.
ASTM Publication Code Number (PCN)
04-012770-27
ASTM
100 Barr Harbor Drive
West Conshohocken, PA 19428-2959
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L i b r a r y o f C o n g r e s s C a t a l o g i n g - i n - P u b l i c a t i o n D a t a
El ect r ochemi cal noi se measur ement f or cor r osi on appl i cat i ons/ Jef f er y
R. K e a r n s . . . [et al.], edso
p. cm. - - (STP 1277)
" ASTM Publ i cat i on Code Number (PCN) 04- 012770- 27. "
Pr oceedi ngs of t he First I nt ernat i onal Symposi um on
El ect r ochemi cal Noi se Measur ement f or Cor r osi on Appl i cat i ons, hel d in
Mont real , Quebec, 15- 16 1994; sponsor ed by ASTM Commi t t ee G-1
on Cor r osi on of Metal s.
I ncl udes bi bl i ogr aphi cal ref erences and i ndex.
ISBN 0- 8031- 2032- X
1. Cor r osi on and ant i - cor r osi ves- - Test i ng- - Congr esses.
2. El ect rol yt i c cor r osi on- - Test i ng- - Congr esses. 3. Pot ent i omet r y- -
- - Congr esses. 4. El ect roni c measur ement s- - Congr esses. I. Kearns,
Jef f ery R. II. ASTM Commi t t ee G-1 on Cor r osi on of Metal s.
II1. I nt ernat i onal Symposi um on El ect r ochemi cal Noi se Measur ement
f or Cor r osi on Appl i cat i ons (1st: 1994: Mont real , Quebec)
IV. Seri es: ASTM speci al t echni cal publ i cat i on: 1277.
TA462. E535 1996
620. 1' 1223- - dc 20 96- 23890
CIP
Copyright 9 1996 AMERICAN SOCIETY FOR TESTING AND MATERIALS, West Conshohocken,
PA. All rights reserved. This material may not be reproduced or copied, in whole or in part, in any
printed, mechanical, electronic, film, or other distribution and storage media, without the written
consent of the publisher.
P h o t o c o p y R i g h t s
A u t h o r i z a t i o n t o p h o t o c o p y i t e m s f o r i n t e r n a l , p e r s o n a l , o r e d u c a t i o n a l c l a s s r o o m u s e , o r
t h e i n t e r n a l , p e r s o n a l , o r e d u c a t i o n a l c l a s s r o o m u s e o f s p e c i f i c c l i e n t s , i s g r a n t e d b y t h e
A m e r i c a n S o c i e t y f o r T e s t i n g a n d M a t e r i a l s ( A S T M ) p r o v i d e d t h a t t h e a p p r o p r i a t e f e e i s p a i d
t o t h e C o p y r i g h t C l e a r a n c e C e n t e r , 2 2 2 R o s e w o o d D r i v e , D a n v e r s , M A 0 1 9 2 3 , Tel : 5 0 8 - 7 5 0 -
8 4 0 0 ; o n l i n e : h t t p : / / w w w . c o p y r i g h t . c o m / .
P e e r R e v i e w P o l i c y
Each paper published in 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 Committee on Publications.
The quality of the papers in this publication reflects not only the obvious efforts of the authors
and the technical editors, but also the work of these peer reviewers. The ASTM Committee on
Publications acknowledges with appreciation their dedication and their contribution of time and ef-
fort on behalf of ASTM.
Printed in Philadelphia, PA
September 1996
Foreword
This First International Symposium on Electrochemical Noise Measurement for Corrosion
Applications was held in Montreal, Quebec, Canada on 15-16 May 1994. ASTM Committee
G-1 on Corrosion of Metals sponsored the symposium. Jeffery R. Kearns, Alcoa Technical
Center, Alcoa Center, PAL, served as chairman of the symposium and was principal editor of
this publication. John R. Scully, University of Virginia, Charlottesville, VA; Pierre R. Rob-
erge, Royal Military College of Canada, Kingston, Ontario; David L. Reichert, DuPont Ex-
perimental Station, Wilmington, DE; and John L. Dawson, CAPCIS Ltd., Manchester, United
Kingdom, served as symposium vice-chairmen and co-editors.
Contents
Overview ix
KEYNOTE ADDRESS
Electrochemical Noise Measurement: The Definitive In-Situ Technique for
Corrosion Applications?--JOHN L. DAWSON
CORRELATIONS TO OTHER ELECTROCHEMICAL TECHNIQUES
A Comparison of Electrochemical Noise and Impedance Spectroscopy for the
Detection of Corrosion in Reinforced Concr et e- - uco BERTOCCI
Electrochemical Noise and Impedance Analysis of Iron in Chloride Medi a- -
FLORIAN MANSFELD AND HONG XIAO
Electrochemical Noise Measurement for Determining Corrosion Rat es- -
DAVID L. REICHERT
39
59
79
DATA ANALYSIS
The Effects of Solution Resistance on Electrochemical Noise Resistance
Measurements: A Theoretical Analysis--R. A. cOTrlS, S. TUR~OOSE, AND
J. MENDOZA-FLORES
Analysis of Electrochemical Noise for Type 410 Stainless Steel in Chloride
Solutions--ROBERT G. KELLY, MARIA E. INMAN, AND JOHN L. HUDSON
Comparison of Spectral Analysis with Fast Fourier Transform and Maximum
Entropy Method. Application to the Role of Molybdenum Implantation
on Localized Corrosion of Type 304 Stainless Steel--LUC BEAUNIER,
JOEL FRYDMAN, CLAUDE GABRIELL[, FRAN(~OIS HUET, AND MICHEL KEDDAM
93
101
114
A Comparison of Spectral and Chaotic Analysis of Electrochemical Noise---
ANDRAZ LEGAT AND EDVARD GOVEKAR 129
Qua nt i f yi ng t he St ochas t i c Be ha vi or of El e c t r oc he mi c a l Noi se Me a s u r e me n t
Du r i n g t he Cor r os i on of Al umi num- - PI ERRE R. ROBERGE
The I dent i f i cat i on of Pi t t i ng a n d Cr evi ce Cor r os i on Sp e c t r a i n El e c t r oc he mi c a l
Noi se Usi ng an Ar t i f i ci al Ne ur a l Net work--THOMAS E. BARTON,
DAVID L. TUCK, AND D. BRE3~F WELLS
142
157
INDUSTRIAL APPLICATIONS
A Revi ew of EPRI Pr oj e c t s Si nce 1984 t ha t Used El e c t r oc he mi c a l Noi se
Me a s u r e me n t I ns t r ume nt a t i on- - BARRY c. SYREqq" AND WILLIAM M. COX
A Pr ogr e s s Re p o r t on t he Use of El e c t r oc he mi c a l Noi se t o I nves t i gat e t he
Ef f ect s of Ze b r a Mus s el At t a c h me n t on t he Co r r o s i o n Res i s t ance of AI SI
Type 304 St ai nl ess St eel a n d Ca r b o n St eel i n La k e Wa t e r - -
A. M. BRENNENSTUHL, BLAIR SIM, AND RENATA CLAUDI
The Use of El e c t r oc he mi c a l Noi se Me a s u r e me n t s wi t h Nuc l e a r Wa s t e T a n k s - -
JOHN I. MICKALONIS, RICHARD J. JACKO, GRAHAM P. QUIRK AND
DAVID A. EDEN
On- Li ne Moni t or i ng Usi ng El e c t r oc he mi c a l Noi se Me a s u r e me n t i n CO-CO2-
a20 Sys t e mSmHENNI E J. DEBRUYN, KEVIN LAWSON, AND EDWARD E. HEAVER
Si mul t a ne ous Cor r os i on a nd Foul i ng Moni t or i ng Un d e r He a t Tr a ns f e r i n
Cool i ng Wa t e r Sys t EmSmMI CHAEL A. WINTERS, PATRICK S. N. STOKES, AND
HENRY F. NICHOLS
El e c t r oc he mi c a l Noi se Me a s ur e me nt s on Ca r b o n a n d St ai nl ess St eel s i n Hi gh
Subc r i t i c a l a nd Supe r c r i t i c a l Aque ous En v i r o n me n t s - -
DIGBY D. MACDONALD, CHUN LIU, AND MICHAEL P. MANAHAN, SR.
The Use of El e c t r oc he mi c a l Noi se t o I nves t i gat e t he Cor r os i on Res i s t ance of
UNS Al l oy N04400 Nuc l e a r He a t Ex c h a n g e r 1~ubes--A. M. BRENNENSTUHL,
G. PALUMBO, F. S. GONZALEZ, AND G. P. QUIRK
The Use of El e c t r oc he mi c a l Noi se Me a s u r e me n t i n t he Eva l ua t i on of Ma t e r i a l s
f or St e a m Ge n e r a t o r s - - P. E. DOHERTY, M. J. PSAILA-DOMI3ROWSKI,
S. L. HARPER, AND w. G. SCHNEIDER
173
186
201
214
230
247
266
288
PITTING
Ana l ys i s of El e c t r oc he mi c a l Noi se f r om Me t a s t a bl e Pi t t i ng i n Al u mi n u m, Age d
AI - 2% Cu, a n d AA 2024- T3- - SHELDON T. PRIDE, JOHN R. SCULLY, AND
JACK L. HUDSON 307
Ef f ect o f Met al l urgi cal Fac t or s o n t he El e c t r oc he mi c al Noi s e Me a s ur e d o n
AI SI Type 430 St ai nl es s St eel s i n Chl or i de - Cont ai ni ng Me d i a - -
DOMINIQUE GORSE, CLAIRE BOULLERET, AND BERNARD BAROLIX 332
The Ef f ect o f S o me Funda me nt a l As pe c t s o f t he Pi t t i ng Co r r o s i o n o f St ai nl es s
St eel o n El e c t r oc he mi c al Noi s e Me a s ur e me nt s - - P. CHRIS PISTORIUS 343
METHODS
Coupl i ng o f Ac ous t i c Emi s s i o n and El e c t r oc he mi c al Noi s e Me a s ur e me nt
Techni ques i n Sl urry Er o s i o n- Co r r o s i o n St udi es--ROLAND OLTRA,
BRIGrVrE CHAPEY, FRAN(~OIS HUET, AND LIONEL RENAUD 361
I nf l uence o f Hy dr o g e n Abs o r pt i o n o n t he El e c t r oc he mi c al Pot ent i al Noi s e of
an I r on El e c t r ode Unde r Co r r o s i o n wi t h Gas Evol uti on--e~ANCOIS HUET,
MICHEL J~ROME, PANAGIOTIS MANOLATOS, AND FRAN(~OIS WENGER 375
El e c t r oc he mi c al Noi s e Re s pons e o f St eel Unde r Hy dr o dy na mi c Co n d i t i o n s - -
JOSI~ M. MALO AND OCTAVIO VELAZCO 387
El e c t r oc he mi c al Noi s e Me a s ur e me nt s Dur i ng Exf ol i at i on o f Al u mi n u m
Al i oys ~JUAN DE DAMBORENEA AND BERNARDO FERNANDEZ 398
Cha r a c t e r i z a t i o n o f Pr e r us t e d St eel s i n S o me I be r o - Ame r i c a n At mo s phe r e s by
El e c t r oc he mi c al Pot ent i al Noi s e Me a s u r e me n t - -
ELISABETE ALMEIDA, LIBORIA MAR1ACA, ABELARDO RODRIGUEZ,
JORGE URUCHURTU CHAVAR[N, AND MARIA A. VELOZ 411
STANDARDIZATION
Reproduci bi l i t y o f El e c t r oc he mi c al Noi s e Dat a f r o m Co a t e d Me t al S y s t e ms m
GORDON P. BIERWAGEN, DOUGLAS J. MILLS, DENNIS E. TALLMAN, AND
BRIAN S. SKERRY 427
AS TM St a nda r di z a t i o n o f El e c t r oc he mi c al Noi s e Me a s u r e me n t m
JEFFERY R. KEARNS, DAVID A. EDEN, MAX R. YAFFE, JEFFERSON V. FAHEY,
DAVID L. REICHERT, AND DAVID C. SILVERMAN 446
I nde xe s 471
Overview
El ect r ochemi cal noi se measur ement (ENM) is a cont roversi al subject. There are no est ab-
l i shed t est met hods, and t here is no consensus on a t heoret i cal f r amewor k for i nt erpret i ng
data. It is unusual for ASTM Commi t t ee G-1 on Corrosi on, Det eri orat i on, and Degradat i on
of Mat er i al s to begi n st andards devel opment under such ci rcumst ances. Nevert hel ess, a t ask
group was f or med by member s that were both concer ned about t he r api dl y growi ng com-
merci al mar ket for t he t echnol ogy and i nt erest ed in pursui ng fundament al wor k on a " ne w"
el ect rochemi cal technique. The basi c quest i ons that ASTM Commi t t ee G-1 asks about any
el ect rochemi cal t echni que that is pr oposed for st andardi zat i on are " What does t he pr oposed
t echni que measur e?, " " Have i nst rument s and met hods been est abl i shed to make rel i abl e
measurement s?, " and " Does t he pr oposed t echni que pr ovi de useful i nformat i on that is not
possi bl e to obt ai n by exi st i ng st andardi zed t echni ques?" To answer t hese quest i ons, the
ASTM Commi t t ee G-1 Task Gr oup on ENM and the symposi um authors represent ed by this
STP were char ged wi t h t he t ask of devel opi ng consensus on t hree basi c issues:
(1) how shoul d a measur ement be made so that it can be compar ed wi t h confi dence to
others,
(2) what el ect roni c measur ement capabi l i t i es and cal i brat i on procedures are necessary to
make a val i d measurement , and
(3) how can the dat a be most effi ci ent l y anal yzed and r el i abl y i nt erpret ed.
It is hoped that progress wi t h t hese i ssues wi l l l ead to the creat i on of new corrosi on t est
st andards and the wi der accept ance of t he t echni que in research and industry.
Gi ven t he cont roversy surroundi ng the subject, it is appropri at e to pr ovi de wor ki ng defi-
nitions for t he t erms used in t he title of this STP.
Electrochemical noise--Fluctuations of pot ent i al or current, t ypi cal l y of low frequency
( <10 Hz) and l ow ampl i t ude. El ect r ochemi cal noi se ori gi nat es, in part, from nat ural varia-
tions in el ect r ochemi cal rate ki net i cs duri ng a corrosi on process. El ect r ochemi cal noi se is
oft en regarded as a r andom (st ochast i c) phenomena coupl ed to det ermi ni st i c ki net i cs.
Electrochemical noise measurement--A t echni que i nvol vi ng the acqui si t i on processi ng and
anal ysi s of el ect r ochemi cal noi se data. Dat a are t ypi cal l y acqui red by moni t ori ng the evo-
lution of a corrosi on process on t wo or mor e coupl ed el ect rodes wi t hout the appl i cat i on of
an ext ernal signal. Al t ernat i vel y, pot ent i ost at i c or gal vanost at i c met hods can be used to mea-
sure el ect rochemi cal current or pot ent i al noise, respect i vel y. Various el ect roni c filtering and
mat hemat i cal met hods can be used to anal yze el ect rochemi cal noi se signals. Wi t h appr opr i at e
corroborat i ng measurement s and observat i ons, ENM dat a can pr ovi de i nformat i on concern-
i ng t he nature of t he corrosi on process and the magni t ude of t he corrosi on rate for a gi ven
system.
Historical Perspective
Fl uct uat i ons of the pot ent i al or current from a cor r odi ng el ect r ode are a wel l - known and
easi l y observabl e phenomenon. Before t he 1970s, el ect r ochemi cal noi se was regarded as a
source of bi as and error that compr omi sed el ect rochemi cal measurement s rat her than as a
ix
X ELECTROCHEMICAL NOISE MEASUREMENT
rich source of i nformat i on. (The r eader is referred to the keynot e address for a revi ew of
much of the earl y work on what is now consi dered to be ENM. ) The use of el ect rochemi cal
pot ent i al noi se measur ement (EPNM) as a corrosi on research t ool has i ncreased st eadi l y
si nce I ver son' s paper in 1968. The measur ement of el ect rochemi cal current noi se (ECN)
bet ween coupl ed el ect rodes combi ned wi t h the measur ement of EPNM was est abl i shed as a
vi abl e i ndust ri al moni t ori ng met hod by workers at the Uni versi t y of Manchest er in the earl y
1980s. The use of the t echnol ogy has grown in l aborat ori es and i ndust ri al pl ant s wor l dwi de,
such that by the end of t he decade it was bei ng cal l ed the "Techni que of the Ni net i es. "
ASTM Commi t t ee G-1 began to consi der t he devel opment of st andards on ENM in 1991
and f or med a t ask group on the t opi c (J. R. Kearns, chair). The scope of t he t ask group is
to "devel op st andards that descri be i nst rument s and met hods for maki ng and anal yzi ng
el ect rochemi cal noi se measurement s. " One of the first act i vi t i es of t he t ask group was to
i ni t i at e the organi zat i on of an i nt ernat i onal conference on ENM to assess this t echnol ogy
and i dent i fy new areas for research and st andardi zat i on.
Summary of the STP
Thi s ASTM Speci al Techni cal Publ i cat i on (STP) resul t ed from the first i nt ernat i onal sym-
posi um on El ect r ochemi cal Noi se Measur ement for Corrosi on Appl i cat i ons hel d in Mont real ,
Quebec, Canada on 16 and 17 May 1994. Of the 36 present at i ons made at the symposi um,
28 papers were approved (3 peers revi ewed each paper) for this STP. The pri nci pal authors
were from ei ght countries, i ncl udi ng Canada (4), Fr ance (4), Mexi co (3), New Zeal and (1),
Sl oveni a (1), Sout h Af r i ca (2), Uni t ed Ki ngdom (3), and the Uni t ed States (10) and repre-
sented a vari et y of i ndust ri al and academi c perspect i ves on ENM. The papers have been
grouped into six sections on Correl at i ons to ot her El ect rochemi cal Techniques, Dat a Anal -
ysis, Indust ri al Appl i cat i ons, Pitting, Met hods, and St andardi zat i on. Thi s STP provi des a
snapshot port rai t of the state of the art for ENM in the earl y 1990s.
The fact that many of the papers in the STP, part i cul arl y in the Indust ri al Appl i cat i ons
section, have one or mor e coaut hors that are associ at ed wi t h the Uni versi t y of Manchest er
reflects the hi st ory of the commer ci al devel opment of the t echnol ogy at this institution. The
r eader shoul d al so note that an even great er number of papers in this STP are coaut hored
by i ndi vi dual s i ndependent of the Manchest er group. Thi s fact not onl y serves to val i dat e
aspect s of the early, i ndust ri al l y ori ent ed wor k done in Manchest er, but it also expl ai ns the
rapi d i ncrease in t he use of t echnol ogy around the worl d duri ng the past five years.
Overview of Papers
The keynot e address (Dawson) is i nt ended pr i mar i l y to pr ovi de backgr ound for the non-
speci al i st . Shoul d the r eader want mor e dept h, an ext ensi ve list of references is i ncl uded
coveri ng the scientific research l eadi ng to ENM, i nvest i gat i ons of vari ous forms of corrosi on
usi ng ENM, and the appl i cat i on of ENM to i ndust ri al cor r osi on- moni t or i ng situations. The
title of the keynot e address poses the quest i on as to whet her or not ENM is the definitive
el ect rochemi cal technique. The answer to the quest i on posed in the keynot e title is No! ENM
is not a panacea and is best used as one of several t echni ques in what is often referred to
as a mul t i t echni que approach. For this reason, the first sect i on of this STP on Correl at i ons
to Ot her El ect rochemi cal Techni ques is very useful in est abl i shi ng the val i di t y of ENM and
in demonst rat i ng how it can be effect i vel y combi ned wi t h mor e est abl i shed techniques.
OVERVIEW x i
Correlations to Other Electrochemical Techniques
Linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS)
are well-established corrosion measurement tools and are logical standards for qualifying
ENM as a method for measuring general corrosion. In the first paper in this section (Bertocci)
note that one must eliminate data from unwanted noise sources, and that trend removal may
also be warranted. Whet her using analog or digital (mathematical) filtering, caution must be
exercised to prevent the elimination of valid data.
The next two papers (Mansfeld and Xi ao and Reichert) found that the relatively new
parameter unique to ENM called the noise resistance, R, , correlated well with polarization
resistance, Rp, as measured by ENM and LPR techniques, respectively. The manner in which
R, should be calculated was debated between the t wo papers ( R , , = V , , I I , , where 17, and 1,
were taken as the root mean square [RMS] values of electrochemical potential noise and
electrochemical current noise, respectively, in the first paper and as standard deviation values
in the second paper). Selection of RMS or standard deviation values depends upon how the
data were collected and filtered.
The second paper of the session (Mansfeld and Xiao) confirmed that frequency plots of
ENM data are similar to EIS data and good agreement can be obtained between ENM and
EIS data at the zero frequency limit. The authors prefer the EIS technique because it provides
more information than ENM, especially for evaluating coated systems. It was observed in
the Reichert paper that for very active systems (1.3 r am/ y) the correlation of corrosion rate
calculated from ENM did not correlate with that from Rp or mass loss data. The interpretation
of the practical studies of uniform corrosion reported in this paper is regarded from a the-
oretical perspective in the first paper of the next session.
Data Analysis
The first paper of the section (Cottis et al.) addresses, in part, the need expressed in
Reichert' s paper for a theoretical basis relating ENM to corrosion rate. The authors concl ude
that the noise resistance parameter is a measure of essentially the same resistance as that
obtained by conventional LPR methods. ENM is superior to LPR in measuring resistance in
high-resistance systems.
The second paper (Kelly et al.) critically evaluates the correlation of two of the more
common noise parameters, noise resistance and the pitting index, to conventional electro-
chemical and physical measures of degradation. The results, for AI SI Type 410 stainless
steel exposed to several test conditions that induce different modes and rates of corrosion,
cast doubts on the credibility of these parameters for all systems. More work needs t o be
done to explain the apparent lack of correlation in the results of ENM and other methods
for the alloy and environments in question.
A common way to analyze noise data in many science and engineering disciplines has
been to transform time records to the frequency domai n t o obtain power spectra. Electro-
chemical noise signals often consist of a compl ex combination of deterministic and stochastic
processes, so a common approach to analysis has been to correlate domi nant frequencies
and deconvolute unwanted signals in an iterative manner using established mathematical
functions. For instance, power spectral density (PSD) plots are comput ed using algorithms
such as the fast Fourier transforms (FFT) or the maxi mum entropy method (MEM). A com-
parison of these two methods is made in the third paper (Beaunier et al.) in which it was
revealed that the validity of the low-frequency plateau obtained by the analysis of noise
results with MEM can yield questionable results. The authors apply the technique to elucidate
x i i ELECTROCHEMICAL NOISE MEASUREMENT
a practical corrosion problem, the influence of mol ybdenum additions (in the case by im-
plantation) to iron-chromium-nickel (Fe-Cr-Ni) alloys on pitting behavior.
The paradi gm of nonlinear dynami cs (also called chaos theory or factals) is impacting
everything from stock price forecasting to corrosion science. Analytical tools have been
developed to detect and characterize deterministic or chaotic features in seemingly random
data. The fourth and fifth papers of the session (Legat and Govekar and Roberge) review
the j argon and some of the mathematics as would seem to be relevant to the analysis of
ENM data. The techniques presented in both papers are illustrated by their use to reveal
important features of compl ex ENM data. Legat and Govekar provide a general introduction
to chaos and then demonstrate the utility of the techniques by identifying in experimental
ENM data records changes in the mode of corrosion for a carbon and a stainless steel exposed
to a changi ng test environment. Roberge describes and then applies two chaos techniques,
the stochastic process detector and rescaled range analysis. The critical pH of a 5000 series
aluminum alloy exposed to a series of salt solution of various degrees of acidity was iden-
tified by these techniques. Extensive lists of references for more in-depth knowl edge in this
important area are provided in both papers.
A quite different computer-based approach concludes the session (Barton et al.). Back-
ground to the t echnol ogy is presented along with a case history that demonstrates the power
of artificial neural networks to classify ENM data. In a case history, an artificial neural
network is trained with many ENM time series records for AI SI type 304 stainless steel in
dilute chloride solution t o identify the onset of localized corrosion.
Industrial Applications
The eight papers contained in this section survey the use of ENM in modern corrosion
monitoring and in industrial service-relevant testing of materials. The goal of industrial cor-
rosion monitoring is to provide a clearer picture of the conditions in an operating plant that
lead to corrosion damage to avoid unscheduled downtime. The operating conditions resulting
in corrosion are often transient and are frequently masked or by other events. Syrett and
Cox present a modern approach to corrosion monitoring as realized through a series of
programs sponsored by the Electric Power Research Institute (EPRI) over the past decade.
This significant body of work demonstrates that corrosion monitoring by multiple techniques,
including ENM, can be used as a sensitive indicator of the conditions within a system for
purposes of corrosion prevention and process control.
In the second paper (Brennensthul et al.) of the section, ENM was successfully used to
detect the effect that zebra mussel settlement has on the corrosion performance for stainless
steel in comparison to steel. The exposure and monitoring was done at a field test site near
the water inlet to Ontario Hydr o' s Nanticoke Thermal Generating Station. A number of
parameters were monitored simultaneously, including coupling current, electrochemical cur-
rent and potential noise, degree of localization, and noise resistance. ENM proved to be
sensitive to changes associated with mollusk settlement, and collaborating evidence revealed
that it was not detrimental to corrosion performance; in fact, the binding bi opol ymers were
actually proposed to inhibit corrosion.
Nuclear wastes at the Savannah River site are partially processed and stored in plain carbon
steel tanks. As described in the third paper of this session (Mickalonis et al.) based on the
encouraging results of a preliminary laboratory study, Westinghouse decided to use an ENM-
based monitoring system to assure that the corrosion inhibitors used to protect these tanks
remained effective. Under inhibited storage conditions, the noise data was fairly stable. ENM
was sensitive to the steel passive-active transition associated with greater solution nitrate
OVERVIEW x i i i
concentrations. The authors proposed that with appropriate calibration, the technique may
also be useful for the detection of stress corrosion cracking (SCC).
Switching from the power industry, the next t wo papers in this section (DeBruyn et al.
and Winters et al.) deal with the use of ENM for on-line monitoring in the oil and gas
industries. At a Mossgas (Pty.) Ltd. (Republic of South Africa) gas plant in a pipeline
downstream of reformer units, ENM was used to provide a continuous indication of the
capacity of the service environment to support SCC and other types of localized corrosion.
Conventional corrosion monitoring was ineffective for the condensing thin-film conditions
in a wet CO- CO 2 gas service environment. A preliminary laboratory study was conduct ed
to establish opt i mum probe and instrument configurations as well as measurement capabil-
ities. Stressed and unstressed sensor probes were inserted directly into the process line. The
ENM-based moni t or was used to identify times when process conditions are such that the
carbon steel pipeline may be susceptible to SCC. By instituting effective countermeasures
at such times, there is the opportunity to prevent SCC of the pipeline by process control.
The second paper about monitoring in the oil and gas industries (Winters et al.) describes
the development of a side-stream syst em that was designed t o overcome many of the short-
comi ngs of fouling monitors currently used in the treatment of cool i ng water. I n addition to
monitoring indicators of fouling, the system simultaneously monitors corrosion with ENM
and t wo other supporting electrochemical techniques. A sensor array is integrated into the
heat exchanger tubing bundle so that critical operating conditions can be monitored. In a
field trial, the system was successfully used to verify the operating limits and scale deposit
control capability of the water treatment packages.
The last three papers of the section (Macdonald et al., Brennenstuhl et al., and Doherty
et al.) offer examples of how ENM can be used to evaluate materials of construction under
test conditions relevant to the actual plant operating environment. The goal of the first ser-
vice-relevant testing paper (Macdonald et al.) is to provide a clearer picture of the devel-
opment of damage in a plant by measuring relevant parameters under actual operating con-
ditions. The simplicity of the coupl ed electrode for monitoring electrochemical current noise
provides for a sensor capable of monitoring changes in key parameters at elevated temper-
atures and pressures. The lack of such a sensor has impeded the introduction of monitoring
systems for the thermal transport circuits of power plants. In quite a different test apparatus,
ENM was explored as a means of detecting and monitoring stress corrosion cracking in
sensitized Type 304 stainless steel in high-temperature water (up to 288~ The magnitude
and pattern of the data were used to detect changes in the chemical and physical properties
of the fluid as well as the mode of corrosion.
The last t wo papers of the session (Brennensthul et al. and Dohert y et al.), describe the
use ENM in a multitechnique approach (ENM, open-circuit potential measurement, and zero
resistance ammetry). From the data collected by the multitechnique approach, several ENM
parameters were t racked versus time (for example, ECN standard deviation, mean coupling
current, noise resistance, degree of localization, and pitting function) and related to subtle
differences in the composition and microstructure of nickel base alloys as well as the sim-
ulated process environment. Workers at Ontario Hydro Technologies (Brennensthul et al.),
suspected that differences in corrosion performance, as observed in-service, were masked in
conventional testing by two factors: the aggressiveness of the test environment and the limited
sensitivity of the corrosion measurement method. In the last paper of the session (Doherty
et al.), workers from McDermott, Babcock, and Wilcox used ENM parameters to compare
differences in simulated cleaning solution (NaOH) corrosivity, crevicing conditions, and com-
position on steam generator tubing performance. The noise resistance, degree of
xi v ELECTROCHEMICAL NOISE MEASUREMENT
localization, and standard deviation of ENM were found to be the most reliable parameters
for making these three types of comparisons, respectively.
Pi t t i ng
The goal of the papers in this session is elucidate the mechani sm of pitting through the
sensitivity of the ENM technique. In the first paper of the session, Pride et al. measure EPN
and ECN by galvanostatic and potentiostatic techniques, respectively, to exami ned the tran-
sition from metastable to stable pitting. High-purity aluminum, A1-Cu binary alloy, and AA
2024-T3 were examined under conditions of increasing applied potentials or chloride-ion
concentration. ECN spikes were directly linked to individual metastable pitting events. Ratios
of pit currents to pit radii at various growth times were analyzed. The formation of a stable
pit was correlated to pit stabilization conditions producing ECN events that continuously
exceeded the threshold ratio of 10 -2 A/ cm. This approach is promising since this ratio is
fundamentally linked to the pit solution concentration required to maintain active pits.
In the second paper, Gorse et al. attempted to examine the effects of sulfur and titanium
on the metastable pitting behavi or of AI SI 430 stainless steel by investigating the shapes of
current transients. Individual ECN events associated with metastable pitting were described
by current spikes which obeyed power law relationships. Attempts were made to relate the
power law behavior of the current spike to the identity of the pit site, such as titanium
carbide and manganese sulfide inclusions.
In the last paper of this session, Pistorius considers the merits of using either ECN or
EPN to predict the transition from metastable to stable pitting in AI SI 304 stainless steel.
By coupling the stainless steel to a platinum cathode, it was shown that a large portion of
the pit charge was supplied by capacitive currents from the adjacent platinum cathode. The
size of potential fluctuations during metastable pit growth was argued to be related mainly
to the pit charge (size) instead of pit current or current density. From prior work it was
known that increasing pit currents for similarly sized pits provide a good indication of the
transition to stable pitting. Therefore, EPN was viewed to have less merit as an indicator of
pit stabilization than ECN. It was theorized that the standard deviation of metastable pit
currents would provide a better indicator of the transition to stable pitting. However, the
presence of heat tint oxides formed during heat treatment of samples complicated the estab-
lishment of straightforward relationships between ECN and conditions for pit stabilization
for a variety of reasons.
Me t ho ds
In this section, ENM methods were applied to a diverse number of corrosion problems.
In each paper, alternative corrosion monitoring tools augmented ENM studies. The first paper
by Oltra et al. examined ECN and acoustic emission (AE) associated with the abrasive action
of a slurry on a metallic target. The fluctuating AE and ECN signals were processed in two
ways (statistical analysis of signals in the time domain and in terms of a spectral density
plot) with the overall goal of quantifying the contributions to metal loss by mechanical wear
and corrosion. A linear relationship was established between abrasive metal loss and the
statistical analysis of acoustic signals. Interestingly, total corrosion currents could not be
considered as the linear superposition of single current transients suggesting that the observed
depassivation-repassivation events were not completely independent.
In the second paper, Huet et al. examined EPN associated with the proton discharge
reaction both at open circuit and under applied cathodic polarization on iron using Devan-
OVERVIEW XV
athan permeation foils exposed to sulfuric acid. Simultaneously with EPN, associated fluc-
tuations in electrolyte resistance on the charging surface and the hydrogen permeation flux
on the exit surface of the foil were characterized. The hydrogen permeation flux is coupled
to the behavior on charging surfaces through solid state hydrogen diffusion and fluctuations
in charging surface lattice hydrogen concentrations could be estimated. These fluctuations
were linked with hydrogen bubble formation and detachment from the charging surface under
cathodic polarization. However, the origins of fluctuations for open circuit hydrogen pro-
duction and ingress remained undetermined. Insight into factors affecting hydrogen absorp-
tion was gained.
In the third paper, Mal o and Velazco sought to distinguish artificial noise signals associated
with a rotating disk electrode device and other sources from noise of fundamental electro-
chemical origins. Artificial sources produced noise signals that did not exceed 10 v~V and
0.1 ixA. Corrosion processes for mild steel in Na2SOa produced much larger noise levels in
this system. In the next to last paper in the session, de Damborenea and Fernfindez examined
ENM during the exfoliation corrosion of AA 8090 in the ASTM Test Met hod for Exfoliation
Corrosion Susceptibility in 2XXX and 7XXX Series Al umi num Alloys (EXCO Test) (G 34).
Power spectral density (PSD) and statistical methods, including noise resistances, were com-
pared to charge transfer resistances obtained from EIS. The early stages of localized corrosion
were detected by ENM, but strong correlations between ENM data and corrosion rates during
severe exfoliation were generally lacking. EPN was used in the last paper of the session
(Almeida et al.) to examine the protective nature of the corrosion products developed on
pretreated and untreated carbon steels exposed at various Ibero-Ameri can atmospheric test
sites. These samples were subsequently immersed in Na2SO4 solutions for linear polarization
resistance (LPR) and EPN measurements at different times. Samples with higher corrosion
rates, because of less protective oxide layers or more aggressive atmospheric conditions or
both, correlated well with increased magnitudes of EPN particularly in the cases in which
localized corrosion was promot ed by chloride ion incorporation into oxide layers during
exposure to marine atmospheres.
St andar di z at i on
The first paper by Bierwagen et al. covers several topics and is the onl y one in the STP
with the goal of evaluating the reproducibility of data obtained for any given system. The
authors present a significant body of data that should serve as a benchmark for future work
in this area. By rigourously controlling test variables and statistically validating test results,
the authors justify the use of ENM for the evaluated coated metal systems. The final paper
(Kearns et al.) of the session and the symposi um reviews the activities of the ASTM Com-
mittee G- i task group on ENM since its beginning in 1991. The paper presents the group' s
first attempt to develop consensus on: (1) terminology, (2) specifications and configurations
for laboratory instrumentation, (3) laboratory apparatus, and (4) data analysis methods. The
pr oof of these deliberations is a test method and instrument specification that when followed
yield a set of data for a given system that can be compared with confidence to others
following the same. To this end, instrument specifications, test procedures, and test results
are presented. It is hoped that this paper encourages participation in future task group activ-
ities and the round robin test program that is planned. An extensive list of terms related t o
ENM technology is defined in the Appendix to the paper, which the reader may find useful
when reading this and other papers in this STP.
XVI ELECTROCHEMICAL NOISE MEASUREMENT
Cur r e nt St at e and Fut ur e Di r e c t i ons
The reliable interpretation of ENM data is the major challenge to the advance of the
t echnol ogy in corrosion research, materials testing, and industrial monitoring. At this time,
it has been established that ENM systems are capable of detecting subtle changes in the
material or environment or both under a wide variety of plant processes and laboratory test
conditions. With strong corroborating information from other sources, ENM data can be
related with confidence to changes in corrosion behavior or environmental conditions or
both. However, until a theoretical framework for interpreting corrosion events from ENM
data are established and standardized testing practices are widely accepted, the reader is
encouraged to be skeptical about detailed physical interpretations of ENM data in the absence
of strong corroboration: As was stated at the symposium, "correlation alone is not sufficient
to establish causality."
In addition to the reliable interpretation of data, other exciting developments are also
anticipated. No doubt there will continue t o be more unique applications for ENM in cor-
rosion monitoring and even process control. The challenges encountered in the field will set
the pace for much laboratory experimentation and research. In addition to successful indus-
trial applications, the next major step toward validating ENM is anticipated to be in regard
its use in elucidating various forms of localized corrosion, such as SCC and pitting. In
addition to comparisons of parameters common to ENM and more established electrochem-
ical techniques, such as LPR and EIS, one can also look forward to the analysis of ENMs
by computer-intensive tools associated with artificial neural networks and nonlinear
dynamics.
Measurement is the final area for future work that is anticipated based on a reading of
this STP and discussions at the symposium. There is a need, in both the lab and plant, for
techniques/instruments that can handle the large amounts of data that are acquired during
real-time monitoring without losing valuable information. Specifically, more work is needed
to define the best methods for electronic filtering, trend subtraction, and localized event
recognition of ENM signals. However, in an era of incredibly powerful, inexpensive, user-
friendly electronics and software, it is very important t o consider just how electrochemical
signals are processed into ENM data to avoid mis- and over-interpretation of data. With this
caution in mind, it is essential that calibration procedures for instrumentation and reference-
corroding systems be established along with diagnostic tests for the validity of data so that
measurements can be compared with confidence. The ASTM Committee G-1 task group on
ENM is an excellent forum to address these latter tasks.
S u mma r y
The combi ned offerings of this STP provide the reader with a review of the state of the
art of ENM in the early 1990s. The integration of ENM parameters with other electrochem-
ical measures of system status demonstrate the opt i mum use of ENM technology. Many
diverse industrial applications for ENM are presented along with the latest laboratory meth-
ods and data analysis techniques. The approaches of the individual groups varied accordi ng
to the anticipated nature of the corrosive environment and the anticipated response of the
material to it. In addition to material-environment considerations, the individual goals of the
monitoring or testing operation also influenced decisions about what is t o be measured and
how data should be acquired and analyzed. Strategies to monitor and control corrosion in
heat exchangers, pipelines, storage tanks, and steam generators using ENM t echnol ogy are
discussed from an industrial perspective. Workers from laboratories around the world are
using ENM to glean new insights into traditional corrosion problems. From this plethora of
OVERVIEW xvi i
knowledge and experiences, a consensus is emerging on how to make ENMs, but the inter-
pretation of ENM data and the optimum use of ENM technology for corrosion prevention
and process control in industrial systems are issues that still present many challenges. It is
hoped that some of the proposed test methods and data analysis techniques presented in this
STP will gain wider acceptance and eventually lead to the development of new ASTM
standards.
Jeffery R. Kearns
Alcoa Technical Center
Alcoa Center, PA; symposium
chair and principal editor.
John R. Scully
University of Virginia
Charlottesville, VA; symposium
vice-chair and editor.
Pierre R. Roberge
Royal Military College of Canada
Kingston, Ontario; symposium
David L. Reichert
DuPont Experimental Station
Wilmington, DE; symposium
John L. Dawson
CAPCIS Ltd.
Manchester, UK; symposium
Keynote Address
J o h n L. Da ws o n t
Electrochemical Noise Measurement:
The Definitive in-Situ Technique for
Corrosion Applications?
REF ERENCE: Dawson, J. L., "El e c t r oc he mi c al Noi s e Me as ur e me nt : The Def i ni t i ve l n -
Si t u Te c hni que f or Corros i on Appl i c at i ons ?, " El ect r ochemi cal Noi s e Me as ur e me nt f o r Cor-
rosi on Appl i cat i ons, AS T M STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge,
David L. Reichert, and John L. Dawson, Eds., American Society for Testing and Materials,
1996, pp. 3-35.
ABSTRACT: A review is presented of electrochemical noise (EN), the generic term given to
fluctuations of current and potential seen in high-temperature corrosion, molten salt corrosion,
and aqueous corrosion. EN levels in corrosion and particularly localized corrosion are signif-
icantly greater than EN observed in redox systems. EN associated with corrosion is the result
of stochastic pulses of current generated by, for example, sudden film rupture, crack propa-
gation, discrete events involving metal dissolution at etch pits, grain boundaries and kink sites,
and hydrogen discharge with gas bubble formation and detachment. EN in corrosion includes
low-frequency, nonstationary, and weakly stationary processes; transients; and cyclic or oscil-
latory phenomena.
The use of EN, obtained either by potentiostatic/galvanostatic measurements or at freely
corroding potentials, has been shown to offer advantages over conventional DC and AC tech-
niques in research studies, testing, and corrosion monitoring. In many cases, reaction mecha-
nisms can be elucidated and corrosion rate information can be obtained.
Under freely corroding conditions, current noise impulses give rise to changes in potential
through the interracial impedance, (1,) - - (E, , )/IZI. Correlation of current and potential noise
from uniform corrosion may be used to obtain the electrochemical impedance of the corroding
interface; these noise signals are produced by weakly stationary or deterministic processes.
Corrosion rates may therefore be evaluated from this low-frequency impedance or from the
associated but simplified noise resistance, obtained from the standard deviations of the current
and potential, trE/tr , = R , .
Localized corrosion events produced by Poisson processes can be easily identified from time
records and spectral density plots. Localized corrosion involves nonstationary systems. The
anodic and cathodic processes can be separated in both time (the anodic event occurring before
the cathodic event or vice versa) and space (at different parts of the electrode surface). The
electrons produced or consumed during these corrosion events are stored temporarily in the
electrochemical double layer and corrosion product film capacitors.
Assessment of individual transients, use of signal analysis techniques, modeling of ensem-
bles of transients as developed for electrocrystallization studies, and use of the chaos theory
have all been used in EN evaluations.
KEYWORDS : electrochemical noise, corrosion monitoring, testing, electrochemical noise im-
pedance, uniform corrosion, localized corrosion, pitting, stress corrosion cracking, coatings
The obj ect i ves o f t hi s paper ar e to pr ovi de a hi st or i cal per s pect i ve and ove r vi e w o f el ec-
t r ochemi cal noi s e ( EN) t hat c ompl i me nt s pr evi ous sci ent i f i c r evi ews by Gabr i el l i , Huet , and
Senior Consultant, CAPCIS Ltd., Bainbridge House, Granby Row, Manchester, M1 2PW, UK.
Copyrighl 9 1996 by ASTM lntcrnational
3
www.astm.org
4 EL ECT ROCHEMI CAL NOI SE ME A S URE ME NT
Keddam [1-3]. The emphasis is on the wider use of electrochemical noise measurement
(ENM) not onl y in corrosion research but also in corrosion testing and on-site monitoring.
Included are a basic introduction for those scientists and engineers who are not familiar with
the subject, an outline of scientific and practical developments to date with appropriate
reference to the literature, and finally, an indication of some areas of possible future study.
EN from many corrosion systems, but particularly uniform corrosion, is observed as spon-
taneous low-frequency fluctuations of current and potential (Fig. 1). In the case of localized
corrosion, distinct anodic or cathodic transients are observed (Fig. 2). EN data are obtained
potentiostatically (Fig. 3a), or galvanostatically (Fig. 4a), or at the natural corrosion potential
(Figs. 1 and 2). In all cases, stochastic processes are involved; that is, naturally occurri ng
events take place in both a random manner across the corrodi ng surface and a random manner
throughout the measurement period.
Sources of electrochemical noise depend on the particular corrosion circumstances. These
may be: (1) the result of mechanical effects, as during the propagation of stress corrosion
cracks (Fig. 5) and abrasion of metallic surfaces by particles (Fig. 6a); (2) the result of
chemical effects, such as adsorption of chlorides on passive films leading to film rupture and
repassivation during pit initiation (Fig. 7); or (3) the growth and detachment of hydrogen
bubbles during active dissolution in acidic solutions (Figs. 3a and 4a). EN can be described
in terms of Poisson processes; the result of a series of random (stochastic) events or bursts
of activity associated with either the anodic or cathodic kinetics.
The growi ng international interest in EN over the past 15 years can be seen in the increase
in papers and publications describing scientific investigations and practical applications.
There is also a growing consensus that EN can be used quantitatively, and it is therefore
appropriate that the First International Symposi um on Electrochemical Noise Measurements
for Corrosion Applications in 1994 was sponsored by ASTM.
Background
EN in corrosion [11,12] and electrochemical studies [13-31] were first reported in the
early 1960s and 1970s. The research on electrochemical processes has been evaluated and
presented in a comprehensive theoretical treatment by Rangarajan and Serclathan [32,33],
but they did not consider corrosion processes. It is onl y since the corrosion publications of
the late 1970s and early 1980s [34-50] that there has been an increasing interest in the
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lime (seconds) "rime ( s e c o n d s )
a ) P o t e n t i a l - t i m e r e c o r d b ) C u r r e n t - t i m e r e c o r d
FIG. l - - Si mul t aneous changes of coupling current and corrosion pot ent i al f rom a mi l d steel and a
sacrificial zinc anode [ 4 ] .
KEYNOTE ADDRESS 5
Potential (V)
-20.00E-04
- 40. 00E- 04
- 80. 00E- 04
Potential Noise
I
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o.oo~.oo l i b I., lJ~ i
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~oo.o ~ ~ v l ~ O
30.00E-09 I
O.OOE+O0 10.00E+02 20.00E+02
"rime (s)
FIG. 2- - Si mul t aneous current and pot ent i al noise transients showi ng pi t initiation and met ast abl e
pi t t i ng [5].
subject. This is partially because the availability of digital equipment makes the measurement
and recording of noise data a relatively easy task. Equally important is the recognition that
EN interpretation provides scientific answers in corrosion research and solves practical prob-
lems in corrosion engineering.
Most workers who have made DC polarization or electrochemical impedance measure-
ments have noticed the apparent "chat t er" on chart recordings or "scat t er" in low-frequency
i mpedance data. Such random signals, often ascribed to instrumentation noise, are now rec-
ogni zed as resulting from distinctive phenomena that are of significant importance in
corrosion. Not e that low-frequency electrochemical corrosion data that do not conform to
the Krammers-Kroni g analysis are stochastic and probably a result of localized corrosion.
There are also sufficient reviews [ 1 - 3 , 4 9 , 5 1 ] , scientific publications [ 9, 52, 53] and informa-
tion on practical applications [ 5 , 5 1 , 5 4 - 5 6 ] available in the literature on EN, including pres-
entations at this symposia, to provide a formalization that will aid future scientific debate
and development of the subject.
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'
4

8 ELECTROCHEMICAL NOISE MEASUREMENT
-18.0
-18.4
-18.8
I L l
-19.2
0
,
' i l : i '
I I t t , ~ i
I ' ' ~ : I ~ , , , i . l I P
i
f l I ~ I , ~ ! ; I ~1 ~ I I i : " q I , I 1 1
" , , . i , ~ i I ~ , ~ . ~ i ~ 1 ! ; I % 1 1 I I I I I
! I I ; I \ ~ I ;
I I I
20 40 60 80 100
"time, s
"~" 0
n
LLI
-1
I I ' l J l r [
t ~ 9 t }
i f [ j
1
! ; i
I " Ii
i [
I ~ i i 9
! : . , ! '
T i [ i i i
0 20 40 60 80 100
~me, $
FIG. 5 - - ECN and EPN transients produced by stress corrosion cracking at the f ree corrosion
potential.
R a n d o m P r o c e s s e s
Al l physi cal processes are di vi ded into det ermi ni st i c or nondet ermi ni st i c (nondet ermi ni st i c
bei ng r andom or st ochast i c) cat egori es. Det ermi ni st i c processes may be peri odi c or nonpe-
ri odi c (t ransi ent ); they are descr i bed by t i me- var yi ng functions, such as t hose pr oduced by
si nusoi dal and pseudor andom pert urbat i ons used in el ect rochemi cal i mpedance studies, or
sawt oot h and st ep functions, as used in pol ari zat i on and el ect r ocr yst al l i zat i on studies. In
convent i onal el ect r ochemi cal studies, the det ermi ni st i c i nput is t ypi cal l y cont r ol l ed by an
ext ernal pot ent i ost at i c or gal vanost at i c pert urbat i on.
EN phenomena bel ong to the general cat egory of r andom l ow-frequency processes. These
stochastic processes are descr i bed ei t her by pr obabi l i t y densi t y function equat i ons or in
st at i st i cal terms. Random processes can be st at i onary or nonstationary. The first moment s
(mean values) of a st at i onary process are invariate wi t h t i me. Some r andom corrosi on noi se
dat a can be descr i bed by a st at i onary r andom process mul t i pl i ed by a det ermi ni st i c factor.
In pract i ce, si ngl e- t i me records may be consi dered st at i onary i f the first moment s comput ed
over short -t i me intervals do not vary more than expect ed from normal st at i st i cal sampl i ng
variations. Hence, it may be possi bl e to treat some corrosi on syst ems, such as t hose with
l ow rates of uni form corrosi on, as weakl y st at i onary r andom processes.
Nonst at i onar y r andom processes have t i me- var yi ng functions that are det er mi ned by ob-
t ai ni ng i nst ant aneous averages over the set (ensembl e) of t i me records formi ng t he process.
One of the most compr ehensi ve st udi es of such ensembl es was by the Har wel l group on
KEYNOTE ADDRE S S 9
.O
m
I
$
0 4
i
i I F
t
- i l l
t I
ZH / ~V',O I. ' NON 1o O S d
V'd ~,ueuno
O N
ILL
o
"7
O
E
"E
2
O "~
' ~"C
C~
L h ' ~
10 E L E CT ROCHE MI CA L NOI SE ME A S URE ME NT
1.1
0.9
0.7
0.5
~ 0.3
0.1
-0.1
0 30 60 90 120 150
" t i me, s
FIG. 7--Current noise transients at 0.2 V versus SCE, A/ S/ 304 stainless steel in (a) 0.075M nCl O 4
+ 0.025M HCI, (b) in O.1M HCIO 4, and (c) specimen passivated in perchloric acid before chloride
addition [9,10].
current noi se t ransi ent s pr oduced duri ng pi t t i ng (Fig. 8). The dat a sets were generat ed by a
met hod in whi ch a pot ent i ost at i c sweep was t ermi nat ed at a fixed pot ent i al [58,59].
St andard met hods of anal ysi s are t ypi cal l y used to show noi se dat a as spectra; t hese are
represent at i ons of the t i me r ecor d as " aver ages " in t he frequency domai n di spl ay. Two
common mat hemat i cal pr ocedur es used to convert t i me domai n records i nt o frequency do-
mai n spect ra are t he fast Four i er t ransform ( FFF) and the maxi mum ent ropy met hod (MEM).
SO I
j ~A , ' i
25 . ~ p : " J ~ : t
- - p s . ~ ~ I f - " -
( - - ' # : o
r , /~&: ; . V ; e
" ~ 9 . k " ~ s
r . ;q, v J ' - ~ . . . , ~ . . .
0 1200 2400
" l i me, s
FIG. 8--Ensemble of current time transients on 18Cr:13Ni:lNb at 50 mV versus SCE in 0.028M
NaCI [57].
KEYNOTE ADDRESS 11
The PTT method [60] is widely used in many branches of engineering and science; it pro-
duces somewhat "noi s y" spectra and is appropriate for repetitive signals and data sets with
a reasonable number of sample points (>1040, 2080, and so forth). MEM was developed
by Burg [61] to analyze a limited number of sample points in geophysical studies and uses
filter coefficients to describe the data. Details of the computational procedures for MEM are
available [62], and MEM is considered by some to produce superior spectral representations
of data [63]. MEM produces smoot her spectral curves from which roll-off slopes and fre-
quency break points can he easily evaluated. Results t o date indicate that FFT and MEM
produce identical spectra from electrochemical noise [64,65]. Selection of the transformation
method (FFT or MEM) and noise data display (PSD or amplitude) would therefore appear
to be a personal choice.
Noise spectra are presented as either power spectral density (PSD) or amplitude (dB) plots.
In both cases, the log of frequency (Hz) is plotted either against l og spectral power density
( V/ Hz or A/ Hz ) or against the amplitude (dB) as log power spectral amplitude ( V/ ~/ Hz or
A/ ~/ Hz) . The noise amplitude is ~v / noise power, given by dB = 20 log (voltage ratio),
correlated according to the measured bandwidth. Not e that spectral analysis provides valid
information below 1/(the time record length) and above 1/ (2 x the sample period).
EN observed in corrosion can be classified under the general heading of low frequency
or 1 I f noise (sometimes referred to as 11f~' noise). This is true of potential noise measure-
ments made at the freely corroding corrosion potential. With some uniform corrosion pro-
cesses, the current noise amplitude spectra appear "whi t e"; with the current fluctuations in
the time domain, records produce a fiat spectral plot in the frequency domain, and the freely
corroding process is slow enough to appear as a weakl y stationary random process. The
major feature of 1/ f noise is that the noise amplitude in each measured bandwidth increases
with decreasing frequency. 1/ f noise is due to the randomness inherent in the system under
investigation and is associated with discrete Poisson stochastic-type processes. In some spec-
tral density plots, distinct peaks are observed in the 1/ f s l ope indicating a repetitive transient
of a specific frequency. This is analogous to the single "spi ke" seen in frequency domain
spectra when a constant frequency sinusoidal signal is used t o perturb a system t o obtain an
impedance value at a specific frequency as part of the overall spectra.
Noise Sources
The maj or sources of noise observed in electrochemistry and corrosion can be ascribed to
macroscopi c random (stochastic) phenomena. They include partial faradaic currents,
adsorpt i on/ desorpt i on processes, surface coverage, and, particularly in the case of localized
corrosion, the initiation of pits and mechanical effects resulting from cracking and erosion
processes. Al t hough similar 1/ f noise spectra are observed in studies from other scientific
fields, including biochemistry and electronics, this does not necessarily mean that the same
processes are involved. Nevertheless, the same basic principles of data interpretation apply
in all fields, even t hough converting this data into process information will be different
[66,67]. A common feature of 1/ f Poisson noise is that improvements in accuracy by in-
creasing the measurement time is not possible because it is a random signal. This is in
contrast to "whi t e" Gaussian noise in which the accuracy increases as the square root of the
measurement time.
The lowest magnitude or intensity of electrical noise generated in systems is the thermal
or Johnson noise as a result of the random mot i on of the electrons and charge carriers in
thermal equilibrium with their surroundings. This vibration occurs at temperatures above
absolute zero and is given by the Nyqui st formula [68,69]. Thermal noise is "whi t e, " with
the noise power directly proportional t o the measured bandwidth. Johnson noise produced
12 ELECTROCHEMICAL NOISE MF_.ASUREMENT
by t he measur ement i nst rument at i on noi se must be mi ni mi zed. In some studies i nvol vi ng
low levels of EN, one wi del y used approach is to use comput at i onal means to r emove the
i nst rument noise. Most pract i cal corrosi on studies pr oduce sufficient EN for the signal l evel
to be well in excess of the i nst rument at i on noise.
Shot noi se in el ect ri cal ci rcui t s is due to t he quant i t i zed nature of the el ect roni c charge
and is t ypi cal l y associ at ed with low levels of current flow in el ect roni c devi ces. Such fluc-
t uat i ons are great er than t hose pr oduced by t hermal noise, but convent i onal el ect ri cal shot
noi se is unl i kel y to be a maj or source of el ect r ochemi cal noi se in corrosi on.
Bet ween 1967 and 1972, Hooge [24-31] i nvest i gat ed noi se in met al s and semi conduct ors
and concl uded that the vari ance of the noi se was const ant with a Gaussi an di st ri but i on.
St udi es of syst ems in aqueous sol ut i ons [29] showed 1/ f and 1/f2 spectra, whi ch l ed to the
concl usi on that 1/ f noi se was due to the fluctuations in t he mobi l i t y of free charge carri ers,
not the change in the act ual number of carri ers. Thi s approach was not ext ended to corrosi on
studies.
Initial studies of noi se in el ect r ochemi cal syst ems by Tyagai [13-19], Baker [21-23], and
Fl ei schmann and Ol dham [31] have been revi ewed by Seral at han and Rangaraj an [32,33].
They have present ed det ai l ed mat hemat i cal model s based on the Langevi n met hod for as-
sessi ng fundament al processes. The Rangaraj an model s consi der el ect rochemi cal noi se as a
process i nvol vi ng faradai c shot noise; t hei r met hodol ogy provi des a fundament al t reat ment
of the previ ous studies of basi c el ect rochemi cal react i ons and part i cul arl y t hose by Tyagai
(but not corrosi on). It involves, first, consi derat i on of pr i mar y noi se sources, whi ch are
fundament al , but i nvari abl y uncorrel at ed (the Langevi n approach), and second, assessment
of macr oscopi c phenomena that provi de the secondar y source of noise. The t reat ment in-
cl udes equat i ons for conversi on of the current into power spectra. The macr ovar i abl es i ncl ude
part i al faradai c currents, el ect ron transfer, and chemi cal ki net i cs, but these are descr i bed as
di scret e Poi sson processes. The f or mal i zat i on was not ext ended to corrosi on studies such as
pit nucl eat i on and growth; it is nevert hel ess an appr oach that coul d be used to f or mal i ze
corrosi on processes.
These earl i er studies hi ghl i ght two maj or drawbacks to the use of EN in studies of redox
syst ems: (1) the noi se signal is rel at i vel y smal l and (2) as poi nt ed out by Barker [21], t here
is no part i cul ar advant age of noi se measurement s compar ed to det ermi ni st i c met hods (i m-
pedance) for t hese syst ems.
The i mport ance of noi se measurement s in the st udy of passi vi t y and its br eakdown was
r ecogni zed by the Japanese researchers Okamot o et al. in the mi d 1970s [35-37]. Thi s work,
t oget her with Ber t occi ' s earl y studies [43-45], were revi ewed in 1981 by Tachi bana and
Okamot o [49].
The devel opment of equat i ons to model pr obabi l i st i c (st ochast i c) processes was used
for bot h el ect r ocr yst al l i zat i on studies [46,72] and corrosi on [38,71,73,74]. A si mi l ar ap-
proach was adopt ed in bot h cases. The publ i cat i ons of Gabri el l i , Keddam, and Huet in Pari s
are part i cul arl y not ewort hy devel opment s [7,8,38,39,71,73,74,75-77], see al so Refs 1-3 for
t hei r reviews. For exampl e, Refs 2 and 3 show how model i ng the current t ransi ent s may be
consi der ed as a nucl eat i on or poi nt process that can be t ransformed to provi de a power
spectral densi t y of det ermi ni st i c events. Thi s part i cul ar corrosi on model uses a Poi sson pro-
cess to show how the frequency may vary wi t h the physi cal or chemi cal process; here a
PSD pl ot of 1/ f2 i ndi cat es a "sudden bi r t h" or "sudden deat h" process, whi l e a "sl ow bi r t h"
or "deat h pr ocess" gi ves 1 ]f4 plot.
The shapes of t ransi ent s pl ay a crucial rol e in det ermi ni ng the spect ral pl ot s [1,3]. In the
case of si mul t aneous measur ement s of current and pot ent i al at the corrosi on pot ent i al , current
t ransi ent s wi t h a slow ri se and a r api d decay will pr oduce spectral plots that are di fferent to
t hose wi t h a rapi d rise and a sl ow decay. Transi ent s wi t h a rapi d rise and fall or st at i onary
KEYNOTE ADDRESS 1 3
noi se sour ces can pr oduce whi t e noi se spect ra. For exampl e, anal ysi s o f powe r spect r al
dens i t y pl ot s f r om pot ent i al noi se on f r eel y cor r odi ng el ect r odes [78-80] gave 1/ f ' - f or pi t
i ni t i at i on and 1//f4 f or unst abl e pi t s (Fig. 9). However , in this cont ext , not e that, in t he f r ee
cor r os i on si t uat i on, it is the t r ans f or mat i on o f t he cur r ent noi se t hr ough t he el ect r ode i nt er-
f aci al i mpe da nc e t hat pr oduces t he pot ent i al noi se. Thus, it woul d a ppe a r t hat a whi t e noi se
cur r ent si gnal is r es pons i bl e f or t he pot ent i al noi se powe r spect r al dens i t y o f 1/ f 2 ( or 1 / f in
t he ampl i t ude pl ot ) whi l e a 1 / f cur r ent noi se s our ce gave ri se t o a p o we r spect r al dens i t y
pl ot o f 1/ f 4 f or t he pot ent i al noi se ( equi val ent t o a 1/ f 2 s l ope in t he ampl i t ude pl ot ).
I t is al so i nst r uct i ve when cons i der i ng noi se sour ces and anal ys i s o f noi se si gnal s, t o
eval uat e t he wor k by Wi l l i ams et al. o f the Har wel l Gr oup [57-59]. The i r me t hodol ogy
i nvol ved a r i gor ous exper i ment al and dat a col l ect i on pr oc e dur e t hat used set s o f dat a r at her
t han st udi es o f s i ngl e- t i me r ecor ds, but the anal ysi s is, in ma n y ways , anal ogous in appr oach
t o t hat adopt ed by t he Pari s school . The Har wel l st udi es l ed t o a gr eat er under st andi ng o f
pi t t i ng pr oces s es by def i ni ng unst abl e and st abl e pi t t i ng pr oces s es ( see be l ow f or f ur t her
det ai l s on pi t t i ng).
Noi s e sour ces in cor r os i on have been s hown t o be ma ny and vari ed. The s e i ncl ude:
(1) hydr oge n evol ut i on i nvol vi ng bubbl e nucl eat i on, gr owt h, and de t a c hme nt
[21,41,42,44]; changes in sol ut i on r esi st ance and di f f usi on i nt o pr opa ga t i ng mi cr o-
cr acks [10]; and di schar ge on f r eshl y e xpos e d met al at pr opagat i ng cr acks [51];
(2) pr opagat i ng st r ess cor r os i on cr acks i nvol vi ng met al di ssol ut i on or wat er di s char ge
[51, 81-86];
6 + X
t
~>
E
P,
CO
9
5 + X
4 + X
3 + X
2 + X
1 + X
O+ X
2 + X
- I + X
- 2 + X
- 3+) (
- 4+X
-4
R I I ' E : N ~ - . . .
[ X = O l ' I ~
- ~
C A S E 3
[ X = 3 !
-3 -2 -1 0
L OG F r e q u e n c y ( H z )
FIG. 9--Corrosion potential noise, pit initiation, and metastable pitting; experimental data and sim-
ulation showing 1/ f 2 and 1/ f 4 [79].
(3) pit i ni t i at i on, met ast abl e pitting, and stable pi t growt h [9-11, 87-92];
(4) crevi ce corrosi on [47,93,94];
(5) mechani cal i mpi ngement and abrasi on [95];
(6) underfi l m cor r osi on [ 95- 97] ;
(7) passi ve syst ems [49,54,98];
(8) hi gh-t emperat ure processes [99-101];
(9) mi cr obi al - i nduced corrosi on [102-104]; and
(10) uni form corrosi on [55,105].
In some cases, mechani cal l y i nduced st ochast i c events occur (2, 3, and 5), in ot her syst ems,
st at i onary processes are i nvol ved (1, 6, and 10), whi l e mi grat i on of charge carri ers and sol i d-
state di ffusi on pr ocesses pr obabl y occur in (7) and (8). In all cases, noi se dat a from corrosi on
studies onl y i ndi cat e possi bl e t ypes of st ochast i c processes. The dat a have then to be inter-
pret ed to pr ovi de corrosi on i nformat i on or an underst andi ng in t erms of model s and corrosi on
pri nci pl es.
ENM Techniques
El ect r ochemi cal noi se dat a can be obt ai ned in a convent i onal manner usi ng pot ent i ost at i c
and gai vanost at i c t echni ques (Figs. 3, 4, 7, and 8). The current t i me records or pot ent i al t i me
records are then anal yzed to provi de i nformat i on on the corrosi on processes. Such measure-
ment s can be useful in research i nvest i gat i ons si nce onl y one measured par amet er varies
wi t h time. However, it must be r ecogni zed that i mposi t i on of a cont r ol l ed pot ent i al or con-
t rol l ed current, al t hough a val i d research met hod, may not al ways provi de a true represen-
tation of an act ual corrosi on situation. For exampl e, spect ra with a posi t i ve 1 I f sl ope coul d
be suspect; ei t her the i nst rument at i on or the t echni que used coul d i nt roduce an artifact.
An al t ernat i ve appr oach to pot ent i ost at i c and gal vani c measur ement s devel oped at UMI ST
[48,50,51,54,106-108] is to al l ow the natural corrosi on process to occur on the el ect r ode
and then to record the pot ent i al changes of the freel y cor r odi ng met al on a sensi t i ve di gi t al
voltmeter. A preferred vari at i on is to combi ne the corrosi on pot ent i al measur ement wi t h a
current measurement by coupl i ng t wo freel y cor r odi ng el ect rodes t oget her t hrough a sensi t i ve
zero-resi st ance ammeter. The t wo met ers provi de si mul t aneous t i me records of t he spont a-
neous changes in coupl i ng current and corrosi on pot ent i al . Anal ysi s of such dat a can be used
in ei t her research studies or pract i cal cor r osi on- moni t or i ng appl i cat i ons. Not e that it is the
nat ural l y occurri ng changes in corrosi on current flow, or the occurrence of current t ransi ent s
as a result of the st ochast i c nature of the basi c processes, that result in the obser ved changes
in corrosi on pot ent i al . In all corrosi on cases, it is the l ocal current flow (current noi se)
t hrough the i nt erfaci al i mpedance that gi ves ri se to pot ent i al changes (pot ent i al noise).
Potentiostatic and Galvanostatic Measurements
The use of pot ent i ost at i c measurement s has been a preferred met hod in many research
studies. The t echni que is part i cul arl y useful for i nvest i gat i ons of passi vi t y and its br eakdown
l eadi ng to pitting. Of maj or concern in earl y i nvest i gat i ons of el ect rochemi cal noi se in cor-
rosi on was the devel opment and use of low noi se pot ent i ost at s and gal vanost at s [38,40,42].
Ini t i al exper i ment s al so favored the use of a t wo-channel cross-correl at i on met hod and t wo
reference el ect rodes, all cont ai ned wi t hi n a faradai c cage. Thi s appr oach was abandoned
when it was r ecogni zed that in corrosi on studies most noi se si gnal s are si gni fi cant l y in excess
of the i nst rument at i on noise. Obvi ousl y, in all studies, it is necessary to use wel l - desi gned
i nst rument at i on wi t h a l ow i nst rument noi se out put to achi eve mi ni mum i nt erference f r om
KEYNOTE ADDRESS 15
the measurement equipment. Examples of the use of potentiostatic and galvanostatic mea-
surements are given below.
One of the most interesting studies of pitting corrosion on stainless steel was through the
evaluation of the statistics of ensembles of current-time transients by the Harwell group
[57-59]. In this approach, the potential is slowly increased, as in a conventional polarization
sweep, and the sweep is terminated when the current starts to rise. Any increasing current
is then logged as a current-time record containing a series of transients. A series of ensembles
of such current-time transients are thus obtained at a fixed applied "pi t t i ng" potential. These
data are then analyzed statistically in terms of the mean, standard deviation, and variance.
The pitting process is modeled as stochastic events randoml y distributed in time and space.
The events giving rise to the transients have a nucleation frequency, a probability of death,
a survival time probability, and an induction time. The pitting potential is shown to be a
statistical mean. The pitting process can be divided into nucleation of unstable (metastable)
and stable pits. The concept is that all pits have a finite lifetime but will terminate at different
pitting stages as either pit initiation events, unstable pits, metastable pits, or stable pits.
The relationships between the electrochemical behavior of the passive film on stainless
steel under potentiodynamic, nonsteady state conditions and the current fluctuations in the
prepitting range have been evaluated further using the probabilistic approach by Keddam et
al. [109]. Pit nucleation is described by a Poisson process. The amplitude and frequency of
the current noise decreased drastically with aging of the passive film. The capacitance mea-
surements correlated with the passive current and suggested an increasing charge storage
with completion of the full passive state.
In contrast to the large number of papers using potentiostatic measurements, there are few
reports of the use of noise measurements obtained galvanostatically. Of particular interest
has been the work by Gabrielli and Keddam [2] on noise generated by iron dissolution and
simultaneous hydrogen generation. The data are analyzed to demonstrate that the fluctuations
are due to the formation and release of hydrogen bubbles (Figs. 3 and 4). This analysis is
an extension of the original postulates by Baker [21] and Bertocci [41] that electrochemical
noise may be due to hydrogen bubble formation. The model has been further extended by
the Paris school to consider the diffusion of hydrogen into the metal [110].
Free Corrosion Measurements
Electrochemical Potential Noise Measurement
Many of the early observations of electrochemical noise were made by monitoring the
corrosion potential of freely corrodi ng electrodes [11,12,47]. Work sponsored jointly at
UMI ST by the United Ki ngdom Ministry of Defence and ICI between 1979 and 1985 was
directed at using this approach as a means of detecting and monitoring localized corrosion
in practical situations [48]. When used in combination with more conventional techniques,
such as linear polarization and electrochemical impedance, EPN monitoring of the corrosion
potential was able to discriminate between periods of uniform corrosion and localized cor-
rosion on-site and in a range of operating plants and test apparatus [111-114], for example,
Figs. 10. Other researchers have also suggested subsequently that potential noise measure-
ments may be used to quantify corrosion rates of steel in concrete [115,116] and active
dissolution of iron [2,117]. A significant number of workers have now reported on the use
of EPN in corrosion studies.
In the case of film breakdown and pitting corrosion, distinct transients with a characteristic
shape are observed for a range of passive metals. These comprise a rapid potential decrease
followed by an exponential type of recovery. Hagyard and Williams [11] in studies on alu-
1 0 O . . . . . . . ~ . . . . . . . .
( m (~)
10O
1 0 2
10 ~
1 0 o
v .
o T i m e ( h ) 1 2
( a ) H i g h I n h i b i t o r / L o w C 1 ~ ( P a s s i v e )
1 0 ~
1 0 0
0 Tirne (h) 1 2
( b ) H i g h I n h i b i t o r / M e d . C 1 ~ ( P i t i n i t i a t i o n )
104
103
102
.ct~ (0),
Ec~(M)
.
~ m ~ m ~ . . ~ , . m ~ . . ~ . m
~.~ (~)
101 ~_. ( ~1
1 0 0
0 ~ r n e (h) 1 2
c ) L o w I n h i b i t o r / h i g h C 1 ~ ( G e n e r a l C o r r o s i o n )
1 0 4
10O ~
L a , = ( = v )
1 0 o i ~
0 Time (h) 1 2
( d ) M o d e r a t e I n h i b i t o r / M e d . C 1 ~ ( P i t t i n g )
FIG. lO--Corrosion monitoring in a cooling water system showing the effect of change of chloride
and inhibitor concentrations [ 121 ].
minum in 1961 ascribed these to a sudden rupture of the oxide film followed by repassi-
vation; the decrease in potential was between 4 to 40 V/ s. Williams [106] suggests that the
exponential type of recovery on stainless steel is due to recharging of the double layer. This
has been subsequently confirmed in other studies, for example, Fig. 11. The magnitude of
the transients and particularly the recovery time is dependent on the metal environment
circumstances. Steel in concrete samples has given rise to transients greater than 300 mV
with recoveries of up to 14 h [53] (Fig. 12). This reflects the slow diffusion of oxygen to
the repassivated electrode. On the other hand, when pitting transients in highly turbulent
fluids, such as stainless steel under an impinging jet, the recovery (Fig. 13) [92] may be a
few seconds or less as a result of the high diffusion rate of the cathodic species. The film
capacitance is also part of the interfacial impedance, hence the transient recovery will rise
quickly for aluminum compared to steels, while valve metals will produce a slower rise.
The analysis of corrosion potential transients on iron has been extended by Hashi mot o et
al. in a recent series of papers [78-80]. They have used spectral analysis to study the film
breakdown and, as discussed above, showed that the power spectral density decreased with
the frequency first to 1/f2 and then to 1/f4. The 1/ f2 Lorentz dependence shows that the
pit initiation follows a Poisson process. The transition to 1/f4 that occurred at about 10
Hz was ascribed to pit growth (Fig. 9). The model assumes that pit growth also occurs during
the rapid decrease in potential. (Simultaneous current transient measurements can provide
further information on this corrosion process, see Fig. 13.)
E
~ 2
Q
O
9
KEYNOTE ADDRESS 17
0 100 200 300
"time (seconds)
FI G. 1 l - - A n a l y s i s of the potential recovery f rom a pi t initiation event indicating a recharge mecha-
nism [91].
- 500
- 550
~ 0 0
~ 5 0
-700
-750
- 800
~ 5 0
~00
- 950
o1000
potential (mV SCE)
0 2 4 6 8 10 12 14 16 18 20
"time (hours)
FI G. 1 2 - - E x t e n d e d pot ent i al time transient f rom passi vat ed steel in chloride-contaminated concrete
[53].
+2.3E-01
E (mV, SCE)
-5,0E-02
POTENTIAL
0 Seconds 204
+1.77E-01
E (mV, SCE)
+0.77E-02
b
0 Seconds 2040
+3.OE+Oo
l ( x l O~c m -z)
CURRENT
I . ,
+2.oE+O0 I CURRENT
1
-1.0E +00 " -1.38E+00
0 Seconds 204( 0 Seconds 2040
U n s t a b l e p i t t i n g S t a b l e pitting
FIG. 13--Current and potential noise transients showing: (a) pit initiation and unstable pitting, and
(b) stable pitting [92].
El e c t r oc he mi c al Cur r e nt Noi s e Me a s ur e me nt s f r o m Coupl e d El ect rodes
The use of coupl ed el ect rodes where t he coupl i ng current flow is moni t ored usi ng a zer o
resi st ance ammet er provi des a met hod of moni t ori ng current noi se on freel y corrodi ng spec-
i mens [107,108[. In most cases, nomi nal l y i dent i cal el ect rodes are used. In pri nci pl e, t here
shoul d be no net current flow bet ween the el ect rodes; however, in pract i ce, the st at i st i cal
vari at i on in corrosi on rates across surfaces means that current flow and el ect r ochemi cal noi se
are observed. Thi s process can be consi der ed as the experi ment al veri fi cat i on of the ori gi nal
Evans' concept of mobi l e anodi c and cat hodi c areas on a uni f or ml y cor r odi ng surface.
Changes in corrosi on pot ent i al of the coupl ed el ect r ode assembl y are measured usi ng a
t hi rd el ect rode, ei t her a reference el ect rode in the case of l aborat ory studies or in the case
of i n-pl ant moni t or i ng a pseudoreference and even a pi ece of met al of si mi l ar composi t i on
as the el ect r ode assembl y. Si nce in this l at t er case there are t wo uncorrel at ed pot ent i al
sources, then V,( . . . . . . . d) = X/ (V~ 2 + V22), where Vj and V2 are t he noi se si gnal s f r om the
coupl e and reference el ect rode, respect i vel y, and it is onl y requi red to di vi de the measur ed
pot ent i al noi se by X/ 2 to correct the signal. The t hree-el ect rode arrangement enabl es changes
in current noi se t hat pr oduce changes in corrosi on pot ent i al to be f ol l owed as t he envi ron-
ment al condi t i ons change.
In the case of l ocal i zed corrosi on, one of t he el ect rodes may generat e a pit, and hence,
the net current t ransi ent is observed. It is al so possi bl e to use speci al l y desi gned el ect rode
assembl i es in whi ch one el ect r ode is stressed; this may be used to eval uat e stress corrosi on
cracki ng [51,86]. Crevi ce corrosi on can be assessed usi ng an el ect rode covered by a cr evi ce
f or mer wi t h t he second el ect r ode act i ng as t he ext ernal cat hodi c ar ea [93,94,118].
Thi s UMI ST appr oach has been furt her devel oped to correl at e the current noi se and po-
t ent i al noi se si gnal s in bot h magni t ude and phase t o pr ovi de the el ect r ochemi cal i mpedance
KEYNOTE ADDRESS 19
of the corrosion system [77] (Fig. 14). In this context, Bierwagen has recently derived an
analysis of stationary noise for corrosion [119] using a probability density function to show
that low-frequency current noise, i,, and potential noise, E,,, are related through the interfacial
impedance, (E,,) ~ [Z] (i,,). This provides a more satisfactory pr oof for the use of simple
statistics [108] and use of the standard deviation, ~, of the low-frequency potential noise,
~r,., and current noise, %, signals to provide a noise resistance, ~r. = ~r i 9 R,,. At sufficiently
low frequencies, IZ] = R,,. This resistance is analogous to the linear polarization resistance
normally obtained by DC polarization techniques. The met hodol ogy is valid provided that
the system under investigation can be considered stationary during the measurement period.
A basic model of the combi ned use of current and potential noise to obtain uniform corrosion
rates is presented by Cottis and Turgoose at this symposi um [120].
When a uniform corrosion system becomes nonstationary (as localized corrosion starts),
then the ratios of the mean coupl i ng current to the standard deviation or the root-mean-
square (RMS) of the current noise can be used to identify the presence of localized corrosion.
For example, the onset of pit initiation increases the potential noise without a corresponding
increase in current noise (the current noise remains virtually white), but the amplitude of the
potential noise changes from pure 1/ f to l / f plus some l / f 2. Thus, the change in the coef-
ficient of variation indicates an increase of localized pitting corrosion compared to the uni-
form corrosion rate,
The simultaneous monitoring of current and potential noise signals was first used in 1984
by Eden [108,121] using simple analog instrumentation (Fig. 10). In 1985, the met hodol ogy
was then extended using digital equipment to identify galvanic corrosion (Fig. 1), uniform
corrosion, and localized corrosion [4,54,118]. This combi ned monitoring of corrosion poten-
tial and coupling current has been particularly useful in research studies of localized cor-
rosion, materials testing, and on-site for troubleshooting and process control. For example,
in the case of pitting, it can be shown that metal dissolution (electron flow from the pit site
l s x l O , , t - t -
I I I
~- - - %- - - - -
E
5 x 1 0 s
" ~ ' I I
- I I
I I
o f 1 "
I I
0 10 x 10 e 2 x 1 0 e
Real I mpedance, ohms
FI G. 14--1mpedance spectra obtained by correlation of current and potential noise, steel corroding
in chloride-contaminated concrete [ 1 2 9 ] .
to externally connect ed metal surfaces) occurs during the initiation and propagation stages,
but there is no metal dissolution during the exponential-type recovery [51,91,92]. This sug-
gests that the anodic and cathodic reactions are separated in both space and time, and that
the electrons produced by metal dissolution are essentially held within the passive film and
double-layer capacitors. The potential recovery is then due to consumption of the increased
electron charge by the subsequent and continuing cathodic reaction that occurs across the
total surface.
ENM Characteristics for Various Modes of Corrosion
Uniform Corrosion
Active dissolution of iron and steel in acidic solutions is controlled by the hydrogen
evolution process. The noise signals obtained under galvanostatic and potentiostatic control
have been interpreted in terms of a stochastic process determined by bubble formation,
growth, and detachment [2].
Monitoring measurements made on mild steel in dilute sulfuric acid at the corrosion po-
tential indicate that resistance noise, charge transfer resistance from impedance measure-
ments, and weight-loss data provide similar results [51,91] (Fig. 15). Here the rate of reaction
increases with time as the carbon remaining from the alloy dissolution builds up to increase
the cathode area. In other systems, for example, in carbon-dioxide-containing brines and
aerated sodium chloride solutions, the corrosion rates fall with time as corrosion product
films develop (Fig. 16). Some organizations now recommend ENM for determining corrosion
rates [55]. It not only gives the same corrosion rate data as linear polarization resistance,
but it also provides information on localized corrosion.
The combi ned corrosion potential and current noise technique has also been successfully
used in a number of studies of coated steel [95-97, 122-128]. ENM and electrochemical
impedance provide similar indications of deterioration trends. However, EN~VI appears more
sensitive in the detection of corrosion resulting from through-film penetration of water during
t = 1
3o0 R e s i s t a n c e noi s e
~ 200 ,
0
100
0
0 20 40 60 80 100 120 140 160 180 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 3 0 0
Time (hours)
FIG. 15--Corrosion of mild steel in 0.5M sulphuric acid: a comparison of resistance noise, impedance
(charge transfer resistance), and weight loss data [91].
KEYNOTE ADDRESS 21
~ 2
i~,1 EN5 in 3 % NaCI ~ l m p e d a n c e
1 9 Noise Resistance
, . O Z R A Current
4 0
30
2 0 --"
e -
t.)
l o r
0 10 2 0 30 40 50 60 7 0 8 0 9 0 100
Time, h
FIG. 16--Corrosion of carbon steel in aerated 3% sodium chloride [70].
immersion in the test environment and the monitored resistance changes are quantified more
easily (Fig. 24).
Pitting Corrosion
As indicated previously, EN has been used by a number of investigators in studies of
pitting. Pitting is a stochastic process, and noise analysis has provided greater understanding
of the initiation and propagation stages. In particular, analysis of individual noise transients
is a useful research method for the study of fundamental corrosion mechanisms. Similar
information can be obtained from potentiostatic and free corrosion data. In studies at the
free corrosion potential, a "chemi cal potentiostat" is usually empl oyed in which small
amounts of ferric chloride are added to the sodium chloride test solution to raise the potential.
Initiation events are observed as short-lived transients. In some cases, transients may con-
tinue and give rise to unstable or metastable pits of limited life (Figs. 2, 7, 13a, and 17).
Onl y a small number of initiation events continue to form stable pits (Fig. 13b).
Most unstable and stable pits on stainless steel grow from an initiation event, which starts
to repassivate, but then appears to continue by a further reactivation process; the partial
recovery in the potential ceases as the anodic metal dissolution recommences. Metastable
pits have only a limited life and repassivate within a few seconds; stable pits continue to
grow for up to a few minutes (Figs. 13b and 18). Even stable pits have a finite life. There
are, therefore, probabilities associated with birth and death of the initiating transients and
the metastable and stable pits. The shape of the initial transients and other transients typical
of unstable and stable pits is of continuing research interest, as seen in the studies presented
by Pistorius at this symposium.
The noise trace from a stable growi ng pit is typically that of an actively corrodi ng metal
surface (Fig. 13b). Analysis of the current and potential relationships [92] show that in the
free corrosion situation, the pit is not driven by an IR effect, as with potentiostatic experi-
Ct.
e*
o
2 0
10
0
0, 0 1.0 2.0 3.0 4.0 5.0
"rime I s
FIG. 1 7 - - Pi t initiation t ransi ent obtained potentiostatically; repassivation occurs wi t hout pi t growth
[10].
ments, but by the retained local environment. In this context, it is significant to note the
observations of Cavalcanti [130], who demonstrated the presence of a preexisting passive
film across a pit mouth, and also the more recent work by Burstein et al. [9, 10, 90] in which
initiation and metastable transients are consistent with the absence or presence of the original
passive film.
The partial coveri ng of a pit mouth would appear to play an important part in controlling
the diffusion processes in the incipient pit environment. This local environment in turn de-
termines the pit life and the type of noise transient observed. This t ype of retained film
model is confirmed by pitting studies at UMI ST [92] conducted under turbulent flow con-
ditions that showed that some stable (propagating) pits can be prematurely terminated by
eddy penetration into the pit from the liquid flow.
The aut hor' s opinion is that initiation transients are due to local film rupture events [98];
electrochemical pitting noise is mechanically triggered. This concept is based on the elec-
trostrictive model suggested by Sato [131] in which internal forces generated within the film
0. 4 1. 3
1.1
0. 9
0.5
0, 3
0.1
J , - - - -
0 ~ -0.1
5 10 15 0. 0 2. 0 4. 0 6, 0 8. 0
" ni ne I s 1 1 r n e I s
FIG. 18- - Met as t abl e pi t t i ng initiated by nucleation transients t hat do not immediately repassivate
[10].
0.3
~E 0. 2
8
0.1
KEYNOTE ADDRESS 23
are relieved by film rupture. The overall mechani sm involves adsorption of negatively
charged chlorine ions, and this adsorption increases as the electrode potential rises towards
the pitting potential. The change in adsorption affects the film surface tension which in turn
changes the pressure within the film. A film rupture event that occurs at an area of high
chloride adsorption (or salt island) has a greater probability of continuing to a metastable or
stable pit. Other authors have considered diffusion processes associated with the formation
of salt islands [132].
Measurements on-site used to moni t or plant corrosion also exhibit stochastic noise pro-
cesses that change in response to the environmental conditions. In general, there are often
gradual changes from uniform corrosion to pitting and back again in many industrial situa-
tions. The presence of active corrosion in combination with pit initiation can be seen in
many noise-monitoring data records. Nevertheless, in-plant data frequently show evidence
of typical pit initiation and metastable pitting processes described above (Fig. 2), but onl y
infrequently is stable pitting detected.
Electrochemical noise measurements on pitting, either by analysis of individual transients
or a series of transients, is able to provide detailed information on the fundamental processes
involved. The actual stochastic processes are influenced by factors such as the age and
thickness of the passive film, the composition of the environment, the electrode potential,
diffusion restrictions as a result of pit geometry, and flow enhancement in turbulent
environments.
Crevice Corrosion
Crevice corrosion on stainless steel is typically observed as pitting, but with the anodic
dissolution assisted by restricted diffusion produced by the crevice geometry. Initial film
rupture or breakdown occurs within the crevice, and then, provided the corrosion potential
is sufficiently anodic, the metal dissolution will continue as a large current transient
[93,94,118,133]. This noise transient is similar to that produced by a stable pit but with an
extended life that continues over a number of hours.
In the case of iron or carbon steel, which has a less protective film, regular potential
oscillations may be observed (Fig. 22). These appear to be characteristic of diffusion control
but are more likely to be due t o the formation and dissolution of unstable films in the
restricted crevice environment [47]. Similar oscillations have been observed with stress-
assisted intergranular corrosion [51] (Fig. 23) and unstable film formation and dissolution
[135].
Stress Corrosion Cracking
Electrochemical noise measurements have been reported for bot h potentiostatic controlled
experiments [81,84,85] (Fig. 21), and corrosion monitoring at the free corrosion potential
[51,82,83,86] (Figs. 19 and 20).
Anodi c transients are the result of metal dissolution at the crack wall and are therefore
similar to pit initiation. In many cases, there could be difficulty in the ability to discriminate
between anodic SCC, pitting, and crevice corrosion. Extensive active corrosion outside the
crack can mask the cracki ng transients [82,118,136].
Cathodic transients can be observed in some SCC systems (Figs. 19 and 20). These result
from the hydrogen generation reaction that occurs on the newly fractured metal surface of
a propagating crack. This freshly exposed surface is highly catalytic, and hence, conversion
of adsorbed water to atomic hydrogen occurs rapidly at the base" of the crack. The fast
cathodic reaction consumes electrons that are removed from the film and the electrochemical
7. 6
> 7.2
E
i
o.
uJ 6.8
6. 4
0 1 O0 2 0 0
"rime, s
-12
-10
-8
z"
o
LLI
-6
-4
. l I I ,
I I I I I L
I , I I I I d i l l , ,
I , I , i1 1 ,1 - I , H I I I d ,
J I L I I I H l i k l , l , H H , I 1 1 1 4
" , ~ ~
0
I
I . I I J .
. 1 1 II I . J l H L
II1,11 I I I 1 ~ 1
I l J l | I d d i l | l
l oo
"lime, S
i , I
J l t i
i i . I I I I I
200
FIG. 19--Rapid stress corrosion cracking; hydrogen discharge within the crack [51].
double layer present on the metal surface, both external to the crack and on the crack walls.
The electrochemical interface is then recharged by subsequent metal dissolution. The ob-
served initial potential and the current transients therefore both increase in a positive direction
during the propagation steps. Rapid branched cracking (Fig. 19) and slowly propagating
single cracks (Fig. 23) have been observed with electrochemical noise. Figure 23 also shows
an anodic metal dissolution transient following the initial cathodic transient.
Laboratory Testing and Product Testing
EN has been used in a number of inhibitor studies and evaluations [88,134,137-140].
Corrosion rate data and indications of pitting are typical examples of these applications.
One of the most significant ongoi ng developments over the past ten years has been the
use of EN in coatings evaluations [141]. Particularly noteworthy is the work by Skerry et
al. [56, 95-97, 122, 124, 125, 128] that has demonstrated that noise can now be considered as
a standard test procedure. Its main advantages are ease of application and production of
quantifiable data which, unlike impedance measurements, are also easy to interpret.
Typical data can be presented as a change of noise resistance with time of exposure. In
Fig. 24, the coatings were assessed as maintenance painting systems in a salt spray test; the
acrylic had a good initial performance but quickly deteriorated to give a value similar to the
mild steel control, and the preferred option was the urethane alkyd. In general, through-
coating corrosion is a relatively slow process with good systems, and measured parameters
KEYNOTE ADDRESS 25
- ~ . o : i ~ I I ' J I ]
I ~ ~ J i t
I I ! ~ i 1
-60.0
> , . . !..k ! . , , ! ' ~ t . . . .
. . ,
- 62. 0
' " I ! i ~ i I I !
- 6 4 . 0 i , i , I ! i i I 1
-66.0 --
0 2 0 40 6 0 8 0 100
Time, s
o 0
tu %
t
i i
b
f l f i l i
"0.8
0 2 0 40 60 8 0 100
~mo, s
FIG. 20--Slow stress corrosion cracking propagation: (a) hydrogen discharge; (b) hydrogen discharge
followed by metal dissolution [51].
do not change rapidly during the test exposure period. EN is, however, very sensitive to any
change, and hence, trends of resistance noise with exposure time are ideal for coating eval-
uations. The data are more amenable to simple analysis involving water uptake and increased
corrosion of the substrate than that provided by electrochemical impedance.
Corrosi on Moni tori ng of Industrial Plants
The advantages of electrochemical noise for corrosion-monitoring applications have
been demonstrated in numerous publications over the past ten years [3,5,51,54,113,114,121,
144-147].
Evaluations have been made of acid dew point corrosion in flue gas exhaust equipment
and duct work [113] (Fig. 25), flue gas desulphurizing systems [142,143] (Fig. 26), boiler
plant [144], cooling water systems [5,121,145], acid cleaning, oil and gas production, process
plant [121], and reinforced concrete [112,115,147].
The mai n emphasis has been troubleshooting, assessment of process control as it affects
corrosion control, effect of environmental changes, and inhibitor evaluation. Assessment of
corrosion rates, identification of the onset of localized corrosion, and trend monitoring are
typical of most studies. Studies of microbially induced corrosion have also been reported
[148].
26 E L E C T R O C H E M I C A L N O I S E M E A S U R E M E N T
500
r
o
U
2
( 1 )
i
O n s e t o f
s t a b l e
c r a c k i n g
P o t e n t i a l ~ ~ . t
J
P o t e n t i a l ,
! ! 1 1 1 g o ~ s m o r e
I C u r r , - t , , - -
~
(to approx, s ~ )
" t i m e f r o m y i e l d I h o u r s
I
1 5 5 . 5
- I O0
- 0 >
E
- l O o
- 2 0 0
F IG . 21- - Cur r ent noise transients obtained in potentiostatically iron in tO-ppm thiosufphate [8 4 ].
a b
E
- 6 L , , . J _ . k L L I . ~ . . . . t . . , I k . ' _ ) ~ , , I
(mV) -8 V'L411hll.adA,t/l~| ~ '
I I I I W I I I I M I I I I I
))IIllliIllll)I I 11
I I I I I m l l l l l l l l l I
0. 1 I i ~ - 12
o_ I I I I l m l l l l l l l l l I I
w I I I l i l l l i i l l l l i l I I
-14 III11111111 I
o I
- 0. 1 100 2 0 0
" r i me , s
- 30 i ' L
i
10 2 0 t ( r ni n)
.2o i i
z l i H i l l i l l ) ,?, :,
0 100 2 0 0
' ~m0, $
F IG . 2 2 - - ( a ) Potential noise f rom crevice corrosion [ 4 7 ] and (b ) pot ent i al and current noise f rom
pl ant monitoring.
KEYNOTE ADDRESS 27
- 4 3 4 i,m
i
- 4 3 6
~ -438
uJ -440
S
t I
0 20
x.=
4 0 6 0 8 0 1 0 0
~me, s
60
40
'~. 20
O 0
iii
-20
-40
0 2 0 4 0 6 0 8 0 1 0 0
"time, s
FIG. 23--Oscillating current noise from stress-assisted intergranular corrosion typical of a micro-
crevice [51 ].
Concl usi ons
The above review has outlined the major parameters and factors to be considered in
undertaking EN measurements and their evaluations. EN has been shown to be useful in
fundamental research studies; for testing of materials, coatings, and inhibitors; on-site for
online corrosion monitoring both for process control and surveillance; and for troubleshoot-
ing or investigation of plant corrosion problems. An appreciation of the likely sources of
noise and their measurement is essential to recogni ze the advantages and limitations of the
techniques.
Noise analysis of time records for research purposes is not necessarily a trivial task. It
may require detailed analysis of individual transients to provide information on the funda-
mental processes that underlie the corrosion mechanisms. In other cases in which a series
of transients are evaluated, a modeling exercise is often used to convert a Poisson process
into a power spectral density plot (the frequency domain representation) by means of the
Fourier transform. This modeled data, which describes the noise transients in fundamental
terms, is then compared with experimental data to propose viable mechanisms.
In practical situations, the shapes of the random noise and the transients can be used to
discriminate between uniform corrosion and various forms of localized corrosion. A simple
28 ELECTROCHEMI CAL NOI SE MEASUREMENT
10 a
9
E 10 s
r
0
8"
9 ~ 1 0 4
O
N
' = 10 3
n o
1 0 2
x - E po xy
9 - U r e l h a n e A l k y d
+ - A c r y l i c
9 9 - M i l d S t e e l
I
. . . / I \ < - , ^ .
5 9 13 17 21 25 29 33 37
T i m e ( d a y s )
F I G . 24- - Changes in coating resistance obtained by monitoring the corrosion current and noise [ 146] .
st at i st i cal i nt erpret at i on of the EN dat a based on the first and second moment s of the random
signal (the st andard devi at i on and the vari ance, respect i vel y) can al so pr ovi de i nformat i on
on uni form corrosi on rates (where ~,./~i -- R,,, ico~ = B/R,,, and B is a St er n- Gear y const ant )
and the degr ee of l ocal i zed act i vi t y (from ~ili . . . . . ). Passi ve syst ems have low levels of noi se
200 . . . . . 9 . . . . . . . . . . . . . . . . . . . . . . . . .
f
i
, ElM
i
i ' ~ = Fl ue gas temperature
_ . ~ . E 0 N . . ~
1 2 3
t i me (hours)
F I G . 25- - Onl i ne monitoring during a boiler startup showing dilute sulfuric aci d condensation [ 1 1 1 ] .
150
G"
~" 100
5O
0
KEYNOTE ADDRESS 29
20K
10k
0
i
Impedance
v m
I m A
lOl.tA
Coupling current
I I _ l t
lOmV
loo~
t ~
1/JA ~Current n o i s e
1 o n A
0 . 1 n A ~ c "i" - -
(~
100
0
Pmbetemp.
, t
m
i
1, / . , , , I
(~ ~Gas temp.
0 6
t
12
L ~
I
Absorber Reheater
o n - l i n e s t a r t - u p
FIG. 26--On-line monitoring in a flue gas desulphurization plant.
with potential fluctuations of about 1 mV and current fluctuations of less than a few
i~A/cm ~ of electrode area. Uniform corrosion has an increased noise level, typically a few
10s mV and up to 10 ~A/ cm 2, while localized corrosion gives rise to distinct transients up
to 100s mV and 100s i~A/cm 2.
As to whether "electrochemical noise is the definitive electrochemical corrosion tech-
nique" will only be fully answered in the long term as further scientific information becomes
available. However, the literature presented demonstrates that ENM provides some of the
most fundamental information on the basic (stochastic) processes involved in electrochemical
corrosion reactions. Some current and potential noise is also sufficiently stationary to be
transformed into electrochemical impedance spectra, and this will provide an alternative way
to present EN data. It is also likely in the future that EN data will be analyzed using chaos
theories.
At a more practical level, EN information has to date been used in the evaluation of
materials, coatings, and inhibitors. In particular, ENM could be adopted as a standard test
method for coatings and used to determine corrosion rates. Technical developments have
also enabled EN to be used on-site for troubleshooting and corrosion control.
Acknowl edgment s
The author wishes to express his appreciation to the many students, research workers,
colleagues, and friends at UMIST, CAPCIS, and RTCML and to researchers overseas who
contributed in many ways to his understanding of electrochemical noise. In particular, the
research support from UK MoD (John Rowtands) and ICI (the late Mervyn Turner) for Les
Callow and Karl Hladky is gratefully acknowledged, as this was responsible for initiating
the electochemical noise development. The research of Pete Searson, Bill Cox, Wai Him
Mok, Ihasan A1-Zanki, Jorge Uruchurtu, and Dave Moore is also appreciated, as were the
stimulating discussions with Dave Eden over the past 15 years. Acknowledgments are also
given to CAPCIS for support in preparing this review and RTCML for the contribution to
expenses in attending the electrochemical noise symposium.
Re f e r e nc e s
[1] Gabrielli, C., Huet, E, Keddam, M., and Oltra, R., Corrosion, Vol. 46, 1990, p. 266.
[2] Gabrielli, C. and Keddam, M., Corrosion, Vol. 48, 1992, p. 794.
[3] Gabrielli, C., Huet, E, and Keddam, M., "Investigation of Metallic Corrosion by Electrochemical
Noise Techniques," in Electrochemical and Optical Techniques f or the Study and Monitoring of
Corrosion, M. G. S. Ferriera and C. A. Melendres, Eds., 1993, p. 135. Electrochemical Society,
Inc., Princeton, NJ.
[4] Warris, A., "The Monitoring of Sacrificial Anode Galvanic Couples," M.Sc. dissertation, Univer-
sity of Manchester, 1985.
[5] Winters, M. A., Stokes, E S. N., Zuniga, E O., and Schlottenmeier, D. J., Corrosion Science,
1993.
[6] Gabrielli, C., Huet, E, and Keddam, M., Journal of Applied Electrochemistry, Vol. 15, 1985,
p. 503.
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[129] Carr, R., Eden, D. E., and Dawson, J. L., patent application, 1993.
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[135] Li, W., Nobe, K., and Pearlstein, J., Corrosion Science, Vol. 31, 1990, p. 615.
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Correlations to Other Electrochemical
Techniques
Ugo Be r t oc c i 1
A Comparison of Electrochemical Noise
and Impedance Spectroscopy for the
Detection of Corrosion in Reinforced
Concrete
REFERENCE: Bertocci, U., "A Comparison of Electrochemical Noise and Impedance
Spectroscopy for the Detection of Corrosion in Reinforced Concrete," Electrochemical
Noise Measurement for Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R.
Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., American Society
for Testing and Materials, 1996, pp. 39-58.
ABSTRACT" Electrochemical impedance spectroscopy (EIS) and electrochemical noise mea-
surements (ENM) were carried out on small concrete blocks with embedded steel rods, im-
mersed in solutions of highway deicers, mainly sodium or magnesium chlorides with corrosion
inhibitors added. Voltage and current fluctuations between identical electrodes were recorded,
and different signal-processing schemes were tested. Various problems experienced in the
course of the work are described. Corrosion polarization resistances obtained by EIS are com-
pared with values of the ratio of the standard deviations of the voltage and current fluctuations.
The results suggest that the type of ENM used in this work is subject to considerable uncer-
tainties, and further work would be necessary before the method can be applied with sufficient
confidence to corrosion monitoring.
KEYWORDS: corrosion, reinforced concrete, electrochemical noise, impedance spectroscopy
This paper presents part of the research carried out at the Turner-Fairbank Research Center
of the Federal Highway Administration on highway deicers. The main purpose of the work
was to examine if the addition of corrosion inhibitors to commercial deicing mixtures, which
contain mainly chloride salts, affects the corrosion behavior of steel in concrete. The solu-
tions used in the testing are listed in Table 1, together with the numerical designation used
throughout this paper.
The principal measurement method used was electrochemical impedance spectroscopy
(EIS), but, at the same time, it was decided to carry out electrochemical noise measurements
(ENM) on the same set of test specimens to learn about the utility of ENM in monitoring
corrosion in steel-reinforced concrete.
Problems encountered in implementing the specific ENM technique selected for this work
are described. The ENM results obtained on electrochemical ceils, which were also being
studied by EIS, are presented and discussed, to compare their electrochemical behavior, as
shown by the EIS measurements, with that obtained from EN data.
Senior research associate, Turner-Fairbank Highway Research Center, Federal Highway Administra-
tion, 6300 Georgetown Pike, McLean, VA 22101.
39
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4

BERTOCCI ON DETECTION OF CORROSION IN REINFORCED CONCRETE 41
ENM Method
Various met hods have been used for ENM studies requi ri ng mor e or l ess compl i cat ed
i nst rument at i on. To si mpl i f y the ci rcui t ry and avoi d t he necessi t y for t ransformat i ons in the
frequency domai n, a number of workers have car ded out ENM bet ween t wo i dent i cal el ec-
t rodes at open ci rcui t [ 1 - 3 ] . Thi s met hod, in its most el abor at e form, uses t wo pai rs of
el ect rodes, al l made of t he mat eri al under st udy and of equal surface area. Two of t he
el ect rodes, separat ed by a short di st ance in the el ect rol yt e, are connect ed by a zero-resi st ance
ammet er ( ZRA) , whi ch records t he fluctuating current s flowing bet ween the two. The ot her
t wo el ect rodes are connect ed t hrough a hi gh i mpedance vol t met er, whi ch records t he vol t age
fluctuations bet ween them. The proponent s of this arrangement [ 4 , 5 ] poi nt out that it is
si mpl er than t hose usi ng a pot ent i ost at , and t hat t he measurement s are per f or med at t he
corrosi on pot ent i al , whi ch makes t hem mor e rel evant to the act ual servi ce condi t i ons.
The anal ysi s of t he dat a is carri ed out by cal cul at i ng the st andard devi at i on of t he current
and vol t age fluctuations over a chosen t i me i nt erval and then consi der i ng t he rat i o of t he
t wo as a measure of the corrosi on resi st ance of t he mat eri al [ 4 , 5 ] .
The si gni fi cance of this t ype of measur ement has been di scussed in a previ ous paper in
cooper at i on wi t h Huet [6]. In it, a model is pr oposed to account for t he vol t age fluctuations
in an i sol at ed el ect rode, whi ch assumes that t he surface can be di vi ded in a l arge number
of pat ches. On each of them, smal l changes at the i nt erface l ead to short -l i ved changes in
the i nt erfaci al resi st ance. These, in turn, cause fluctuations in the anodi c and cat hodi c part i al
currents. Inst ant aneous devi at i ons f r om a zero net current in each patch, summed over the
whol e ar ea A, wi l l dri ve the el ect r ode pot ent i al , posi t i vel y or negatively, so as to reach
compensat i on bet ween anodi c and cat hodi c current. It is al so assumed that t he resi st ance
changes of the vari ous surface pat ches are st at i st i cal l y uncorrel at ed; therefore, the size of
the pat ch is det er mi ned by t he spat i al ext ent of the correl at i on.
Al t hough the descr i pt i on of the model is easi er starting from t he current fluctuations as
the " caus e" of t he vol t age fluctuations, bot h are the consequence of the physi cal changes
on the surface, and it is i dl e to argue over which, current or vol t age, causes the fluctuations
of the other.
The i nst ant aneous devi at i on of the current f r om zero is the sum of the l ocal fluctuations
over al l M pat ches, each fluctuation bei ng the pr oduct of a scal i ng factor, i o , wi t h t he di -
mensi ons of a current density, and a r andom number, Pk, wi t h an average val ue of zero and
st andard devi at i on, or, so t hat the t ot al current, I ( t ) , is
k - M
z ( t ) = io ~ p~ (1)
k- I
Assumi ng that the fluctuations are nor mal l y di st ri but ed, the vari ance of the current I ( t ) is
then proport i onal to the number of pat ches, that is, t o t he surface area of the el ect rode, and
the st andard devi at i on of the current fluctuations, s~, wi l l be pr opor t i onal to t he square r oot
of the area A
sz = KV~ (2)
where K is a proport i onal i t y constant. Because the fluctuations are smal l , one can assume
that t here is a l i near rel at i onshi p bet ween t he faradai c part of t he current densi t y of the
fluctuations and t he el ect r ode pot ent i al . The resul t i ng rel at i onshi p for the vol t age is
V(t) = R i(t) - C dt ] = R k:,~ Ok-- C- - ~
(3)
where i is the corrosion (or exchange) current density and R and C are the unit values of
the electrode resistance and double layer capacitance, respectively. From this formula it can
be seen that high-frequency current fluctuations are shunted by the capacitance and cause a
smaller effect on the voltage than low-frequency fluctuations of the same amplitude. Whereas
the standard deviation of the total current defined above varies with surface area as shown
in Eq 2, that of the current density is inversely proportional to the square root of the area
and, because of Eq 3, so will the standard deviation of the voltage fluctuations, sv
(4)
FIG. 1--Shape and size of the cast concrete specimens.
where B is a proportionality constant. Therefore, for the measurement of the voltage fluc-
tuations, it is better to use as small a surface area as possible t o increase the amplitude of
the signal.
The current fluctuations are driven by the voltage fluctuations that occur independent of
each other on the t wo electrodes. I f the current flowing between the two electrodes is neg-
ligible compared to the partial currents within each one, the electrical connection will not
affect significantly the random current fluctuations within each electrode. With the same
reasoning as that used t o describe the influence of the surface area on the voltage fluctuations,
it can be shown that the standard deviation of the current density i e x t is inversely proportional
to the square root of the area. Therefore, the standard deviation of the total external current
s~r t, whi ch is the quantity being measured, increases as the square root of the area. As a
consequence, although small electrodes may be more suited for voltage measurements, the
current measurements favor the use of large electrodes.
The current density generated by the voltage fluctuations of the t wo electrodes, i e x t , de-
pends on the admittance of the circuit, whi ch is formed by a faradaic impedance in parallel
to a double layer capacitance C, followed by the resistance of the solution, R,, between the
electrodes. Here this circuit is simplified by assuming that the faradaic branch is a simple
resistance, R. From Eq 3 we have
v R c ( d r R
i"x' = R + R------~ + R + R'-----~, - ~ - " d t ] ( 5 )
It is easy t o see that, for R s = 0, substitution of Eq 3 into Eq 5 gives Eq 1, the external
current is identical to the fluctuations within an electrode. Because the current to be measured
decreases as R, increases, it is convenient to keep the solution resistance small. This justifies
the practice of using t wo electrodes facing each other at a short distance.
Accordi ng t o this model, because of the existence of a capacitative branch in the electrode,
the amplitude of the current iext should be larger for high-frequency fluctuations. It would,
therefore, be more reasonable to presume that the ratio, X, of the standard deviations woul d
be proportional to the modul e of the impedance at some frequency larger than zero, so that
X woul d not necessarily be a good measure of the corrosion rate, that is, to the zero frequency
limit of the electrode impedance.
The model describes above presupposes uniformity of conditions on all the electrodes, a
thing that may not be easily realized i f the mai n form of corrosi on is, for instance, pitting.
Therefore, experimental testing is of great interest to build confidence in the usefulness of
this ENM technique.
Experimental Procedures
The measurements were car ded out on steel rods embedded in concrete, exposed to various
solutions by immersion, over about seven months. The shape and size of the specimens are
shown in Fig. 1. To promot e uniform corrosion conditions for the four carbon steel rods in
each block, they were kept short-circuited unless measurements were being performed.
To maintain an oxygen-ri ch environment inside the concrete, the specimens were subjected
to a regular regime of i mmersi on in the solution from Monday t o Friday and let to dry over
the weekend. This regime was followed, with a few exceptions, for several months.
Immersi on of the specimens was done in 600- mL glass beakers, in which about 150 mL
of solution was poured. The level of the liquid reached about 1 cm below the top of the
COMPUTER
FIG. 2--Schematic view of the EN measurement system.
concret e bl ock, and car e was t aken to prevent the sol ut i on from wet t i ng bet ween the pr o-
t rudi ng rods.
Measurement Scheme for EN
Data Acqu&ition
The el ect ri c ci rcui t for ENM used t hree of the f our r ods in each concret e bl ock: one of
t hem was common to the current and vol t age measur ement circuits. The current bet ween it
and anot her rod was measur ed by means of a ZRA, whereas t he vol t age fluctuations bet ween
the common rod and t he t hi rd one were r ecor ded by a hi gh-i nput i mpedance voltmeter. The
use of t hree el ect rodes rat her than four does not al t er t he pri nci pl e of t he measur ement
scheme [7], but si mpl i fi es the groundi ng of the circuitry. The onl y observabl e di fference is
that, wi t h t hree el ect rodes, some correl at i on bet ween current and vol t age fluctuations has to
be expect ed.
No hi gh-pass filters were i nst al l ed to el i mi nat e DC and very l ow-frequency si gnal s, what
we may cal l " DC" drift, but it was deci ded to try to mi ni mi ze t hei r effect by di gi t al proc-
essing. Di fferent schemes were tried, whi ch wi l l be di scussed later.
A t wel ve-bi t , mul t i channel , i nput / out put ( I / O) card i nst al l ed in a personal comput er al-
l owed t he si mul t aneous r ecor di ng of current and vol t age from four concret e bl ocks. On each
of t he ei ght si gnal channel s, an ant i al i asi ng t ow-pass t hree-pol e filter was i nst al l ed, wi t h a
BE RT OCCI ON DE T E CT I ON OF C O R R O S I O N I N R E I N F O R C E D C O N C R E T E 45
~ >
E
J ~
" O
d
a .
o ~
<
J ~
" O
c~
a .
u ~
~ >
E
J O
0 . .
U ~
- 6 0 - ' , , , , , j
- 7 0
eo 4 so B l oo 12o
Fr e que nc y , Hz
- 4 0 , , , , ,
- 5 0
-60
- 7 0 ' ~ 6 1 0 ~ , I
2 0 4 8 1 0 0 1 2 0
Frequency, Hz
-40 , , , , ,
-50 ~
-60
-70
- 8 0 ' ~ , ~ I ,
0 2 0 4 6 0 8 1 0 0 1 2 0
Fr e que nc y , Hz
-40
: >
E -5o
"~ d
~ -60
-70
0 2 4 6 8 1 0 1 2 1 4 1 6
Frequency, Hz
FIG. 3- - Spectr a of the i nstrumental noi se: (a) Voltage channel O. Ampl i fi cati on -~500. Acqui si ti on
rate = 256 pts/s. (b) Current channel 1. Ampl i fi cati on = 100. ZI A ampl i fi cati on = 105 V/A. Acqui si ti on
rate = 256 pts/s. (c) Voltage channel 6. Ampl i fi cati on = 500. Acqui si ti on rate = 256 pts/s. (d) Voltage
channel 6. Ampl i fi cati on = 500. Acqui si ti on rate = 32 pts/s.
46 E L E C T R O C H E MI C A L N OI S E M E A S U R E M E N T
cut of f frequency o f 15 Hz. A schemati c circuit is gi ven in Fig. 2. For the acqui si ti on and
processi ng o f the signals, commerci al software produci ng virtual instruments was used.
Efforts were made to decrease the instrumental noi s e o f the s ys t em by electrical shi el di ng
o f the cel l s and the instruments and usi ng battery-powered component s. The instrumental
noi se was much affected by the amplification, whi ch coul d be applied t o the input signals.
For the vol t ages, the I / O card provi ded four levels: 1, 10, 100, and 500. Each l evel corre-
sponded to different maxi mum signals, respecti vel y, 10 V, 1 V, 100 mV, and 20 mV. For the
current si gnal s, besi de the same amplification choi ces in the I / O card, the ZRAs coul d be
set for conversi on factors f rom 104 to 107 VI A. Because the instrumental noi se was l owes t
when the amplification o f the I / O card was the largest, a major factor limiting the sensi ti vi ty
was the presence o f a DC si gnal that compel l ed a reduction in amplification t o stay wi thi n
79
O
C
P
O
Z
UJ
78
77
76
75
74
73
72
71
- 18
5 0 0 1 0 0 0 15 0 2 0 0 0
Ti me, s
- 19
- 20
-21
- 22
>
E
=;
O
>
Z
UJ
' ' ' 0 5 0 0 1 0 0 0 15 0 0 0 0
Ti me, s
F I G. 4- - - E N recordi ngs bef ore pr ocessi ng (Sol uti on 3 ) : ( a ) Vol tage. Acqui si ti on rate = 0.5 pts/ s. (b)
Current. Acqui si ti on rate = 0.5 pts/s.
the allowed input limits. It was also found that the instrumental noise varied from channel
to channel. Cross-talk between adjacent channels was found to be significant. This problem
was solved by using onl y every other channel of a 16-channel I / O card.
For the voltage-measuring channels, the standard deviation of the instrumental noise (mea-
sured with inputs short-circuited) was between 8 and 16 ixV at the maxi mum amplification
of 500, but it was about four times larger if the amplification had to be reduced to 100. For
the current-measuring channels, the instrumental noise (measured with inputs open-circuited)
ranged from 4 to 0.04 nA, but the settings most often used had an instrumental noise from
0.1 to 0.4 nA. Despite the antialiasing filters, some structure was observed in the spectra of
the instrumental noise. Figure 3 shows the examples of instrumental noise spectra. Al t hough
the spectrum of Channel 0 (Fig. 3a) did not show any peaks, that of the noisiest channel
(Channel 6, Fig. 3c), had several peaks, some ten times larger than the background and up
to - 4 5 db mV, which is equal to 6 ~V. When measuring at low acquisition rates (31 ms/pt,
in the example of Fig. 3d), these peaks were aliased and appeared as l ow-frequency peaks,
as shown in Fig. 3d.
Data Processing
Al t hough the acquisition of the time series could be observed in real time, the data proc-
essing for the calculation of the standard deviations and their ratios was done subsequently.
For the purpose of testing different processing schemes, it is clearly advantageous t o apply
t hem to the same data sets. However, i f EN measurements have t o be used for monitoring
corrosion, processing in real time, with immediate display of the results, would be necessary.
Methods for doing so are being developed, and onl y preliminary results are available.
The time series of N voltage and N current readings were taken mostly at a rate of a point
every 2 s (v = 0.5 Hz), generally with N = 1000 or 1024. The acquired data immediately
indicated that the assumption of a zero average difference in voltage and current between
the supposedly identical electrodes was not fulfilled. Substantial voltage differences between
rods embedded in the same concrete bl ock had already been observed in open circuit poten-
tial (Eo~) measurements. As soon as the short circuit was broken, in many instances the Eo~
would drift apart rapidly. Figure 4 shows voltage and current recordings before any proc-
essing: the drift in voltage is evident, but the current data (Fig. 4b) also show a large DC
component. Standard deviations calculated from the raw data would be quite large because
of the low-frequency components. Therefore, it was necessary to eliminate both the DC
component and slow drift. For this, the value of the first point (n = 0), was subtracted from
all following values, and then the time series was passed t hrough a fifth order, high-pass,
Butterworth digital filter, with a cut off frequency vc = v/N, or approximately 0.5 mHz. The
result of such a treatment is illustrated in Fig. 5, which shows the same curves of Fig. 4
after filtering. Here it is possible to see that some of the spikes that appear in the current
record coincide in time with transients in the voltage, which were almost impossible to detect
in the original recording.
Anot her scheme for the elimination of DC and slow drift was tried. This consisted of
fitting the raw data to a second- or third-order pol ynomi al and then using the residuals as a
measure of the noise. The method gave results similar to high-pass filtering, except when
the fluctuations appeared to have extremely low frequencies, close t o the cut off limit of the
digital filter.
Because sporadic transient spikes generated by other electrical equipment in the laboratory
could not be completely avoided, and because they considerably affected the standard de-
viations, the high-pass-filtered time series were additionally processed, when necessary,
48 E L E C T R O C H E MI C A L NOI S E M E A S U R E M E N T
E
. ~
0
= >
Z
u J
c
e .
P
i .
0
Z
UJ
F I G. 5- - Same
0 , 6
0 , 4
0 , 2
0 , 0
- 0 , 2
- 0 , 4
- 0 , 6
0
I
5 0 0 1 o l o o 1 5 1 0 o 2 0 0 0
Ti me, s
-1
- 3
o
, i
I
5 0 0 1 0 1 0 0 1 5 1 0 0 2 0 0 0
Ti me, s
recordi ng as i n F i g . 4 a f t e r f i l t e r i n g : ( a ) vol tage and (b) current.
through a digital filter to remove the unwanted spikes. The occurrence of these spikes coul d
be detected easi l y because they were much larger than normal and appeared at the same
ti me on all measuring channels.
Once the ti me series were adequately filtered, running standard devi ati ons (Sv). and (st).
values coul d be computed. Thi s was done usi ng either all points from 0 to n for the value
of index n or a shorter record length L (L < N) for n > L. In this work, the first alternative
was used. From these standard deviations, their ratios X. = ( sv) ./ ( st) . were obtained, a typical
exampl e of whi ch is shown in Fig. 6. In general, the running ratio tended to stabilize after
a few hundred points. It is therefore reasonable to try to summari ze the curves by a si ngl e
number. To do so, running means and standard deviations of (Sv)., (st)., and X . were com-
puted for record lengths L = N / 2, one hal f of the original time record, N. The last value of
the mean can be considered as an indication of the average val ue of these quantities, whereas
B E R T OC C I O N DE T E CT I ON OF C O R R O S I O N I N R E I N F O R C E D C O N C R E T E 49
8 0
7 0
6 0
E 50
t -
O
4 0
, , =
3 0
2O
10
0
0
I I I
5 0 0 1 0 0 0 1 5 0 0
T i me , s
2 0 0 0
FI G. 6--Typical standard deviation ratio X. . Acquisition rate = 0 . 5 p t s / s .
the standard devi at i on i s an i ndi cat i on o f thei r st abi l i t y wi t h t i me. The val ues report ed i n
Tabl e 1 we r e c omput e d thi s way.
EI S Re s u l t s
To c ompar e the ENM data wi t h the e l e c t r oc he mi c al behavi or as s hown by EI S, the resul ts
o f the i mpe danc e me as ur e me nt s wi l l be bri efl y s ummari zed. Al l me as ur e me nt s we r e carri ed
7 , o
_ ' I ' - - - * - L o g q z l l
6 - - 2 0
0
E ~
t -
O 5 - -4o
N
n r . .
O1 0 .
O
- - I 4 - - 6 0
3 t - 8 0
- 4 - 3 - 2 - 1 0 1 2
L o g ( F r e q ) , Hz
FI G. 7--Typical Bode plot showing high Ro and only one time constant (Solution 5).
5,0 0
i i i i i i
9 -10
4, 5
% 2~
t~ "o
x
E - - 30 &
0 4,0
c
~,, - -4o
t~
O - -50 ' -
--I 3,5 O.
I
,--.o--- Log IZl -60
3,0 -70
-4 -3 -2 -1 0 1 2
L o g ( F r e q ) , Hz
FIG. 8--Typical Bode plot showing lower Ro and two time constants (Solution 1).
out at the Eoc. The ci rcui t s that best si mul at ed t he exper i ment al dat a were ei t her a si mpl e
RC paral l el fol l owed by a resi st or or t he one wi t h an addi t i onal const ant phase el ement
(CPE) of Sl ope 1 (45 ~ in seri es to the resistor. The CPE pr obabl y is t he effect of di ffusi onal
t ransport in the concret e, as a Warburg i mpedance over a finite-length di ffusi on layer. The
fitting rout i ne was abl e to pr ovi de an ext rapol at i on to zero frequency, gi vi ng a val ue for the
-100 m
[] a m ~ B , ~ m - - - m n
- o ~ q~.~_ _ ~ =
t,l,,I -200 m ~ ~ 1 ~
O
(t'}
-300
S -400 [] m B" " ~ - - I~
% l ,
-500 m m
y = - 2 9 5 . 4 2 - I 0 3 . 0 1 X R ^ 2 = 0 . 8 2 9
-600 I 11 I I
3 -2 - O 1
l o g ( l / R) , l l S/ cm 2
FI G. 9--Cumulative plot of measurement potential E m v e r s us electrode admittance.
E
O~
O
Z
LU
5 0 0 1 0 0 1 5 0 0 2 0 0 0
Ti me, s
i i i i
1
0
1-
r
= b
P
i . - 1
( J
Z
I L l
- 2
- 3 I
5 0 0 1 0 l o 0 1 5 1 0 0 2 0 0 0
Ti me, s
FIG. l O- - Fi l t er ed EN recordings. Solution 1: (a) Voltage. Acqui si t i on rate = 0. 5 pt s / s . (b) Current.
Acqui si t i on rate = 0. 5 pt s / s .
overall electrode resistance. This value, however, is, in general, not very accurate because
the measurements had to be extended to very low frequencies where the scattering of the
experimental points was large.
The simpler RC circuit was associated with very large values of the electrode resistance,
R o, 10 MI I cm 2 or more, and with double-layer capacitance values, Cdt, between 30 and
60 p~F/cm 2, indicating very low corrosion rates. A typical Bode plot is shown in Fig. 7,
obtained in Solution 5. In the range of frequencies sampled by the ENM, the slope of the
absolute impedance I~ with respect to the logarithm of the frequency, v, is about - 1 , and
its value is of the order of 1 MI-I x cm 2 at 1 mHz. The equivalent circuit with t wo time
constants fits better the experimental results when the steel is corrodi ng more rapidly. The
resistance associated with the first time constant may vary from a few kl'~ cm 2 t o almost
- 2 0
I I I I I
- 4 0
" 0
{E
I ' l - 6 0
( / )
- 8 0
-I00 I I I I I
- 3 , 5 - 3 , 0 - 2 , 5 - 2 . 0 - 1 , 5 - 1 , 0 - 0 , 5
L o g ( F r e q ) , H z
4O
20
,<
C
J ~
"o o b
O.
i f )
- 2 0
-40 I I I I I
- 3 , 5 - 3 , 0 - 2 , 5 - 2 , 0 - 1 , 5 - 1 , 0 - 0 , 5
L o g ( F r e q ) , H z
FIG. 11- - Power spectra of the EN recordings shown in Fig. 10: (a) vol tage and (b) current.
1 mI~ x c m 2, whereas Cd~ i s larger than in the previ ous case, but in general l e s s than
100 ~ F / c m 2. The Bo de pl ot ma y be as in Fi g. 8 ( Sol ut i on l ) , wi t h a s l o pe o f about - 0 . 5 at
1 mHz , whi c h changes t o about - 1 be t we e n l 0 and 100 mHz , dependi ng on the val ue o f
the resi st ance. The val ues o f I ~ in the f requency range s ampl e d by EN can be qui te di fferent,
f r om 1 Ml ) x c m 2 t o l e s s than 1 kI~ x c m 2. The res i s t ance in s eri es Rs o f the e l e c t r ol yt e
permeat i ng the concret e wa s o f the order o f 5 0 t o 100 12 The resul ts o f the EIS me as ur e me nt s
s ho we d a g o o d correl at i on be t we e n R o and the pot ent i al at whi c h the me as ur e me nt was
made, as s hown in Fi g. 9. Corros i on rates coul d be cal cul at ed f r om EIS data s uppl e me nt e d
by pol ari zat i on me as ur e me nt s t o e s t i mat e the coef f i ci ent s as s oci at ed wi t h the Tafel s l ope s .
BERTOCCI ON DETECTI ON OF CORROSI ON IN REI NFORCED CONCRETE 53
0 4
E -20
O
X
E
. C
o
- 4 0
m
- 6 0 I ! i BI 0
0 2 0 4 0 6 0 1 0 0
5 , 0
Z', k Oh mx c m2
i i i i
- 1 0
4 , 5 - 2 0
o Q
X
E -30
,,..
O 4 , 0 O' ;
C
. ~ - 4 0 t ~
u
0 - 5 0 ~ "
. . . I 3 , 5 I 1 .
I
- - - - o - - - L o g I Zl - 6 0
3 , 0 I 7 0
- 4 - 3 - 2 - 1 0 1 2
Log ( Fr eq) , Hz
FIG. 12--Nyquist and Bode plots obtained from the same galvanic cell from which the EN recordings
of Fig. 10 were taken. E~ = -393 mV versus SCE.
E N M Re s u l t s
We wi l l gi ve s o me e x a mpl e s o f the t ypes o f resul ts obt ai ned by ENM. Nume r i c al val ues
are c o l l e c t e d in Tabl e 1, t oget her wi t h Ro (the z e r o f requency l i mi t o f 1~), and, whe n avai l -
abl e, Rc, ( t he charge transfer res i s t ance as s oci at ed wi t h the shorter o f the t i me cons t ant s ) ,
obt ai ned f r om EIS on the s ame concret e bl o c ks and wi t hi n t wo or three days f r om the date
o f the ENM.
The first three r ows o f Tabl e 1 concern c as e s in whi c h the corros i on res i s t ance i s not very
large: the corros i on rate, f r om EIS, wa s es t i mat ed t o be about 0. 5 ~ A / c m 2 for the t wo
s ampl e s i mme r s e d in 0. 2M s o di um chl ori de ( NaCI) ( Sol ut i on 1, first and s e c ond row) , and
about 0. 2 ~ A / c m 2 for the s pe c i me n in Sol ut i on 2, third row. Bot h vol t age and current no i s e
l e ve l s we r e we l l above the i nst rument al l i mi t s (as gi ve n in the s e c t i on ent i t l ed "Dat a Ac -
E
c-
o
Z
UJ
0,0
0,2
-0,2
-0,4
-0,6
0
0 , 3
I
500 10100 I 5L00
Ti me, s
1 I I
0,2
E
O 0,1
e -
~ o,o
0 -OJ
-0,2
0,4
000
54 EL ECT ROCHEMI CAL NOI SE ME A S U R E ME N T
-0,3 I / i
500 1000 1500 000
Ti me, s
F I G. 13- - F i l ter ed E N recordi ngs. Sol uti on 2: (a) Vol tage. Acqui si ti on rate = 0.5 pts/ s. (b) Current.
Acqui si ti on rate = 0.5 pts/ s.
qui si ti on"). Al s o, the choi ce o f the digital filtering procedure was in general o f little i m-
portance, increasing conf i dence in the results.
Figure 10 s hows filtered ti me records o f vol t age and current fluctuations. In this case, the
correlation bet ween the t wo i s good, i ndi cati ng that the el ectrode in c o mmo n to the t wo
gal vani c cel l s was generating mos t o f the noi se. The correspondi ng power spectra are s hown
in Fig. 11. The vol t age spectrum flattens above 50 mHz because it approaches the instru-
mental noi se ( compare Fig. 3a) , whereas the spectrum o f the current fluctuations, whi ch is
still more than one order o f magni tude larger than the instrumental noi s e at the hi ghest
frequency o f 0. 25 Hz ( compare Fig. 3b), has throughout a sl ope o f about - 1 . EIS spectra
on the same speci men are s hown in Fig. 12. Al l these data were obtai ned in Sol ut i on 1.
The ENM recordi ngs obtai ned in Sol ut i on 2 are s hown in Fig. 13 in whi ch the correlation
i s onl y partial. Here, al though the current fluctuations are o f the s ame order as in t hos e in
BERTOCCI ON DETECTI ON OF CORROSI ON IN REI NFORCED CONCRETE 5 5
E
O~
O
Z
t/J
1,0
0,8 t
0,6
0,4
0,2
0,0~
-0,2
-0,4
-0,6
-0,8
-1,0
i
I
500
10100 15100 2000
Ti me, s
i i i
a
u
4 . ,
e-
= =
I .
O
Z
i l l
0
-1
-2
-3
f
' o o 500 10 0 15 0
Ti me, s
1;
200
FIG. 14- - Fi l t er ed EN recordings. Solution 3: (a) Voltage. Acqui si t i on rate = 0. 5 pt s / s . (b) Current.
pure NaC1, the standard devi ati on o f the vol t age fluctuations is larger, l eadi ng to a larger
val ue o f X, , in agreement wi th EIS results.
On the speci men e xpos e d to a magnes i um chl ori de (MgCi2) sol uti on wi th a citrate inhibitor
( Sol ut i on 3), fairly regularly spaced transients were observed, as s hown in Fig. 14. Such
behavi or suggest s l ocal i zed corrosi on, but both ENM and EIS results gi ve a fairly hi gh
resistance, at about 5 0 0 kl ~ c m 2, whi ch shoul d correspond to a l ow corrosi on rate o f the
order o f 50 nA/ c m 2. Becaus e the transients occurred in both vol t age and current at the same
time, the curve o f the standard devi ati on ratio X, is not affected, as s hown in Fig. 15.
Therefore, si mpl e moni tori ng o f X, woul d not have reveal ed this behavior.
The last t wo rows in Table 1 refer to data taken on a dei ci ng salt wi th an organic l i gno-
sulfate inhibitor ( Sol ut i on 4) and on an alternative deicer, cal ci um magnes i um acetate ( CMA)
( Sol ut i on 5), whi ch both exhibit hi gh Ro wi th EIS, i ndi cati ve o f a very l ow corrosi on rate.
E
c-
O
v
X
40
30
20
10
i 1 i i j
o J 9 ,
0 500 100 0 1500 2000
Ti me, s
FIG. 15--Standard deviation ratio X, obtained from the recordings of Fig. 14.
Here the EN, particularly in the voltage channels, is barely above the instrumental limit, and
the time records seem to be devoid of meaningful content, as shown in Fig. 16. In these
cases, the instrumentation appears to have insufficient sensitivity.
Di s cus s i on
One of the major problems that affect the ENM presented here stems from the lack of
corrosion uniformity in the electrodes, which leads to large DC differences and slow drifts.
This undermines one of the assumptions made in the model used in the analysis of the
fluctuations. It may be argued that a zero average in the current and voltage would be
achieved if the measurements were extended for arbitrarily long times, but this does not
solve the problem in most practical cases. It can be conceded that differences in behavior
are, in general, more pronounced in slowly corrodi ng systems, of which steel in concrete is
obvi ousl y an example, but experience suggests that such differences are common. I f vanish-
ing differences in Eoc were a necessary requirement, the applicability of this method would
be severely restricted.
A second problem is that of the most appropriate way to eliminate the noise below a
certain frequency, including the DC component. Results presented here show that onl y when
the choice of the filtering procedure has little influence on the value of the standard deviation
can there be confidence that significant fluctuations in the frequency range under examination
have been detected. Many authors have preferred to use analog high-pass filters in noise
measurements. This may turn out to be a better approach, but it should be remembered that
analog filters affect the signals just as digital filters, so that the issues about the validity of
the experimental data are present in this case too, although they may be less obvious.
In some of the data obtained in this work, the values of X, were smaller than expected.
This was the case when the corrosion rate was low, the noise in the voltage measuring
channel was onl y marginally greater than that produced by the instrumentation, and signif-
icant fluctuations could be detected in the current channel. This is in contradiction to our
understanding of the phenomenon: i f the electrode impedance is large, whatever causes
BERTOCCI ON DETECTI ON OF CORROSI ON IN REI NFORCED CONCRETE 5 7
0,2 i i i
0,1
ca o, o a
..=.
o
>
z
tJJ
-o,1
-0,2
0 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0
Time, s
0, 3 j , ,
0 , 2
0, 1
c
o,o b
e=
,-.t
(=) -0, I
Z
tkl
-0, 2
- 0 , 3 i * I 20100
5 0 0 1 0 0 0 1 5 0 0
Time, s
FI G. 16- - Fi l t er ed EN recordings. Solution 4: (a) Voltage. Acquisition rate = 0. 5 pt s / s . (b) Current.
vol t age fl uctuati ons s houl d i nduce s mal l currents. Such a puz z l i ng resul t cannot be di s mi s s e d
as an ef f ect o f l i mi t e d s ens i t i vi t y o f the i nst rument at i on, whe n the current fl uctuati ons are
cl earl y above the i nstrumental l i mi t .
In c onc l us i on, the data present ed here i ndi cat e that EN moni t ori ng has cons i derabl e l i m-
i tati ons whe n appl i ed t o corros i on i n rei nf orced concret e, and that further st udi es on ot her
e l e c t r oc he mi c al s y s t e ms , as we l l as c ompar i s on wi t h di fferent experi ment al t echni ques are
neces s ary bef ore the me t hod can be us ed wi t h conf i dence.
Re f e r e n c e s
[1] Searson, P. C., Dawson, J. L., and John, D. G., UMIST Conference on Electrochemical Methods in
Corrosion Testing and Research, UMIST, Manchester, UK, 1982, p. 1.
[2] Zevnik, C., "Electrochemical Noise Corrosion Monitoring Method in Laboratory Use," Proceedings
of the International Conference on Metallic Corrosion, Madras, Oxford & IBH Publ. Co., New
Delhi, 1987, p. 4061.
[3] Kendig, M., Jeanjaquet, S., and Mahoney, M., "Electrochemical Noise Analysis of the Corrosion of
Aluminum Alloys and Composites," Paper 383, CORROSION 88, NACE, Houston, TX, 1988.
[4] Rothwell, A. N. and Eden, D. A., "Electrochemical Noise Techniques for Determining Corrosion
Rates and Mechanisms," Paper 223, CORROSION 92, NACE, Houston, TX, 1992.
[5] Eden, D. A. and Rothwell, A. N., "Electrochemical Noise Data: Analysis, Interpretation and Pres-
entation," Paper 292, CORROSION 92, NACE, Houston, TX, 1992.
[6] Bertocci, U. and Huet, E, Corrosion, Vol. 51, 1995, p. 131.
[7] Legat, A. and Zevnik, C., Corrosion Science, Vol. 35, 1993, p. 1661.
F l ori an Mansfel d 1 and Hong Xi ao 1
Electrochemical Noise and I mpedance
Analysis of I ron in Chloride Medi a
REFERENCE: Mansfeld, E and Xiao, H., "Electrochemical Noise and Impedance Analysis
of Iron in Chloride Media," Electrochemical Noise Measurement f or Corrosion Applications,
ASTM STP 1277, Jeffery R. Keams, John R. Scully, Pierre R. Roberge, David L. Reichert, and
John L. Dawson, Eds., American Society for Testing and Materials, 1996, pp. 59-78.
ABSTRACT: Potential and current noise data have been collected for pure iron foils exposed
to 0.5N sodium chloride (NaC1) that was aerated, deaerated, or aerated with sodium nitrite
(NaNO2) added as inhibitor. Potential and current noise data were obtained at the beginning
of each hour over a 24-h period either sequentially or simultaneously. Statistical and spectral
analyses were performed resulting in noise resistance values. For the noise resistance R, =
~rVIo-l, where ~rV and crl are the standard deviation values of potential and current, respectively,
similar values as for the polarization resistance Rp determined with electrochemical impedance
spectroscopy (EIS) at the end of the tests were obtained. The spectral noise resistance R~
obtained from spectral analysis of simultaneously collected current and potential data agreed
satisfactorily with Rp and R, for aerated and inhibited solutions. Electrochemical noise and
impedance data have also been obtained for two polymer coatings on cold-rolled steel during
immersion in 0.5N NaC1 for five months. The two types of measurements clearly distinguished
between the relatively poor performance of the alkyd system and the excellent performance of
the epoxy polyamide system. Similar trends with exposure time were observed for the pore
resistance Rpo and R e, on the one hand, and R. and R~ on the other hand. However, the
numerical values of the parameters obtained with EIS were different from those obtained with
electrochemical noise analysis (ENA).
KEYWORDS: noise resistance, spectral noise resistance, polarization resistance, iron, inhib-
itor, polymer coating, electrochemical noise analysis, electrochemical impedance spectroscopy
El ect r ochemi cal noi se anal ysi s ( ENA) is uni que among al l el ect r ochemi cal t echni ques used
i n cor r osi on research because no ext er nal si gnal needs to be appl i ed for t he col l ect i on of
exper i ment al data. Ther ef or e, ENA is of great i nt er est for cor r osi on st udi es especi al l y i f one
consi der s t he addi t i onal benef i t t hat t he cost s of i ns t r ument at i on are great l y r educed i n c om-
par i son wi t h ot her popul ar t echni ques. I n general , a zero r esi st ance ammet er ( ZRA) and one
or t wo vol t met er s under comput er cont r ol are suffi ci ent . It is obvi ous t hat ENA has great
pr omi s e not onl y for basi c l abor at or y st udi es, but perhaps even mor e so for cor r osi on mon-
i t ori ng. Ther ef or e, it is not t oo sur pr i si ng t hat a n u mb e r of r esear ch gr oups have r epor t ed
resul t s obt ai ned ma i nl y wi t h t he me a s ur e me nt of pot ent i al noi se. Ther e has been a t endency
to rel at e al l el ect r ochemi cal noi se dat a to l ocal i zed cor r osi on; however, recent l y, t he pr esent
aut hors have f ound [1-5] t hat pot ent i al noi se can be mi s l eadi ng i n cases i n whi ch s mal l
f l uct uat i ons i n mass t r anspor t cont r ol can pr oduce l arge changes i n t he cor r osi on pot ent i al
Ecorr. Such is t he case for met al s and al l oys t hat are i mmu n e to cor r osi on such as pl at i num
Professor and Ph.D. student, respectively, Corrosion and Environmental Effects Laboratory (CEEL),
Department of Materials Science and Engineering, University of Southern California, Los Angeles, CA
90089-0241.
59
www.astm.org
(Pt) or are passive such as stainless steels in neutral, aerated environments. Mansfel d and
Xi ao [1-3] have shown that potential noise as analyzed with the use of power spectral density
(PSD) plots was similar for Pt and for an AI / Si C metal matrix composite, which pits severely
in aerated 0. 5N sodium chloride (NaCl). However, the current noise PSD plots were very
different for the two materials. To obtain more information about experimental and theoretical
details of ENA, the well-known syst em Fe/ NaCI has been investigated in three solutions of
different corrosivity. Dat a analysis has been carried out using both spectral and statistical
analysis. The system Fe/NaC1 was also of interest because Lumsden et al. [6] found poor
agreement between the noise resistance R, obtained with ENA and the polarization resistance
Rp obtained with electrochemical impedance spectroscopy (EIS).
As discussed in a recent review [7], one of the most successful applications of EIS has
been in the evaluation of the protective properties of pol ymer coatings and their degradation
with exposure time. It was of interest in this study to evaluate whether similar information
concerning the coating degradation can be obtained with ENA. Mills et al. recently deter-
mined R, and the mean current I,~ for a number of different pol ymer coatings and concl uded
in tests lasting 185 h that ENA distinguished between paints that were blistering and those
that were not [8].
Experimental Approach
Materials and Methods
Materials--Pure iron foils (99.999%, 0. 1-mm thickness) were exposed to 0. 5N NaC1 that
was open to air or deaerated. Samples were polished to 1200-grit finish, then degreased in
50~ hexane for 20 min. Pol ymer-coat ed cold-rolled steel with an alkyd coating system (CR-
2) or an epoxy pol yami de coating (CR-9) was exposed to the 0. 5N NaCl (open t o air). These
two coatings have been studied earlier in detail with EIS [9-11].
Methods--The experimental arrangement for the measurement of potential and current
noise is shown schematically in Fig. 1. Two pieces of the same iron foil or pol ymer-coat ed
steel with 5-cm 2 exposed area each were used as test electrodes. These two samples were
placed vertically and parallel to each other in a specially designed test cell and connected
to a Schlumberger model 1286 potentiostat, which was used as a ZRA to apply 0 mV
potential between the two electrodes. A saturated calomel electrode (SCE) reference elec-
trode was placed between the t wo electrodes. The potential of the coupl ed electrodes versus
the reference electrode was measured using a Hewlett Packard (HP) 3457A multimeter. The
current output of the potentiostat was connected to the rear channel of a computer-controlled
HP 3478A multimeter providing the current noise record (see Fig. 1).
For the iron foil couple, the electrochemical potential and current noise were initially
recorded sequentially during a 24-h period. The t wo test electrodes were kept at 0- mV
potential difference from the start of immersion until the end of the test. At the beginning
of every hour of immersion time, the potential noise was recorded first, immediately followed
by the coupling current noise measurement. For both the potential and current measurement,
a 2-poi nt sl s sampling rate was used for 500 s in each measurement for the tests with iron
as in the tests by Lumsden et al. [6]. The timing and measuring mode switching were
controlled by an IBM-AT compatible computer. A comput er program was developed to read
and store the noise data as well as to remotely control the experiment through the general-
purpose interface bus (GPIB) (IEEE-488) interface [1-4]. The simultaneous sampling of
current and potential noise data makes it possible to reveal the relationships between potential
and current fluctuations in the frequency domain [4,5].
MANSFELD AND XlAO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 61
".~
I
~5
To determine the noise behavior of iron in solutions of different corrosivity and at different
potentials, three solutions were used: (1) 0. 5N NaC1 open to air, (2) 0. 5N NaC1 deaerated
with N2, and (3) 0. 5N NaC1 + 0. 01M sodium nitrite (NaNO2) ad inhibitor, open to air. After
recording the electrochemical noise data for 24 h, the impedances of the samples were
measured using a two-electrode arrangement. The experimental noise data were further pro-
cessed using bot h statistical analysis and simple spectral analysis.
In addition to the sequentially collected data, potential and current noise were recorded
simultaneously for iron in the aerated and inhibited solutions. For the coated steel, mea-
surements were made using a slightly different two-voltmeter arrangement and a more ad-
vanced control program [4,5]. The sampling rate was 2 poi nt s/ s, and each test was carded
out for 1024 s.
Dat a Anal ysi s
For all tests, the mean value and the standard deviation of the potential and current fluc-
tuations were determined. From these data the noise resistance R. defined as
R . = ~ V / ~ I (1)
was calculated, where crV is the standard deviation of potential fluctuation and crl is the
standard deviation of current fluctuations [12]. Experimental values of R. for carbon steel
in NaC1 have been reported by Lumsden et al. [6], who tried to correlate R. with R. deter-
mined with EIS.
In addition to the statistical analysis, the noise data obtained by simultaneous collection
of potential and current noise were anal yzed in the frequency domain using fast Fourier
transform (FFT). To evaluate the frequency dependence of the electrochemical noise data,
the spectral noise response Rs . ( f ) was calculated at each frequency f as
R ( f ) = V ( f ) / I ( f ) (2)
and
R s . ( f ) = j R( f ) [ = [Rre 2 ql_ R i , n 2 ] l / 2 (3)
where V( f ) and I( f ) are compl ex numbers obtained from FFT [4,5]. A new term called
the spectral noise resistance R~ introduced by the authors is defined as the value of R s . ( f )
at f = 0:
R~ = lim {R, , (f)} (4)
f ~0
Experimental Results and Discussion
The experimental results obtained for iron in NaCI with sequential collection of potential
and current noise data and the results of the data analysis are displayed in Figs. 2 through
7. Figure 2 shows experimental potential and current noise data after exposure for 1 h to
the deaerated NaC1 solution. For the example in Fig. 2, Eco, decreased by about 10 mV in
500 s. For the current, fairly rapid fluctuations of low amplitude ( <0. 3 ~LA) were observed.
The mean values of Ecor~ for iron exposed to NaC1, which was open to air, deaerated, or
MANSFELD AND Xl AO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 6 3
0 . 5 " c u r r e n t - - pot ent i al - 7 5 0
i - 7 5 5 ~ -
0 . 2 5 " ~ ' ~ i i : ., : , : , ! i : , : ,
~ , , . , ~ ' ' , " " , ~ . , , , , ' ~ ; t ~ . ' . . . . . . , , ~ ' ~ ~ . ' ; ? , ' " , ' , . " ~ , ; . ' , ' ~ , ' , ' ' * . , , t " , , " , , , , '
o ~ : , : ~ : ~ : , , , . , , , . , , , . , , : ' . . , , ~ . : , . , , , . . . . , . . . . , , , , . . , ,
' ' ' " " " ' :" - 7 6 5 uJ
- 0 . 2 5 ~ ~ , , , - 7 7 0
0 1 2 0 2 4 0 3 6 0 4 8 0
S a m p l i n g t i m e ( s e c . )
FIG. 2--Potential and current noise recorded f or iron in 0.5N NaCI (deaerated) after exposure f or
l h .
open to air with addition of 0. 01M NaNO2, are shown in Fig. 3. Figure 4 presents the mean
values of the coupling current I,,. Eco . in the aerated solution decreased slowly with time as
the rust layer formed. In the deaerated solution Eco ~ was more negative and fairly constant
after a few hours of immersion. In the aerated solution containing NaNO2, positive potentials
typical for this type of inhibitor were observed. I,, was very small for the deaerated and the
inhibited solution. Bot h positive and negative current peaks occurred in the aerated solution.
The data shown in Fig. 4 are different from those reported by Lumsden et al. [6], in which
a very large DC current of 700 to 750 I~A occurred, indicating large differences in the
corrosion kinetics of the two steel samples used by these authors.
Figures 5 and 6 show the standard deviation values of potential and current, respectively.
The largest ~rV values in the range between 1 and 10 mV are observed for the inhibited
solution in which iron is in the passive state and the fluctuations of E~o,~ are larger, whi ch
is similar to the results reported previously for platinum [1-3]. For the deaerated solution,
the potential fluctuations are very small and fairly constant (about 0.1 mV). These obser-
vations are consistent with earlier findings [1-3] that mass transport of oxygen can play a
large role in potential noise. The (rl values are the largest and show the highest variations
with time for the aerated solution in which significant corrosion occurs (see Fig. 6). For the
deaerated and the inhibited solutions, much smaller values of (rl are observed with larger
fluctuations for the inhibited solution. In these solutions the sample surfaces remained shiny
during the 24-h test.
The noise resistance R, , which is derived from the data in Figs. 3 t hrough 6 accordi ng
to Eq 1, is shown in Fig. 7 for the three test solutions. The highest values of R, (10 to 100
kO) are observed for the inhibited solution. For the deaerated solution, a very stable time
-100,
-200
ua -300
(..)
r
> -400
>
E
"-" -500
E
O
-600
--~ NaCI / ai r
-800
0
-700
+ " ~ I I - ~ [ I I I t I I t I I I I I I I I i i
6 12 18 24
Exposure Ti me (hours)
FIG. 3- - Ti me dependence of the mean Ecorr f or iron in three solutions.
- - NaCI / N2
NaCI/NaNO,~
f l -
y
E
3 o
20
10
0
-10
-20
-30
0
l J-
6 12 18
FIG. 4- - Ti me dependence of the mean coupling c u r r e n t I m f or iron in three solutions.
24
MANSFELD AND Xl AO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 65
E
v
>
1 O 0 1 4 _
NaCI / ai r
/
t - F NaCI / N2
' ,. ~ NaCI/NaNO21
I
0.1
0 . 0 1 J I I
0 6 12 18 24
Exposur e Ti me (hours)
FIG. 5--o' V values f or iron in three solutions.
v
b
100
10
0,1
0.01
0
-=- NaCI / ai r
- r - NaCI / N2
->~ NaCI / NaNO2
I I I
6 12 18 24
Exposur e Ti me (hours)
FIG. 6--o' 1 values f or iron in three solutions.
1E+07
1E+06 t
1E+05
E
c-
O 1E+04
v
C
r r
1E+03
I E+02
1E+01
0
4- NaCI / ai r
-}- NaCI / N2
NaCI / NaN02
6 12 18 24
Exposure Time (hours)
FIG. 7--Noise resistance R. for iron in three solutions.
behavior is observed with R, slowly increasing from about 1 to about 10 kl'l after 24 h. The
sample exposed to NaC1/air has the lowest R, values with the largest fluctuations between
10 fl and 5 kll
Figure 8 shows the impedance spectra for the iron samples after exposure in the three
solutions for 24 h. The spectra have been fit to a one-time-constant model to obtain Rp,
which is listed in Table l for comparison with R, determined for 24 h of exposure. Fairly
good agreement between these two parameters is observed. Lumsden et al. reported much
larger values of R, than Rp for carbon steel in NaCI [6]. Some of these differences could be
due to the dissimilar nature of the steel samples used by these authors.
The results of the analysis of simultaneously recorded potential and current noise data are
presented in Figs. 9 through 11 for the aerated NaCI solution with and without NaNO2.
Similar R, values were determined (Fig. 9) as in the experiments with sequential recording
of potential and current noise (see Fig. 7). This result demonstrates that for relatively short
sampling times sequential and simultaneous recording of noise data provides similar results.
However, for spectral analysis, in which potential and current fluctuations are correlated in
the frequency domain, simultaneous recording of potential and current noise data is neces-
sary. Figure 10 shows the spectral noise response R,, calculated from Eqs 2 and 3 as a
function of frequency for the first (see Fig. 10a) and last hour (see Fig. 10b) of exposure.
The frequency independent low values of Rs, (see Fig. 10) for the aerated solution indicate
uniform corrosion at high rates in contrast to the curves with higher and frequency-dependent
Rsn values for the inhibited solution, which show larger scatter (see Fig. 10). From curves
obtained for each hour of exposure, such as those shown in Fig. 10a and b, the spectral
noise resistance R~ was determined by extrapolation to f = 0 according to Eq 4. These
R~ values are plotted in Fig. 11 as a function of exposure time for both solutions. A
comparison of the results in Fig. 9 and Fig. 11 shows that R, as defined in Eq 1 (see Fig.
MANSFELD AND XlAO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 67
1E+05
90
E
t -
O 1E+03
N
-=- NaCI / ai r
-><- NaCI / NaNO2
- - NaCI / N2
1E+04
) _
1 E + 0 2
1 E + 0 1 I I I I L . . . . 0
0.01 0.1 1 10 1 O0 1000 10000
Frequency ( Hz)
FIG. 8 Bode-plots for iron after immersion in three different solutions f or 24 h.
60 (B
" 0
fl)
O3
c "
<
Q ~
30 ~
I -
9) and R~ as defined in Eq 4 (see Fig. 11) have similar values at each exposure time. A
compari son of the 24-h values of R, , R~ and Rp is given in Table 2 for the t wo test
solutions. Good agreement between R, and R~ obtained with t wo different experimental
and analysis techniques and Rp determined with EIS is observed.
The potential fluctuations for the alkyd coating CR-2 after 28 and 130 days of exposure
are shown in Fig. 12a; the corresponding current fluctuations are displayed in Fig. 12b.
Considering that the E28 scale in Fig. 12a is ten times larger than the E13o scale, it is clear
that the potential fluctuations in the early stages of exposure are much larger than after
longer times. On the other hand, in Fig. 12b, the current fluctuations at the 28th day were
much smaller than at the 130th day of exposure (note the ten times difference between the
12g and lj3 o scales). This qualitative evaluation of the experimental data suggests that, initially,
potential noise levels are high and current noise levels are low. As the coating degrades,
potential noise levels decrease and current noise levels increase, For the more protective
epoxy pol yami de coating CR-9, no systematic changes of noise levels with time could be
detected [13].
The time records for potential and current noise were first analyzed statistically by cal-
culating the mean and the standard deviation for each data set to obtain R, (Eq 1). The
TABLE 1--Comparison of R, and Rp f or three different test
environments,
Environment Open to Air Deaerated (N2) Inhibited (NaNO2)
R,(kfl) 0.8 8.3 54.7
Rp(kD) 1.6 15.9 22.1
6 8 ELECTROCHEMI CAL NOISE MEASUREMENT
A
E
r
O
r
r l -
10 6
1 0 5
10 4
10 3
1 0 2
, N a C l / a i r
~< N a C I / N a N O 2
I I I
0 6 12 18 2 4
FIG. 9- - Noi s e resistance R n determined f rom simultaneously recorded pot ent i al and current noise
data f or iron in aerat ed and in aerated, inhibited 0. 5N NaCI.
experimental data were also transformed from the time domain into the frequency domain
by FFF to determine R,.( f ) (Eqs 2 and 3). The R,.( f ) functions for CR-2 and CR-9 after
28 and 130 days of exposure in Fig. 13 show that the noise spectra for CR-2 and CR-9 after
28 and 130 days of exposure are independent of frequency. At the 28th day of exposure,
the R s. values (Eq 3) for CR-2 are about one order of magnitude lower than for CR-9,
indicating the CR-2 had already started to degrade. At the 130th day of exposure, the dif-
ference in Rs. for CR-2 and CR-9 was about four orders of magnitude over the entire
frequency region.
Figure 14 shows R. and R~ as a function of exposure time for CR-2 and CR-9. For
CR-2, the same trend of R. and R~ to decrease with time can be found as was observed
for Rp and Rpo determined from EIS. For CR-9, R. and R~ remained at much higher values
and did not change significantly with time, indicating that degradation had not occurred,
which is consistent with previous conclusions [9-11]. Similar to the Fe/NaC1 system dis-
cussed above, R. and R~ had very similar values despite the fact that they are mathemati-
cally unrelated.
Figure 15 shows that the time dependence of Rp, Rpo, R . , and R~ for CR-2 is very
similar. However, the numerical values of the parameters obtained from ENA are much lower
than those obtained from EIS, which raises questions concerning the relation of R. and R~
to the corrosion/coating degradation processes for the systems under investigation.
Another important part of spectral analysis is the calculation of the power spectral density
(PSD) functions of the noise data. Being another frequency domain representation of a given
signal, the PSD function is defined as the power of a signal at a given frequency and can
be obtained by FFF or the maximum entropy method (MEM) [14]. A previously developed
MANSFELD AND XIAO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 6 9
1 0 7
1 0 6
. . . , 1 0 5
E
e -
o
v
= 1 0 4
M )
1 0 3
1 0 2
. =
iT"
: e )
w
N A N 0 2
i I I I i i i ]
. 0 0 1 , 0 1 .1 1
1 0 7
1 0 6
1 0 5
1 0 4
1 0 3
1 0 2
. 0 0 1
F r e q u e n c y ( H z )
b )
N A N 0 2
a i r
A - 1 1 - ~ " W - ' a ' ' ~ t ' ~ ' A 1 l i i i i i i i
i i i I I I I t I J i i i i t l I I i I i i I I
. 0 1 . I I
F r e q u e n c y ( H z )
FIG. lO--Frequency dependence of spectral noise resistance Rs, for iron in aerated and for aerated,
inhibited 0.5N NaCl after exposure for 1 h ( a ) and 24 h ( b ) .
70 ELECTROCHEMI CAL NOISE MEASUREMENT
A
E
t , -
o
v
c
r162
O
nr-
106
10 5
10 4
103
10 2
, NaCI / ai r
~ NaCI / NaNO2
I _ _ I [
0 6 12 18 24
FIG. 1 l--R~ values as a function of exposure time f or iron in aerated and aerated, inhibited
0.5N NaCl.
MEM comput er program was applied in these experiments to calculate the PSD functions
for potential and current fluctuation. Figure 16 presents potential (Fig. 16a) and current PSD
curves (Fig. 16b) for CR-2 at different exposure times, whereas Fig. 17 shows the potential
(Fig. 17a) and current (Fig. 17b) PSD plots for CR-9. As the exposure time increased, the
potential PSD curves for CR-2 decreased in magnitude with similar slopes except for the
130th day (see Fig. 16a). This is another presentation of the results in Fig. 12a indicating
that potential PSD decreased with increasing degradation of the protective properties of the
coating. In Fig. 17a, which shows the potential PSD for CR-9, no obvious pattern of changes
with exposure time can be seen. Potential fluctuation levels were higher for CR-9 than for
CR-2 at all exposure times. The current PSD for CR-2, which presents the frequency de-
pendence of the experimental results in Fig. 12b obtained in the time domain, increased with
exposure time maintaining a constant slope of about - 2 0 dB (Fig. 16b). On the other hand,
TABLE 2--Comparison of R., R~ and Rp for simultaneously
recorded data in two solution environments, a
Environment Open to Air Inhibited (NaNO2)
n,(kl2) 0.4 195.8
R~ 0.4 79.1
R ~ ( k f l ) 1 . 4 220.0
a The exposed area of each sample is 5 cm2; the values of R,
and R~ were recorded at 24-h exposure time.
M A N S F E L D A N D X I A O O N A N A L Y S I S O F I R O N I N C H L O R I D E M E D I A 71
u. I
r
W
>
==
uJ
-490
-500
-510
a )
0
>
J
J
<
' I ' I ' I
300 600 900
Sampling Time (sec.)
-0.07
-0.09 -
g
-0.11
-0.13
b )
2 8 t h day
<
- 4 4 8
o
-449
>
E
- 4 5 0
0.0
- - 0. 2
- !
J
-0.4
-0.6
' I ' I ' I
0 300 600 900
Exposure Time (sec.)
FIG. 12- - l i me records of potential ( a ) and current fluctuations ( b ) f o r CR-2 after 28 and 130 days
of exposure.
7 2 E L E C T R O C H E M I C A L N OI S E MEASUREMENT
A
E
t -
O
r
c / )
n--
1010
109
108
107
106
105
104
103
102
.001
--c--CR-2 ( 2 8 d a y )
o c a - 9 ( 2 8 d a y ) , . ~ T ! - , I N , a N
CR-9 ( 1 3 0 d a y ) " . ,. ~ , ' I S . ! : " '
~ ~ ~176 L o ' ~ t = k t k r L l ~ l l t l ~ i t l l ~
!
' d
[ I
.01 .1
Frequency ( Hz )
FIG. 13--Noise spectra for CR-2 and CR-9 after 28 and 130 days of exposure.
A
E
r
0
C
clJ
t , , -
r r -
1 0 9
1 0 8
107
1 0 6
105
104
103
- - t ~- Rn
- - ~ - - R * s n
C R - 9
' I t I '
50 100
Exposure T i me (day)
FIG. 14--Time dependence of R. and R~ CR-2 and CR-9.
1 5 0
MANSFELD AND XIAO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 7 3
E
t -
O
t --
r
r r
0
rr-
Q.
r r
10 9
10 8
10 7
10 6
10 5
104
10 3
0 150
' I ' I
5 0 100
E x p o s u r e T i m e ( d a y )
FIG. 15--Time dependence of R., R%, R~, and Rpofor CR-2.
the current PSD for CR-9 (see Fig. 17b) had much lower levels than for CR-2 without an
obvious relation with exposure time. The four PSD plots (see Figs. 16a and 17b) indicate
that the PSD level is correlated qualitatively with loss of corrosion protection provided by
the coating system. From Figs. 16 and 17, it is clear that the frequency bandwidth in the
present study was t oo narrow to show the DC limit po, which apparently occurs at extremely
low frequencies ( < 1 mHz). Therefore, the PSD values at 1 mHz for potential (P%) and
current (P~ PSD plots were used for comparative purposes. The P% and p o values obtained
in this way are shown in Fig. 18, whereas the values of the slope Sp in the linear region of
Figs. 16 and 17 are shown in Fig. 19 as function of exposure time. For CR-2, P% decreased
and P~ i increased with exposure time, whereas for CR-9, P% remained high and p o was very
low (see Fig. 18). The slopes for potential (Sew) and current (Spi) PSD remained constant at
about - 2 0 dB for CR-2 and CR-9, except for Sp~ of CR-2 at the 130th day of exposure.
This constant value of Sp is consistent with previous suggestions [15] that the slope of PSD
plots is a characteristic parameter for a given corrosion mechani sm independent of extent of
corrosion activity.
Summary and Conclusions
The main goal of this study was t o determine whether parameters obtained by statistical
and spectral analysis of potential and current fluctuations agree with those obtained from
EIS, which served as a reference technique. For pure iron in 0. 5N NaC1, which was either
aerated, deaerated, or aerated containing NaNO2 as inhibitor, the mean and the standard
deviation values of Ecor~ and the coupling current between two electrodes of the same material
have been determined on an hourly basis for a 24-h period. Noise data have been collected
74 EL ECT ROCHEMI CAL NOI SE ME A S URE ME NT
A
E
r
Cz
r
. m
Q
r
6 0
3 0
-30
- 6 0
. 0 0 1
--c-- 28 day
32 day
- c - 83 day
, 80 day
a ) ~ - ~ . ~ %. ~ . . ~ , __~
I L
. 0 1 .1 1
Frequency (Hz)
~ L
" O
r
Q .
t . -
P
3
O
1 0
--c- 28 day
-s3 day
| . ~ _ ~ - + - 8 0 day
-20 ~ ~ - ~- 1 3 0 day
- 5 0 - ~
b )
- 8 0 I I
. 0 0 1 . 0 1 .1 1
F r e q u e n c y (Hz)
FIG. 16--Potential ( a ) and current ( b ) PSD curves of CR-2 for different exposure times.
sequentially and simultaneously. The latter approach allows construction of spectral noise
plots from which the spectral noise resistance R~ can be determined as the DC limit. R.
and R~ have been determined as a function of exposure time. Satisfactory agreement be-
tween the polarization resistance Rp obtained from EIS and R~ and R. has been observed.
The most relevant parameters obtained from analysis of electrochemical noise data for the
polymer-coated steel exposed to NaC1 are R. . R~ and the PSD parameters revealing in-
MANSF EL D AND XI AO ON ANAL YSI S OF I RON I N CHL ORI DE MEDI A 75
A
E
" o
r',,
cn
13.
E
o .
A
. <
=I .
n~
" 1 0
O'3
O,1.
"E
z, -
C.)
6 0
3 0
-30
- 6 0
- 32 day
- 0 - 6 3 day
, 80 day
- ~ 1 3 0 day
I I
. 0 0 1 . 01 .1 1
Frequency (Hz)
10
i 1)) ---o-- 28 day
x 32 day
--=- 83 day
t 80 day
-20 ~ 130 day
- 5 0
- 8 0 l I
. 0 0 1 . 01 .1 1
F r e q u e n c y ( Hz)
FIG. 17--Potential ( a ) and current ( b) PSD curves of CR-g f or different exposure times.
formation concerning coating degradation and corrosion of the substrate from different as-
pects. Very similar values have been obtained for R. and R~ despite the fact that these
parameters have been determined using different methods of data analysis. The decrease of
R. and R~ with time for the coating with relatively poor performance is similar to that of
EIS parameters related to coating disbonding (Rpo) and corrosion at the metal/coating in-
terface (Rp); however, the numerical values are quite different. As far as the PSD parameters
7 6 E L E C T R O C H E M I C A L N O I S E M E A S U R E M E N T
, - , z
a:z
o_
=r
>
E
" O
o
a .
6 0
30
- 3 0
- 6 0
-90
O
0 ....
..... " . . O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
~
....,.--'" "
- 0 - P~ ( CR- 2)
--~--P~ ( CR- 2)
..o,-P~ ( CR- 9)
- - + - P~ ( CR- 9)
I
0 1 0 0 1 5 0
T i me ( d a y )
I
5 0
E x p o s u r e
F I G. 18- - T i me dependence of PSI:)parameters po for potential (P~ and current ( P ~ noise for CR-
2 and CR-9.
N
. q r -
0
" O
- 1 0
- 2 0
O
| - 3 0
>
E
t o
" D
r - 4 0
- o - Spv ( CR- 2)
--~--Spi (CR 2)
. . . . Spv ( CR- 9)
- ( CR- 9)
' I ' I '
0 5 0 1 0 0 1 5 0
E x p o s u r e Ti me ( d a y )
F I G. 19--Time dependence of PSD parameters Spfor potential ( S p y ) and current ( S v i ) noise for CR-2
and CR-9.
MANSFELD AND XIAO ON ANALYSIS OF IRON IN CHLORIDE MEDIA 77
are concerned, the increase of P~ i obtained from current PSD data and the decrease of P~ v
derived from potential PSD data seem to be useful indicators of coating degradation or
substrate corrosion or both. The slopes Spy and Sei with values of about - 2 0 dB independent
of exposure time and coating performance seem to be characteristic values of the coat i ng/
steel/NaC1 system and the prevailing corrosion mechanism.
Recommendations f or Future Work
Several points require further theoretical and experimental examination. In the PSD plots
for the pol ymer-coat ed steel, a DC limit was not observed even at 1 mHz. On the other
hand, the spectral noise plots were independent of frequency in the examined frequency
range (0.001 < f < 1 Hz). Analysis of EIS data obtained over a very wide frequency range
results in a number of parameters that allow assessment of the changes of coating properties
such as water uptake and decrease of coating conductivity, determination of the extent of
the disbonded area, and estimation of the average corrosion rate of this area [7]. Statistical
analysis of noise data results in onl y one par amet er - - t he noise resistance R, , whereas spec-
tral analysis of the same data produces another par amet er - - t he spectral noise resistance
R~ In future work, it needs to be established to which of the parameters characterizing a
coating system exposed to a corrosive environment R, and R~ are related. A similar ap-
proach is needed for correlation of parameters obtained from PSD and spectral noise plots
with coating properties. At the present state of our understanding of ENA, it has to be
concl uded that this technique can produce qualitative information concerning coating per-
formance and is, therefore, suited for corrosion-monitoring purposes. Important advantages
of ENA are low equipment cost and relative ease of data collection using appropriate soft-
ware, which allows collection of data from multiple corrosion sensors and data transmission
t o a central control facility. 2 This approach is used by the authors in a study of the effects
of microorganisms on the protective properties of pol ymer coatings applied to steel exposed
to natural seawater [16].
Acknowledgment
This project has been funded in part by Mont ana State University under Subcontract
291435-01 and in part by the Office of Naval Research (Dr. A. J. Sedriks) under Contract
N00014-94-1-0026. The simultaneously collected noise data for the Fe/NaC1 system have
been displayed and analyzed by L. T. Han, who is a graduate student at CEEL.
Re f e r e nc e s
[1] Mansfeld, E and Xiao, H., "Evaluation of Electrochemical Techniques for the Study of Localized
Corrosion Phenomena in MIC," NSF-CONICET Workshop on Biocorrosion and Biofouling, Mar
del Plata, Argentina, Oct. 1992, Buckman Laboratory, 1993.
[2] Mansfeld, E and Xiao, H., "Electrochemical Techniques for the Detection of Localized Corrosion
Phenomena in MIC," in Microbiologicatty Influenced Corrosion (MIC) Testing, STP 1232, Amer-
ican Society for Testing and Materials, West Conshohocken, PA, 1994, p. 12.
[3] Mansfeld, E and Xiao, H., "Development of Electrochemical Test Methods for the Study of Lo-
calized Corrosion Phenomena in Biocorrosion," in Proceedings of Biofouling and Biocorrosion in
Natural Waters, ACS, Aug. 1992, Lewis Publishing, 1994, p. 265.
[4] Mansfeld, F. and Xiao, H., Journal of the Electrochemical Society, Vol. 140, 1993, p. 2205.
2 H. Xiao and E Mansfeld, unpublished data, 1994.
[5] Mansfeld, E and Xiao, H., in Proceedings, 12th International Corrosion Congress, Houston, TX,
Sept. 1993, NACE, p. 1388.
[6] Lumsden, J. B., Kendig, M., and Jeanjaquet, S., presented at CORROSION/92, Paper 224, NACE,
1992.
[7] Mansfeld, E, "The Use of EIS for the Study of Corrosion Protection by Polymer Coatings," Journal
of Applied Electrochemistry, Vol. 25, 1995, p. 187.
[8] Mills, D., Bierwagen, G., Tallman, D., and Skerry, B., in Proceedings of the 12th International
Corrosion Congress, Houston, TX, Sept. 1993, NACE, p. 182.
[9] Mansfeld, F. and Tsai, C. H., Corrosion, Vol. 47, 1991, p. 952.
[10] Tsai, C. H. and Mansfeld, F., Corrosion, Vol. 49, 1993, p. 726.
[11] Mansfeld, E and Tsai, C. H., in Proceedings, 12th International Corrosion Congress, Houston, TX,
Sept. 1993, NACE, p. 128.
[12] Rothwell, A. N. and Eden, D. A., presented at CORROSION/92, Paper 223, NACE, 1992.
[13] Xiao, H. and Mansfeld, F., Journal of the Electrochemical Society, Vol. 141, 1994, p. 2332.
[14] Fougere, P. F., Maximum Entropy and Bayesion Methods, Kluwer Acad. Publ., Boston, 1990.
[15] Searson, P. and Dawson, J. L., Journal of the Electrochemical Society, Vol. 135, 1988, p. 1908.
[16] Mansfeld, F., Xiao, H., Han, L. T., Lee, C. C., Little, B., Ray, R., and Jones-Meehan, J., "Evaluation
of the Effects of Microorganisms on Corrosion Protection of Steel by Polymer Coatings," presented
at 1995 International Conference on Microbially Influenced Corrosion, NACE and AWS, New
Orleans, May 1995.
Davi d L. Rei chert ~
Electrochemical Noise Measurement for
Determining Corrosion Rates
REF ERENCE: Reichert, D. L. , "El e c t r oc he mi c al Noi s e Me a s ur e me nt f or De t e r mi n i n g
Corros i on Rates," Electrochemical Noise Measurement for Corrosion Applications, ASTM
STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John
L. Dawson, Eds., American Society for Testing and Materials, 1996, pp. 79-89.
ABSTRACT: Electrochemical noise measurements (ENM), linear polarization tests and mass
loss measurements were performed in sulfuric acid, acetic acid and other solutions. The ENM
data were converted to corrosion rates by calculating the noise resistance, R, = crV/trI where
trV and crl are the standard deviations of the potential and current. Good correlation among
the three methods was obtained for low to moderate corrosion rates, but poor correlation was
observed for high rates. ENM has proven valuable for determining corrosion rates in low-
conductivity solutions, which are not suitable for linear polarization resistance (LPR) testing,
and for measuring very low corrosion rates in which mass loss tests would have required at
least 30 days exposure to provide meaningful results.
KEYWORDS : electrochemical noise, current noise, potential noise, corrosion rate, noise
resistance
Electrochemical noise measurements (ENM) record the fluctuations in current and poten-
tial generated by corroding metals. These phenomena were first reported by Iverson in 1968
[1]. Since then, a number of researchers have been involved in evaluating ENM [2-5].
Roberge et al. collected current noise by measuring voltage drop across a resistor rather than
using a zero resistance ammeter [6]. Scully et al. examined a novel way of analyzing the
data by applying chaos theory [7]. This paper presents a number of systems in which ENM
data were analyzed to determine corrosion rates and correlated with independent measure-
ments such as mass loss or linear polarization resistance (LPR). Systems generating good
and poor correlation are reported. Explanations for the observations are suggested in the
discussion of the results.
Experi ment al
Because ENM was being evaluated as a possible tool for field monitoring, all the ENM
tests were run using three identical electrodes. This avoids the issue of possible noise con-
tribution from a saturated calomel (SCE) reference electrode [8]. The LPR tests used two
identical electrodes. The electrodes were cylindrical and polished to a 600-grit finish. All
electrodes used in a given environment were made from a single heat of material to minimize
differences between the coupons. For sulfuric acid tests, where sample area was a variable,
a long rod was cut into different lengths to obtain 1-, 3-, 5-, and 15-cm 2 samples. In the
n Semorresearch enginee~ DuPont Experimental Station, Rou~ 141, Box 80323, Wilmington, DE
19880-0323.
Copyright 9 1996 by ASTM lntcrnational
7 9
www.astm.org
acetic and sulfuric aci d ENM tests, el ect rodes were mount ed in a t ri angul ar pi t ch spaced
about 2 cm apart. The cyl i ndr i cal el ect rodes were t hreaded on a gl ass- encl osed met al rod
and seal ed wi t h a Teflon | gasket. The gamma- but yr ol act one (gBL) tests used a field probe
wi t h a st acked ri ng desi gn. The el ect rodes were each 4.5 cm 2 in area and separat ed by 0.03-
cm- t hi ck Teflon gaskets. The hi gh-puri t y wat er tests used 0. 3- cm- di amet er rods spaced about
2.5 cm apart i nsert ed into an aut ocl ave t hrough Tefl on-l i ned hi gh-pressure fittings. The t ot al
i mmer sed ar ea for the rods was 12 cm 2.
Test sol ut i ons were made in l arge bat ches so t here woul d be no vari at i ons in sol ut i on
composi t i on from cel l to cel l . LPR and ENM tests were run concurrent l y usi ng separat e
el ect rodes and cells. Thi s was to prevent any resi dual effects of pol ar i zi ng the el ect rodes
from affect i ng the ENM data.
Cor r osi on rates were est i mat ed bef or e the t est and el ect rode area was fact ored in to mi n-
i mi ze sol ut i on depl et i on effects. Thi s was especi al l y i mport ant for the l arger el ect rodes in
the hi ghl y corrosi ve sulfuric aci d tests. The test cel l s were pl aced in a wat er bat h to mai nt ai n
a st eady t emperat ure. The aut ocl aves were heat ed wi t h heat t ape power ed by a pr opor t i onal
t emperat ure cont rol l er and wr apped wi t h i nsul at i on to mi ni mi ze t emperat ure drift.
ENM dat a were obt ai ned usi ng CML di gi t al noi se moni t ori ng equi pment and DENI S
software. Thi s comput er - cont r ol l ed syst em has a l ower sensi t i vi t y l i mi t of 10 ~2 A and 1 0 - 7
V. These val ues were obt ai ned by col l ect i ng dat a wi t h t he pot ent i al measur ement l eads
short ed and t he current measur ement l eads l eft as an open circuit. A si ngl e dat a set consi st ed
of 600 dat a poi nt s col l ect ed at a rate of 1 poi nt per second. Mul t i pl e dat a sets were gat hered
for each envi ronment . The LPR tests were run wi t h an EG&G Model 273 pot ent i ost at and
352 soft ware package. The el ect rodes from all but the hi gh-puri t y wat er exper i ment s were
al so used as mass loss coupons.
Data Analysis Method
The ENM dat a were convert ed to cor r osi on rates by cal cul at i ng t he noi se resi st ance, R,
and i nsert i ng it into the St er n- Gear y equat i on in pl ace of R e. R, , was cal cul at ed accordi ng
to the f ol l owi ng equat i on [9, 10]:
R n = ( t rV/ ~rl )
where
r = st andard devi at i on of the pot ent i al noi se and
t rl = st andard devi at i on of the current noise.
( 1 )
Not e that this equat i on is for unfiltered di gi t i zed data. Anal og equi pment t ypi cal l y uses filters
and, in some cases, act ual l y col l ect s a r oot mean square ( RMS) val ue of the pot ent i al and
current noise. In the anal og case, R, is the rat i o of t he mean RMS pot ent i al noi se to the
mean RMS current noi se [11].
For bot h di gi t al and anal og noi se measurement s, when the reference el ect r ode used to
obt ai n t he pot ent i al noi se is a t hi rd i dent i cal el ect rode, t he pot ent i al noi se must be nor mal i zed
to account for t he noi se generat ed by the reference el ect r ode [12]. ~ Because t hey are i dent i cal
el ect rodes in the same envi ronment , the st andard devi at i on of the pot ent i al noi se from each
2 D. A. Eden, personal interviews, Sept. 1990-Dec. 1995.
REICHERT ON DETERMINING CORROSION RATES 81
electrode will be the same. The measured potential noise will be the combined noise from
both electrodes, but the potential noise from one electrode is the quantity used to calculate
R, . Therefore, ~rVmeas is divided by X/2 to obtain ~V. The %/2 factor comes from the fol-
lowing relationships:
~V. , 0. , = (,~V, ~ + o v ~ ) ~
(2)
given:
crV1 = trV: = oV (3)
then:
, r v = ~ V m o a s / X / 2
where
crVmeas = standard deviation of measured potential noise,
~V~ = standard deviation of potential noise from first electrode, and
trV2 = standard deviation of potential noise from second electrode.
(4)
The LPR and ENM corrosion rates reported are averages of the multiple scans run peri-
odically during the immersion time. The mass loss corrosion rate data are the average rate
of all electrodes. In the sulfuric acid tests, there was considerable variability in the mass loss
rates from test to test despite identical solutions and nominally identical electrodes. There-
fore, separate averages were calculated for the mass loss rates from LPR electrodes and
ENM electrodes. In the other tests, mass loss results were highly reproducible.
Test Results
Ac e t i c A c i d
The first set of tests used 304L stainless steel in 50% acetic acid at 30 and 60~ The
LPR data were corrected for solution conductivity and correlated well with the ENM cor-
rosion rate (Table 1). An inspection of the coupons by optical microscopy did not reveal
evidence of any attack. The low corrosion rate and short test duration resulted in very small
mass loss values. Coupled with the sensitivity level of the balance, the uncertainty in the
mass loss corrosion rate exceeded the calculated rates. Because the LPR technique is an
established method for obtaining general corrosion rates and the LPR and ENM data
matched, this test was not repeated for a longer duration.
TABLE 1- - 316L stainless steel in 50% acetic acid.
Temperature, ~ ENM, mm/y LPR, mm/y Weight Loss, mm/y
30 0.0005 0.0005 0.023"
60 0.0008 0.0008 0.005 ~
a Error as a result of small weight loss and accuracy of balance = +0.025 mm/y.
b Error as a result of small weight loss and accuracy of balance = +0.018 mm/y.
Hi gh- Pur i t y Wat er
The low corrosi on rate of AI SI 1018 carbon steel in dei oni zed wat er at 230~ was hi gh
enough to generat e sufficient cor r osi on product s causi ng cont ami nat i on pr obl ems. The ex-
t ended t i me requi red for meani ngful mass l oss tests was unaccept abl e to t he pl ant request i ng
the data, so el ect rochemi cal t echni ques were investigated. A stable corrosi on pot ent i al was
not obt ai ned wi t h an EG&G Model 273 pot ent i ost at . Thi s may have been caused by ground
l oops bet ween the grounded pot ent i ost at and the el ect ri cal l y heat ed aut ocl ave. The very l ow
sol ut i on conduct i vi t y woul d have posed a pr obl em for t he LPR t echni que even i f a st abl e
pot ent i al had been obt ai ned. An at t empt was made to col l ect i mpedance spectra, but dat a
were t oo noi sy even at frequenci es above 1000 Hz.
The ENM t echni que successful l y di fferent i at ed bet ween t he i nhi bi t ors and the noni nhi bi t ed
wat er (Table 2). The di spar i t y in the cor r osi on rates for the t wo cal ci um hydr oxi de Ca( OH) 2
i nhi bi t ed sol ut i ons was expl ai ned by t he di fference in t he pH levels of t he sol ut i ons. Ca(OH)2
sol ut i ons are hi ghl y suscept i bl e to a l oweri ng of the pH from absorpt i on of carbon di oxi de
from the air, and this was the suspect ed source of the pH di screpancy. Fi el d trials usi ng
Ca(OH)2 were al so inconsistent.
Sul f uri c Ac i d
Sul furi c aci d (H2SO4) at 40~ offered the abi l i t y to obt ai n a wi de range of general cor-
r osi on rat es on 316L st ai nl ess steel whi l e changi ng onl y one vari abl e. The concent rat i ons
s el ect ed- - 10, 20, 30, and 4 0 %- - we r e expect ed to pr ovi de a range of corrosi on rat es from
hundredt hs t o tens of mi l l i met er s per year [13]. Al t hough this range was observed, t here was
a t remendous amount of scat t er in the data. In 30 and 40% H2SO4, t he initial passi ve film
somet i mes prot ect ed t he 316L from at t ack for mor e than 10 h even t hough i so- cor r osi on
di agr ams put t he corrosi on rat e at l ess than 10 mm/ y for 30% H2SO4 and great er t han 10
mm/ y for 40% H2SO4 [13]. In one LPR test, one el ect r ode was vi gor ousl y gi vi ng off hy-
dr ogen gas, whereas t he ot her coupon was inert. A sl i ght scrat ch wi t h a steel screwdri ver
caused r api d corrosi on at t he scrat ch mark, and wi t hi n art hour the ent i re coupon was r api dl y
corrodi ng.
The l arge amount of var i abi l i t y in the cor r osi on behavi or caused l arge vari at i ons in the
i ndi vi dual corrosi on rat es cal cul at ed from LPR. For one 30% H2SO 4 test, the i ni t i al LPR
rat e was 0.06 mm/ y and t he rate i ncreased over t he next 50 h until it was 43 mm/ y at the
end of t he test. In most of t he 30 and 40% concent rat i on tests, corrosi on rat es di d not fol l ow
a definite trend, j umpi ng up and down and di fferi ng by as much as a fact or of 5.
The 10 and 20% H2SO 4 tests showed r epr oduci bl e behavior. A represent at i ve pl ot of dat a
f r om t he 10% H2SO 4 1-cm 2 dat a set is shown in Fi g. 1. These ENM dat a are t ypi cal of
TABLE 2--Carbon steel in deionized water + inhibitors
at 230~
Inhibitor pH ENM, mm/ y
None 5 0.0075
l0 mg/ L Ca(OH) 2 l 0 0.0004
10 mg/ L Ca(OH)z 8 0.0032
25 mg/ L Na2MoO4 + 25 mg/ L Na2SiO 3 9 0.0007
75 mg/ L Na2SiO 3 9 0.0008
100 mg/ L NaNO 2 9 0.0495
E
E
c
? ,
-0. 4400
-0. 4405
-0. 4410
-0. 4415
-0. 4420
-0. 4425
-0.4430
Pot ent i al Noi se f or 316L in 10% Sul f uri c Aci d at 40"C
! i i I :
100 200 300 400 500 600
Ti me [S]
Cur r ent Noi se f or 316L in 10% Sul f uri c Aci d at 40"C
6, 50E-05
i i i I
0 100 200 300 400 500 600
6. 48E-05
6~46E-05
6. 44E- 05
6. 42E-05
6. 40E-05
6. 38E-05
6. 36E-05
Ti me [ s]
FIG. I - - ENM data f or 316L in 10% H2SO 4 at 40~
TABLE 3- - 316L i n 10% HzS04 at 40~
Weight Loss of LPR
Area, cm 2 LPR, mm/y Electrodes, mm/y ENM, mm/y
Weight Loss of ENM
Electrodes, mm/y
1 0.4318 0.3048 0.3556 0.3302
3 0.4318 0.2540 0.0051 0.0051
5 0.0025 0.0000 0.0178 0.0025
15 0.1178 0.2540 0.0762 0.0279
samples exhibiting general corrosion rates below 1.3 mm/y. A common potential noise trait
was an overall trend toward a higher or lower potential with superimposed random fluctu-
ations. The current noise did not tend to form patterns during general corrosion. An exception
to this was found when the current noise had regular oscillations that were found to correlate
with a heater cycling on and off. This effect was avoided by using water baths when possible
or proportional heating controllers to minimize temperature cycling.
Although there was some variation from cell to cell in the 10 and 20% HzSO 4 tests, the
mass loss rate correlated well with the values calculated from the electrochemical technique
used (Tables 3 and 4), In the cases in which LPR- and ENM-calculated corrosion rates
differed, the mass loss data for those coupons confirmed the different electrochemically
determined rates.
The 30 and 40% H2SO 4 results are listed in Tables 5 and 6. Significant end grain attack
was observed on the electrodes used in the tests, so the change in diameter was used as a
means of calculating the corrosion rate while discounting any grain dropping that may have
been caused by the end grain attack. It was found that the difference between corrosion rates
from mass loss and diameter change was less than 5% for the all 30% H2SO4 tests and for
the 15-cm 2 electrodes in 40% H2SO4. In 40% H2SO 4, the diameter change determined a
lower corrosion rate by 30, 15, and 10% for the 1-, 3-, and 5-cm 2 samples, respectively. This
correlation between electrode size and the relative impact of the end grain attack was not
surprising. Because all electrodes were of the same diameter, the larger electrodes were
longer and had a smaller relative amount of end grain area. Because electrochemical tech-
niques do not measure metal lost by grain dropping, the rates predicted by ENM and LPR
would have been expected to show the same level of disparity as the diameter change mea-
surements. In practice, end grain attack was insignificant compared to the overall scatter in
the data.
Tri-lso-Propanolamine.Hydrochloric Acid (TIPA.HCI)
Above about 160~ TIPA.HC1 has a corrosivity similar to 35% HC1. Below 160~ HC1
is bound to TIPA, and TIPA.HCI is noncorrosive to carbon steel. Plant conditions indicated
TABLE 4--316L in 20% H2S04 at 40~
Weight Loss of LPR Weight Loss of ENM
Area, crn 2 LPR, mm/y Electrodes, mm/y ENM, mm/y Electrodes, mm/y
1 1.0668 1.1684 1.3970 0.9906
3 0.8636 0.9906 0.7874 0.7894
5 0.5080 0.6096 0.0610 0.2794
15 0.5537 0.5588 0.5458 0.4318
REICHERT ON DETERMINING CORROSI ON RATES
TABLE 5 - - 3 1 6 L i n 30% H2SO 4 at 40~
85
Area, cm 2 LPR, mm/y Electrodes, mm/y ENM, mm/y Electrodes, mm/y
1 2.1 5.6 0.2 5.9
3 6.5 5.2 0.6 5.8
5 18.0 5.0 0.0 1.8 a
15 18.0 4.3 0.1 4.8
"Average of three electrodes with rates of: 0.0051, 0.0102, 5.3340 mm/y.
that there was a possibility of TIPA.HC1 being present under the elevated, corrosive condi-
tions. Plant inspections, however, showed no corrosion attack. Corrosion monitoring was
performed in the lab at 190~ to determine if the steel formed a protective layer of corrosion
products.
Mass loss coupons provided corrosion rates of 190 mm/ y for a 30-min exposure and 250
mm/ y for a 60-min exposure. A coupon left overnight (16 h) was consumed, indicating a
rate on the order of 250 mm/ y.
The ENM tests were run as nine consecutive 10-min scans. The initial data set showed a
corrosion rate of 15 mm/ y. After 20 min, the measured corrosion rate decreased to 5 to 8
mm/y. The ENM data followed a predictable decline in corrosion rate as a layer of loosely
adhered corrosion product grew on the electrode, slowing mass transport. If the ENM data
after the first 20 rain are considered representative of long-term corrosion behavior, then the
ENM corrosion rate calculated was about 30 times smaller than that determined by mass
loss.
Gamma-Butyrolactone (gBL) + Trace Contaminants
gBL was tested by ENM simply to evaluate the ability of ENM to measure corrosion rate
in a low-conductivity organic system. ENM data were collected on carbon steel and 316L
stainless steel at 130~ in gBL with unidentified trace impurities. The conductivity of the
gBL used was less than 10 ~mho/cm. Mass loss rates were 0.042 and 0.0038 mm/ y, whereas
noise resistance calculated rates were 0.043 and 0.0023 mm/ y for carbon steel and 316L,
respectively. The electrodes were threaded onto glass-coated stainless steel rods. The rods
were held in a plastic spacer so the electrodes were spaced approximately 0.03 cm apart to
minimize the effects of solution resistance.
D i s c u s s i o n
Potential noise data for the ENM tests performed ranged from 10 -5 to 10 z V, whereas
the current noise data ranged from 10 -~~ to 1 0 - 4 m. The baseline potential and current noise
TABLE 6--316L in 40% H2 S O 4 a t 40~
Area, cm 2 LPR, mm/y Electrodes, mm/y ENM, mm/y Electrodes, mm/y
1 8.9 32 1.2 31
3 15 21 1.3 21
5 12 19 0.51 18
15 67 16 0.051 9.1
levels from t he moni t ori ng equi pment were bot h t wo orders of magni t ude smal l er than the
noi se generat ed by the corrosi on processes studied. Therefore, t he i nst rument at i on was suit-
abl e for col l ect i ng EN data. The basel i ne noi se dat a were col l ect ed by l eavi ng the pot ent i al
l eads as an open ci rcui t and short ci rcui t i ng the current leads.
The corrosi on rates measured by R, fluctuated over t he durat i on of the i mmer si on t i me
for all t e s t s - - whe t he r the correl at i on to R e or mass l oss was good or poor. The magni t ude
of t hese vari at i ons t ended to mat ch t he magni t ude of the corrosi on rate. For exampl e, i f the
average corrosi on rate was 0.1 mm/ y, then i ndi vi dual ENM dat a sets woul d measure cor-
rosi on rat es from 0.01 to 0.2 mm/ y. Despi t e t hese vari at i ons, trends were still e vi de nt - - s uc h
as an i ncrease in the corrosi on rate measur ed i f the t emperat ure i ncreased. The i ncreased
cor r osi on rate was observed as an i ncrease in the mean val ue of the current noise. An i ncrease
in sol ut i on corrosi vi t y duri ng a scan (such as by addi ng an aci d) resul t ed in an i mmedi at e
j ump in the current noise. The magni t ude of the i ncrease in current noi se refl ect ed the degree
of change in the aggressi veness of the solution.
Variations in corrosi on rates were al so obser ved in the LPR tests, al t hough the magni t ude
of the vari at i ons was about hal f as large. Because general corrosi on is a st ochast i c process,
i t fol l ows that the corrosi on rat e wi l l vary wi t h t i me and that the average of t hose vari ed
rat es wi l l correl at e wi t h rates obt ai ned by a technique, such as mass l oss, that measures an
average corrosi on rate.
The sulfuric aci d tests were desi gned to l ook at the effect of el ect r ode area in addi t i on to
the val i di t y of usi ng R, to cal cul at e corrosi on rat es from ENM. For the 10 and 20% H2SO 4
tests, corrosi on rates det er mi ned by the mass loss met hod and by the R, t echni que mat ched
regardl ess of el ect r ode size. Thi s meant that the magni t ude of the current noi se correl at ed
wi t h el ect r ode area for t he 1- to 15-cm 2 areas tested.
In t he cases in whi ch cor r osi on rates were high, the ENM dat a di d not correl at e wel l wi t h
mass loss data. In the 30 and 40% H2SO 4 experi ment s, the st andard devi at i on of t he pot ent i al
noi se was very hi gh and t ended to domi nat e (crV > > ~/ ) t he R, value. The ~V val ue for
t hese tests gener al l y r anged bet ween 1 and 10 mV. Much of the vari at i on was due to sub-
stantial dri ft i ng of the corrosi on pot ent i al (Fi g. 2). Some of this dri ft may have been due to
the hi gh corrosi on rates obser ved in many tests. Anot her source for t he hi gh pot ent i al noi se
was the l arge amount of hydr ogen bubbl i ng occurri ng on the surface, Mansf el d has report ed
that fluctuations in mass t ransport cont rol can pr oduce l arge changes in the corrosi on pot en-
t i al [14].
A t hi rd aspect of the poor correl at i on may be sat urat i on of the noi se data. The TIPA.HC1
t est al so showed poor correl at i on bet ween R, and mass l oss corrosi on rates. In this case, crV
was much smal l er than in t he 30 and 40% H2SO 4 experi ment s and di d not domi nat e the
rat i o R, = ~rV/~l. The ENM pat t ern for the TIPA.HC1 tests (Fig. 3) appears very si mi l ar to
that shown in Fi g. 1 for t he 10% HzSO4 tests, yet the magni t ude of the current noi se does
not reflect the hi gh cor r osi on rate.
Based on current noi se val ues from t he 10 and 20% HzSO 4 tests, current noi se roughl y
cor r el at ed wi t h corrosi on rate. The current noi se ranges for vari ous corrosi on rat es are l i st ed
in Tabl e 7. Ignori ng the apparent t rend that t he i ncrease in current noi se is faster than the
i ncrease in corrosi on rate, a l i near ext rapol at i on of Table 7 woul d ant i ci pat e a current noi se
on the or der of 10 -2 A/ c m z for the cor r osi on rat e of 250 mm/ y obser ved in TIPA. HCI. Such
a l arge current noi se magni t ude woul d requi re a subst ant i al segregat i on of the anodi c and
cat hodi c sites bet ween t he current measuri ng el ect rodes. As t he corrosi on rat e i ncreases and
segregat i on becomes mor e difficult to achi eve, t he current noi se wi l l saturate, resul t i ng in
poor correl at i on bet ween ENM and mass l oss data.
9.00E-03
B
o
Pot ent i al No i s e f o r 3 1 6 L i n 3 0 % Sul f ur i c Ac i d at 4 0 ~
(J
8.50E-03
8.00E-03
7.50E-03
7,00E-03
6,50E-03
6.00E-03
5.50E~
5.00Eo03
4.50E-03
4.00E-03
I I r I I
100 200 300 400 500 600
I Ti me Is]
Cu r r e n t No i s e f o r 3 1 6 L in 3 0 % Sul f ur i c Ac i d a t 4 0 ~
4.00E-06
I I I I I
0 100 200 300 400 500 600
Ti me [s]
3.50E-06
3,00E-06
2,50E-06
2.00E-06
1.50E-06
1,00E-06
FIG. 2- - ENM data f or 316L in 30% H2SO 4 at 40~C.
-0.0006
= :
~ o
a.
Pot ent i al Noi se f or Car bon Steel i n TI PA. HCl
i i b i i
100 200 300 400 500 600
Time Is]
-0.0008
-0.001
-0.0012
-0.0014
-0.0016
-0.0018
Cur r ent Noi se f or Car bon Steel i n TI PA. HCl
O.OOE+O0
c
-2.00E-05 -
-4.00E-05 -
-6.00E-05
-8.00E-05
-1.00E-04
-1.20E-04
-1.40E-04 i i b i i
1 O0 200 300 400 500 600
Time [s]
FIG. 3- - ENM data f or carbon steel in TIPA.HCt at 190~
REICHERT ON DETERMINING CORROSION RATES
TABLE 7--Corrosion rate approximations f or current
noise ranges.
Current Noise Range, A/ cm 2 Corrosion Rate, mm/ y
10- 9~ 10 8 0.003
10 -8 ~ 10 -7 0.03
10 -6 ~ 10 -5 0.3
1 0 - 5 ~ 10 4 1,3
89
Conclusions
The R, anal ysi s met hod pr oved hi ghl y effect i ve for det er mi ni ng corrosi on rates for syst ems
exhi bi t i ng general cor r osi on rat es bel ow 1.3 mm/ y. Agr eement bet ween R, , Rp and mass
loss values was very good for bot h carbon steel and st ai nl ess steel in di fferent envi ronment s.
Correl at i ons bet ween R, and mass loss measurement s broke down at hi gh corrosi on rates.
Hi gh pot ent i al noi se coupl ed with l ower - t han- pr edi ct ed current noi se resul t ed in l ow cal cu-
l at ed corrosi on rates usi ng R, . Hydr ogen bubbl i ng cont ri but ed to the pot ent i al noise, t hereby
i ncreasi ng the cal cul at ed val ue of R, . Anot her pr oposed source for l ow corrosi on rat es
cal cul at ed by R, was sat urat i on of t he current noi se at hi gh corrosi on rates. Ext r apol at i ng
t he current noi se ranges obser ved for l ow to moder at e corrosi on rat es to hi gh rat es i mpl i es
a very hi gh coupl i ng c ur r e nt - - on the order of tens of mA/ c m2 - - f o r hi gh corrosi on rates.
The l arge segregat i on of the anodi c and cat hodi c sites requi red to generat e such currents
woul d be difficult to achieve, and current noi se of this magni t ude was not obser ved even for
corrosi on rat es of 250 mm/ y.
References
[1] Iverson, W. P., Journal of the Electrochemical Society, Vol. 115, No. 6, 1968, pp. 617-618.
[2] Hladky, K. and Dawson, J. L., Corrosion Science, Vol. 22, No. 3, 1982, pp. 231-237.
[3] Bertocci, U., Journal of the Electrochemical Society, Vol. 127, No. 9, 1980, pp. 1931-1934.
[4] Gabrielli, C., Huet, E, Keddam, M., and Oltra, R., Corrosion, Vot. 46, No. 4, 1990, pp. 266-278.
[5] Mansfeld, E, Research in progress, CORROSION/94, NACE, Baltimore, MD, 1994.
[6] Roberge, E R., Beaudoin, R., and Sastri, V. S., Corrosion Science, Vol. 29, No. 10, 1989,
pp. 1231-1233.
[7] Scully, J. R. and Hudson, J. L., Oral presentation, T-3L-15, ENM Task Group, CORROSION/93,
NACE, New Orleans, LA, 1993.
[8] Hladky, K. and Dawson, J. L., Corrosion Science, Vol. 21, No. 4, 1981, pp. 317-322.
[9] Eden, D. A., Hladky, K., and John, D. G., NACE CORROSION/86 Conference, NACE, Houston,
TX, 1986, Paper 274.
[10] Dawson, J. L., Farrell, D. M., Aylott, P. J., and Hladky, K., NACE CORROSION/89 Conference,
NACE, New Orleans, LA, 1989, Paper 31.
[11] Rothwell, A. N. and Eden, D. A., NACE CORROSION/92 Conference, NACE, Nashville, TN,
1992, Paper 223.
[12] CML Technology Transfer, "Mathematical Analysis of Electrochemical Noise Signals," Capcis
March Limited, Manchester, UK, circa 1993 (not dated).
[13] Davis, J. R., Ed. Metals Handbook, 9th ed., Vol. 13 Corrosion, ASM International, Metals Park,
OH, 1987, p. 1150.
[14] Mansfeld, E and Xioa, H., Journal of the Electrochemical Society, Vol. 140, No. 8, 1993,
pp. 2205-2209.
Data Analysis
R. A. Cottis, l S. T u r g o o s e , 1 and J. Me ndoz a- Fl or e s ~
The Effects of Solution Resistance on
Electrochemical Noise Resistance
Measurements: A Theoretical Analysis
RE F E RE NCE : Cottis, R. A., Turgoose, S., and Mendoza-Flores, J., " Th e Ef f e c t s o f So l ut i o n
Re s i s t a nc e o n El e c t r o c h e mi c a l No i s e Re s i s t a n c e Me a s u r e me n t s : A The o r e t i c a l Ana l y s i s , "
Electrochemical Noise Measurement f or Corrosion Applications, ASTM STP 1277, Jeffery R.
Keams, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds.,
American Society for Testing and Materials, 1996, pp. 93-100.
ABSTRACT: The theoretical basis of electrochemical noise resistance measurements in the
presence of significant solution resistance is examined with a simple linear circuit model. A
shot noise model of the noise generation process is assumed to develop the dependence of
electrochemical potential and current noise on corrosion rate, although the conclusions in re-
spect to electrochemical noise resistance do not depend on this. It is concluded that the elec-
trochemical noise resistance method measures essentially the same resistance as is measured
by a conventional linear polarization resistance measurement, although it is found to be capable
of making measurements in higher resistance systems.
KEYWORDS: electrochemical noise, noise resistance, polarization resistance, corrosion rate
measurement
It has been shown by several workers (see, for example, the other papers in this volume)
that electrochemical noise resistance measurements compare well with other electrochemical
techniques, such as linear polarization resistance and electrochemical impedance spectros-
copy, for the estimation of corrosion rate (although not all investigations have given a good
correlation). However, recent work has shown that noise resistance measurements are subject
to errors as a result of the resistance of the solution between the measuring electrodes. This
paper is concerned with the analysis of the effects of solution resistance, although this com-
mences with the development of a simple theoretical basis for noise resistance measurements.
Note that more detailed mathematical analyses of a range of possible electrochemical noise
generation processes have been performed, and Gabrielli provides a good summary of these
[11.
A s s u m p t i o n s
For the purpose of our analysis, several simplifying assumptions are made. The physical
system considered is the conventional three-electrode noise resistance measurement with the
electrochemical current noise being measured between two electrodes, and the electrochem-
ical potential noise of the pair of electrodes being measured with respect to a third electrode,
Senior lecturer, lecturer, and research student, respectively, Corrosion and Protection Centre, UMIST,
PO Box 88, Manchester M60 IQD, UK.
9 3
www.astm.org
whi ch may ei t her be a l ow-noi se reference el ect r ode or a t hi rd el ect rode of the same mat eri al
as the ot her two. For the purposes of this paper, t he reference el ect r ode is assumed to be
noi se-free, but it is a si mpl e mat t er to add the noi se generat ed at a " noi s y" reference el ec-
trode. Bot h t he anodi c and cat hodi c react i ons are consi der ed to be processes that generat e
current. Hence, current noi se is a fundament al out put of the corrosi on react i on, whereas
pot ent i al noi se is an i ndi rect output that results from the act i on of t he current noi se on the
component s of t he el ect r ochemi cal syst em.
Bot h anodi c and cat hodi c react i ons are assumed to result in pul ses of charge of rel at i vel y
short durat i on. For the cat hodi c react i on of oxygen reduct i on, it is expect ed that the current
pul ses wi l l be smal l , pr obabl y consi st i ng of j ust the four el ect rons pr oduced by t he reduct i on
of one oxygen mol ecul e (mass t ransport fluctuations may pr ovi de a mor e si gni fi cant source
of noi se in pract i ce, but t hese are not consi der ed here). This wi l l pr obabl y al so appl y to
hydr ogen evol ut i on at l ow current densi t i es, such that the hydrogen gas mol ecul es diffuse
into the solution, but at hi gher current densi t i es the maj or source of noi se wi l l be the fluc-
t uat i on of exposed el ect r ode area and mass t ransport processes as a result of hydr ogen bubbl e
evol ut i on, whi ch wi l l cl ear l y not fit our assumpt i on. For the anodi c process, i t has been
argued [2] that act i vat i on-cont rol l ed corrosi on wi l l generat e bursts of charge of t he or der of
10 3 el ect rons, whereas it is wel l est abl i shed that noi se generat ed by met ast abl e pi t t i ng wi l l
consi st of pul ses of charge wi t h durat i ons of a few seconds and wi t h a charge of t he order
of 1 p.C. Ot her forms of noi se generat i on process for the anodi c react i on may not produce
pul ses of charge, wi t h chaot i c [3] and peri odi c [4] behavi or havi ng been report ed. It is
assumed that the pul ses of charge pr oduced by t he anodi c and cat hodi c react i ons are i nde-
pendent. Thi s seems a r easonabl e assumpt i on, al t hough it is cl ear that t he average DC cur-
rents must be equal to mai nt ai n charge neut ral i t y (short -t erm di fferences can be accommo-
dat ed by chargi ng and di schargi ng of the doubl e- l ayer capaci t ance).
To use st andard st at i st i cal results for t he anal ysi s of the noi se charact eri st i cs, it is assumed
that the charge pul ses are i ndependent of one anot her and that t he anodi c and cat hodi c
react i ons are uncorrel at ed and can t herefore be t reat ed as i ndependent sources of current
noise. At first sight, the l at t er assumpt i on is invalid, at l east at l ow frequenci es, because the
average anodi c and cat hodi c current s must be the same, ot herwi se the speci men pot ent i al
wi l l change as a resul t of the accumul at i on of charge. However, the l i nk bet ween the t wo
react i ons is bot h compl ex and indirect. The det ai l s of this l i nkage are not yet compl et el y
clear, and at present, t he assumpt i on of i ndependence is t he onl y vi abl e approach.
The anal ysi s present ed here wi l l be rest ri ct ed to the l ow-frequency l i mi t of the noi se
behavior, so that current pul ses may be t reat ed as del t a functions (that is, i nst ant aneous pul ses
of charge), al t hough it is rel at i vel y st rai ght forward to ext end the anal ysi s to the full frequency
spectrum.
Current Noise
Gi ven the assumpt i ons made, it is cl ear that each el ect rochemi cal react i on can be t reat ed
wi t h a shot noi se anal ysi s. Essent i al l y, this assumes that the noi se arises as a resul t of the
r andom vari at i on in the number of pul ses ari si ng in a gi ven t i me interval. Through a si mpl e
st at i st i cal anal ysi s [5], this resul t s in a current noi se power gi ven by
= 2qI b (1)
where
CO'I-I'IS ET AL. ON EFFECTS OF SOLUTION RESISTANCE ON ENM 95
m
I , ~ = mean squared noi se current or current noi se power,
q = charge in each pulse,
I = mean current, and
b = bandwi dt h of measurement .
Not e that, as is common in si gnal processi ng, the t er m p o w e r is used t o descri be bot h
currenF and voltage, 2 on t he basi s that the power di ssi pat ed in a resi st i ve l oad is gi ven by
V 2 R or 12R.
I f we consi der t he react i ons occurri ng at the met al - s ol ut i on i nt erface, we can see t hat
t here are act ual l y t wo currents fl owi ng on each el ect r ode as a resul t of t he anodi c and
cat hodi c react i ons. These are assumed to be i ndependent and may t herefore be anal yzed
separat el y, and the noi se powers are summed to obt ai n t he t ot al noi se power. Thi s l eads t o
a total current noi se power gi ven by
1,2 = 2(qa + qc)Icor~b (2)
where
qa = charge in anodi c react i on pul se,
q,. = charge in cat hodi c react i on pulse,
Icor~ = cor r osi on current on t he el ect rode, and
b -- bandwi dt h of measurement .
I f t wo such el ect rodes are coupl ed t oget her t hrough a ci rcui t of zero resi st ance, t he noi se
current power det ect ed bet ween the t wo el ect rodes wi l l be t he same as t hat of t he i ndi vi dual
el ect rodes (because hal f of the power wi l l be di ssi pat ed on t he same el ect r ode as t he current
source and, hence, wi l l not be det ect ed). However, when a sol ut i on resi st ance is i nt erposed
bet ween the t wo el ect rodes, this reduces t he noi se current; effectively, t he sol ut i on resi st ance
forces a great er part of t he noi se current to r emai n l ocal i zed on t he i ndi vi dual el ect rodes. To
anal yze this situation, we need to devel op a si mpl e met hod of t reat i ng the pot ent i al noi se
pr oduced by the passage of the noi se current.
Electrochemical Potential Noise
I f we consi der a noi se generat i on process such as act i vat i on-cont rol l ed corrosi on, i t can
be seen that an exact descr i pt i on of t he pot ent i al noi se generat i on process wi l l consi der t hat
t he current noi se consi st s of current pul ses that have a pot ent i al dependent rat e of generat i on,
and that the pot ent i al noi se arises by t he chargi ng and di schargi ng of t he i nt erfaci al capac-
i t ance by the anodi c and cat hodi c current pulses. Thi s syst em is bei ng model ed numer i cal l y
by the authors but is rat her compl ex for use in a si mpl e anal ysi s. However, we can obt ai n
a si mpl er met hod of t reat i ng t he pot ent i al dependence by not i ng that the pol ari zat i on resi s-
t ance (Rp) wi l l be pr oduced by t he act i on of ext ernal l y i mposed pot ent i al changes on exact l y
the same pul se generat i on processes. Thus, it seems r easonabl e t o model t he pot ent i al noi se
generat i on process as t he response of t he pol ar i zat i on resi st ance t o the noi se current. The
exact val i di t y of this approach r emai ns to be tested, because it may be not ed t hat t he charge
pul ses and t he apparent pol ari zat i on resi st ance that results are pr oduced by t he same process.
Hence, t he i mpl i ed assumpt i on of st at i st i cal i ndependence is not st ri ct l y correct. Conversel y,
when t wo pol ar i zat i on resi st ances are in paral l el , as when measur i ng el ect r ochemi cal current
noise, it is not cl ear t hat the behavi or wi l l be model ed correct l y by the val ue cal cul at ed f r om
conventional circuit theory because the currents through the two resistances will be uncor-
related. For the purposes of this paper and for consistency, we have assumed that the use of
Rp is valid; any errors resulting from this assumption are likely to be a factor of ~ or less
(because this is the difference between adding correlated and uncorrelated noise currents),
and errors in potential and current noise may cancel in calculating noise resistance. Al so
note that we are working in terms of currents and polarization resistances for the electrode
area, not with normalized current densities and polarization resistances.
I f we adopt this simplified approach, the electrochemical potential noise power is obtained
by the application of Ohm' s law
u
Not e that this relationship should not be taken as a theoretical justification of the noise
resistance method because, to a certain extent, we are assuming the validity of the method.
Rather, the experimental applicability of the noise resistance method lends support to this
model. Not e also that the potential and current noise power terms in Eq 3 are generalized,
rather than the specific values for this analysis (that is, a potential noise power of E~, will
be produced i f a current noise of ~ is applied to the polarization resistance).
Because of the relationship between Rp and Icorr that is implied by the Stern-Geary
equation,
B
Ic~ : pR-- (4)
where B = the Stern-Geary coefficient, we can derive two useful relationships:
B 2 - 2BZ(qa + q c ) b
VE-] I ] (6)
( q " + q~) = 2 B b
Equation 5 suggests that potential noise power will be i n v e r s e l y proportional to corrosion
rate. This result is inconsistent with the results of early work that suggested that potential
was proportional to corrosion rate [6]. This apparent contradiction may possibly be ration-
alized by consideration of changes in the value of qa or qc- Equation 6 provides a met hod
for determining the value of (q, + qc), which may provide useful information on localized
corrosion processes. These questions will be treated in more detail elsewhere.
Effect of Solution Resi stance
To model the influence of solution resistance, we shall consider an equivalent circuit model
of the process (Fig. 1). Not e that both the noise current sources and the polarization resis-
tances ( R p ) associated with the working electrodes in Fig. 1 are at the met al -sol ut i on
interface.
This model considers that the reference electrode is equidistant from the two working
electrodes, such that it samples the potential halfway between the two electrodes. We also
assume that a noise-free reference electrode is used; i f a reference electrode of the same
material as the working electrode is used, this will add to the potential noise power.
COI-IIS ET AL. ON EFFECTS OF SOLUTION RESISTANCE ON ENM 97
I R e f e r e n c e ]
E le c tr o d e I
S o l u t i o n
I . . . . . . . .
Current ~ ~ C u r r e n t saole tu tailo'n
T S ~ i n t e r f a c e
s~ Y z.,~, zm . . . . . . . .
J W o r k i n g
E le c t r o d e I ] J W o r k i n g
E le c t r o d e 2 ] M e t a l
I Q i
FIG. 1--Equivalent circuit for three-electrode noise resistance measurement.
In the absence of solution resistance, the currents resulting from the t wo noise current
sources pass through the polarization resistance of the two electrodes to give a potential
noise as a result of each current of
m
I 2 R~ (7)
~ n n ( d u e t o o n e c u r r e n t ) - - 4
The potential noise powers caused by the two independent noise sources add to give a
total potential noise
~ . = ~ R~ ( 8 )
2
Not e that, from Eq 2, ft, is proportional to Icon, and hence to specimen area (because Icor~ is
the corrosion current density times the specimen area). When combi ned with Eq 8, and
remembering that Rp is inversely proportional to specimen area, this leads to the somewhat
counterintuitive relationship between potential noise and area,
E - ~ 1
Area (9)
I f the solution resistance is non-zero, we may apply a simple circuit analysis to determine
the effect of the noise current on the potential detected at the midpoint of the solution
resistance and the corresponding current through the solution resistance.
Considering one current source, the current will flow through the polarization resistance
associated with the same working electrode as the current source, Rp, in parallel with the
solution resistance, Rs, plus the polarization resistance of the other working electrode.
The noise potential across this resistor network can be calculated, and the potential noise
at the reference electrode can be determined by considering the potential divider consisting
of the t wo part s of the sol ut i on resi st ance pl us the r emot e pol ari zat i on resi st ance. The po-
t ent i al noi se power as a resul t of the t wo i ndependent current sources is then t wi ce that
resul t i ng from the one current source, gi vi ng the same resul t as Eq 8. Thus, t he measured
pot ent i al noi se is unaffect ed by the sol ut i on resi st ance.
Electrochemical Current Noise
In the absence of sol ut i on resi st ance, t he measured noi se current caused by each source
wi l l be hal f the total current from the source (because the ot her hal f wi l l flow t hrough t he
pol ari zat i on resi st ance on t he same el ect r ode and wi l l not t herefore be det ect ed; as t he
current s are correl at ed, because t hey come from the same current noi se source, the current s
wi l l be hal ved, not the current powers). The current noi se powers as a resul t of t he t wo
i ndependent sources wi l l add, gi vi ng a measur ed noi se current power
. . . . red - - T ( 10)
Not e that this anal ysi s is correct f o r the equivalent circuit, in whi ch t he separat i on of the
noi se current s bet ween the t wo el ect rodes results in the di vi si on of the current power by 4
(22 ) because the t wo current s are not i ndependent (bei ng due to t he same vol t age appl i ed
across t wo resistors). However, in t he real el ect rochemi cal interface, it seems pr obabl e that
the t wo current s wi l l be i ndependent , in whi ch case t he separat i on of currents wi l l resul t in
di vi si on of the current power s by onl y 2. Hence, the measured noi se current wi l l be equal
to t he noi se current on one el ect rode. Thi s quest i on wi l l be consi der ed further el sewhere,
and for the present anal ysi s i t is assumed t hat the equi val ent ci rcui t resul t is val i d (because
the result for the sol ut i on resi st ance case necessar i l y makes this assumpt i on).
When the sol ut i on resi st ance is non-zero, the di st ri but i on of current bet ween t he t wo
el ect rodes is modi fi ed. Consi der i ng the current source on one el ect rode, i t can be seen that
the proport i on of current flowing to the ot her el ect r ode (and hence bei ng measured) is Re/
(Rs + 2Rp). Therefore, t he measur ed current power wi l l be gi ven by
h
( 2 , 2
12 . . . . . d = ( R s + 2 e p ) ]
(11)
Compar i son of Eqs 11 and 12 shows that the measured current wi l l be in error by a fact or
2Rf f ( R, + 2Rp), as mi ght perhaps be expect ed intuitively, and as woul d al so be obt ai ned for
a pol ari zat i on resi st ance measurement . Hence, the measured resi st ance wi l l si mpl y be in-
creased by t he sol ut i on resi st ance, and, i f the sol ut i on resi st ance is known, t he resul t can, in
pri nci pl e, be correct ed (al t hough errors are l i kel y to l i mi t the possi bi l i t y for correct i on i f the
sol ut i on resi st ance is si gni fi cant l y great er t han the pol ari zat i on resi st ance).
Experimental Results
To test the effects of sol ut i on resi st ance on noi se resi st ance measurement s and compar e
the results of el ect rochemi cal and wei ght l oss measurement s, a series of exper i ment s have
been per f or med wi t h mi l d steel cor r odi ng in sodi um sulfate (Na2SO4) sol ut i ons wi t h a range
of concent rat i ons from 0.001 to 1% and at a t emperat ure of 60~ Ful l det ai l s of t hese
exper i ment s are present ed el sewher e [7], but t he results are summar i zed here in Fi g. 2. The
corrosi on rate, as det er mi ned wi t h wei ght l oss measurement s over a per i od of 15 days, was
CO'I-i-IS ET AL. ON EFFECTS OF SOLUTION RESISTANCE ON ENM 99
FIG. 2--Comparison of corrosion rate measurements (without compensation f or solution resistance).
essential l y independent of Na2SO4 concentration. The corrosion rate is compatibl e with ox-
ygen mass-transport control . Hence, the Na2SO4 is thought simpl y to provide sufficient so-
l ution conductivity to coupl e the anodic and cathodic reactions. With high N~2SO 4 concen-
t rat i ons, such that the sol ution resistance is much smal l er than the pol arization resistance,
all three el ectrochemical techniques give reasonabl y good resul ts in comparison with weight
l oss measurements. ( Note that the weight l oss measurements are necessaril y made over a
reasonabl y l ong period, whereas the el ectrochemical measurements reported here were made
af ter 3-h exposure, thus it is not expected that a perf ect correl ation wil l be obtained.) I n
more dil ute sol utions, the el ectrochemical techniques become more difficult. El ectrochemical
impedance al l ows the separate measurement of Rp and R,, but when Rs becomes l arge rel ative
to Rp, noise renders the discrimination of R e impossibl e. Linear pol arization resistance and
noise resistance measurements appear to measure the same thing, but the noise resistance
method is abl e to make measurements in more dil ute sol utions ( al though it is, of course,
measuring R, + Rp rather than Rp al one). I f the sol ution resistance is known, both pol arization
resistance and noise resistance measurements can be corrected to determine Rp, al though the
error increases rapidl y as Rs becomes l arge comp ared to Rp. This is il l ustrated in Fig. 3.
Concl usi ons
For corrosion processes that resul t in bursts of charge, the noise current p ower is expected
to be proportional to the corrosion rate, whereas the potential noise p ower is expected to be
inversel y proportional to corrosion rate. Both current and potential noise powers are expected
to be proportional to the quantity of charge in each pul se.
I n l ow-resistivity sol utions, noise resistance measurements appear to be comp arabl e to
el ectrochemical impedance spectroscopy and l inear pol arization resistance measurements in
their abil ity to estimate corrosion rate.
FIG. 3--Comparison of corrosion rate measurements (with compensation f or solution resistance).
Linear pol arization resistance and noise resistance measurements both measure the sol ution
resistance in addition to the pol arization resistance.
The noise resistance technique can make measurements in sol utions of much higher re-
sistivity than either pol arization resistance or impedance (al though the resul ts are, of course,
l argel y measuring sol ution resistance).
Ref erences
[1] Gabrielli, C., Huet, E, and Keddam, M., "Investigation of Metallic Corrosion by Electrochemical
Noise Techniques," in Electrochemical and Optical Techniques f or the Study and Monitoring of
Metallic Corrosion, M. G. S. Ferreira and C. A. Melendres, Eds., NATO AS1203, Kluwer, Dordrecht,
1991, pp. 135-190.
[2] Cottis, R. A., "Modelling of Electrochemical Noise Due to the Activation-Controlled Dissolution of
Metals," in Modelling Aqueous Corrosion, K. R. Threthewey and P. R. Roberge, Eds., NATO ASI
Series E, Vol. 266, Kluwer, Dordrecht, 1994, pp. 369-379.
[3] Li, W., Nobe, K., and Pearlstein, A. J., "Electrodissolution Kinetics of Iron in Chloride Solutions
VIII: Chaos in Potential/Current Oscillations," Journal of the Electrochemical Society, Vol. 140,
1993, pp. 721-728.
[4] Russell, P. and Newman, P., "Current Oscillations Observed Within the Limiting Current Plateau
for Iron in Sulfuric Acid," Journal of the Electrochemical Society, Vol. 133, 1986, pp. 2093-2097.
[5] Schottky, W., Annals of Physics, Vol. 57, 1918, p. 541. (See King, R. A., ElectricalNoise, Chapman
and Hall, London, 1966, for a more recent description.)
[6] Iverson, W. P., "Transient Voltage Changes Produced in Corroding Metals and Alloys," Journal of
the Electrochemical Society, Vol. 115, 1968.
[7] Mendoza-Flores, J., "Electrochemical Techniques Applied to the Study of Mild Steel Corrosion in
1%, 0.1%, 0.01% and 0.001% Na2SO4 Solutions," MSc dissertation, UMIST, 1993.
Rober t G. Kel l y, 1 M ar i a E. I nman, 1 and J ohn L . H udson 1
Analysis of Electrochemical Noise for Type
410 Stainless Steel in Chloride Solutions
REFERENCE: Kelly, R. G., Inman, M. E., and Hudson, J. L., "Analysis of Electrochemical
Noise for qPype 410 Stainless Steel in Chloride Solutions," Electrochemical Noise Measure-
mentfor Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R. Scully, Pierre
R. Roberge, David L. Reichert, and John L. Dawson, Eds., American Society for Testing and
Materials, 1996, pp. 101-113.
ABSTRACT: The electrochemical noise resulting from the corrosion of Type 410 stainless
steel under open circuit conditions in solutions of widely different corrosivity has been ex-
amined. Parameters derived from electrochemical noise measurements and conventional elec-
trochemical measurements were correlated with one another and with post-test examination of
the specimens. Both the noise resistance and the polarization resistance increased with de-
creases in solution corrosivity. In all of the solutions studied, the noise resistance was found
to be consistently higher than the polarization resistance. In solutions in which pitting occurred,
the open circuit potential of the electrode versus a true reference electrode was more sensitive
to the transition to stable pitting than was the pitting index.
KEYWORDS: stainless steel, pitting, uniform corrosion, polarization resistance, electrochem-
ical noise
The corrosion of 13Cr stainless steels is a concern in the oil and gas industry because of
the use of this material for downhole tubulars. Although chemical inhibition is used to
combat degradation, its effectiveness is difficult to monitor. The emergence of electrochem-
ical noise measurement (ENM) as a monitoring technique is of particular interest because
of its noninvasive character. This paper describes the preliminary investigation of a variety
of analysis methods to determine what correlations exist among electrochemical noise mea-
surements, conventional electrochemical measurements, and the nature and extent of the
observed corrosion attack of Type 410 stainless steel (SS410) in room temperature solutions.
Electrochemical noise measurement has been investigated as a monitoring tool for the last
20 years [1]. One way to categorize the types of electrochemical noise is by the electro-
chemical signal that is collected. Potential noise refers to measurements of the open circuit
potential of an electrode versus either a reference electrode or versus a nominally identical
electrode. Although measurements with a conventional reference electrode have the advan-
tage of being relatable to thermodynamic conditions, these reference electrodes have their
own noise associated with them, which could complicate analysis. In addition, the application
of ENM to field conditions is much more attractive if maintenance of the reference electrode
is not required. Because the fluctuations of the signal are typically considered to be the most
important aspect of electrochemical potential noise (EPN), rather than the absolute value of
Assistant professor, postdoctoral research associate, Department of Materials Science & Engineering,
and professor, Department of Chemical Engineering, respectively, University of Virginia, Thornton Hall,
Charlottesville, VA 22903.
101
www.astm.org
the pot ent i al , the use of an el ect r ode nomi nal l y i dent i cal to the wor ki ng el ect rode has become
popular. Al t hough the average pot ent i al di fference bet ween t rul y i dent i cal el ect rodes woul d
be zero, under condi t i ons for whi ch l ocal i zed corrosi on is possi bl e, large DC di fferences can
devel op. For exampl e, i f pi t t i ng were to i ni t i at e on onl y one el ect rode, its pot ent i al wi l l fall
wi t h respect to the other. Electrochemical current noise (ECN) is oft en measured as the
fluctuation in the current that passes bet ween t wo nomi nal l y i dent i cal el ect rodes that are
exposed to the same envi ronment and connect ed t hrough a zero resi st ance ammet er (ZRA).
The fluctuations in this coupl i ng current are due to each el ect rode becomi ng mor e or less
anodi c with respect to the ot her as a funct i on of time. The initiation, short -t erm pr opagat i on
and repassi vat i on of a pi t on one el ect r ode whi l e the ot her remai ns passi ve is an exampl e
of a physi cal ori gi n of such a phenomenon. Al t hough the el ect rodes are nomi nal l y i dent i cal ,
mi nor di fferences in el ect rochemi cal behavi or do exi st (or somet i mes devel op), whi ch l ead
to di fferences in pot ent i al and t herefore the coupl i ng current. These t ransi ent di fferences are
the basi s for the ENM. As with the pot ent i al , duri ng l ocal i zed corrosi on, subst ant i al DC
currents can pass bet ween el ect rodes short ed through a ZRA, i f onl y one i ni t i at es a pit.
Most field appl i cat i ons of ENM have i nvol ved a t hree-el ect rode pr obe system. Two nom-
i nal l y i dent i cal el ect rodes are connect ed vi a a ZRA, and the ECN is measured. The pot ent i al
of this coupl e is then measured agai nst the t hi rd nomi nal l y i dent i cal el ect r ode to moni t or
the EPN associ at ed wi t h t he same processes. This approach has been found useful in that it
al l ows an addi t i onal correl at i on (bet ween the t wo t ypes of noi se measurement s) to be made.
Successful correl at i ons bet ween noi se measurement s and corrosi on processes have been
demonst r at ed for uni form corrosi on as wel l as pi t t i ng in i ndi vi dual syst ems. Dawson et al.
[2] found that the rat i o of the st andard devi at i ons of the pot ent i al and current noi se (whi ch
t hey t er med the noi se resi st ance, R, ) correl at ed wel l with bot h the pol ari zat i on resi st ance
det er mi ned by convent i onal met hods and wei ght l oss of carbon steel in acid. By usi ng
di fferent sol ut i on composi t i ons, di fferent t ypes of at t ack were created, and t hey found qual -
itative di fferences bet ween the el ect rochemi cal noi se si gnat ures for uniform, pi t t i ng, and
crevi ce corrosi on. A number of workers have correl at ed noi se measurement s to the occur-
rence of l ocal i zed corrosi on. Pitting has been the most studied, wi t h appl i cat i ons wi t h steels
[3], st ai nl ess steels in C1 [4-6], and al umi num al l oys [7,8]. The pi t t i ng i ndex (PI) is cal -
cul at ed as shown accordi ng to Eden et al. [9]:
P I ~-- ~
Irm ~
where a~ is the st andard devi at i on of the ECN and Irm~ is the r oot mean square of t he coupl i ng
current. Because the ECN may vary with t i me, t hese quantities shoul d be cal cul at ed over
the same t i me peri od.
The pi t t i ng i ndex can have a val ue bet ween 0 and 1. Eden et al. have report ed the cl as-
sification for the pi t t i ng i ndex shown in Tabl e 1. The reasoni ng behi nd the formul at i on of
TABLE 1--Correlation between pitting index (PI) and type of
corrosion expected [9].
Pitting Index Value Range Type of Corrosion Expected
0.001 < PI < 0.0l uniform corrosion
0.0l < PI < 0.1 mixed corrosion
0.1 < PI < 1.0 localized corrosion
KELLY ET AL. ON ANALYSIS OF ELECTROCHEMICAL NOISE 103
the PI is that pi t t i ng occurs on i ni t i al l y passi ve el ect rodes, whi ch exhi bi t smal l coupl i ng
currents, and the i ni t i at i on of l ocal i zed attack can be det ect ed by the rel at i vel y l arge current
transients, whi ch l ead to a large st andard devi at i on in t he current. The r oot mean square of
the current signal is used i nst ead of the mean current to account for all current passi ng
bet ween t he t wo el ect rodes, i ndependent of its di rect i on.
The present wor k report s the results of exper i ment s whose ai m was to eval uat e cri t i cal l y
the correl at i on among ENM, convent i onal el ect r ochemi cal measurement s used in corrosi on,
and physi cal measurement s of attack.
Experimental Procedure
Resul t s are report ed for the exper i ment al arrangement shown in Fi g. 1. Three nomi nal l y
i dent i cal SS410 el ect rodes (24.5 by 19 by 1.6 mm thick) were i mmer sed 15 mm into the
sol ut i on so t hei r spot - wel ded el ect ri cal connect i ons were not in cont act wi t h solution. Thi s
Stabilizing holders
_ I
L_
L
SCE
J
$410 identical electrodes
1 L beaker - quiescent solution
~ A u x i l i a r y
ctrode (Pt)
Reference ~ ~ " ---~ sldentical
electrode ( S C E ) ~ electrodes
FIG. l--Experimental arrangement of electrodes in solution. The electrical connections were made
above the waterline to avoid crevice corrosion. No preferential attack at the waterline was observed.
arrangement was used to avoi d crevi ces and resul t ed in an exposed area of 13.5 cmL One
of the nomi nal l y i dent i cal el ect rodes served as a reference el ect r ode (referred to herei naft er
as the E-el ect rode), whereas t he ot her t wo (referred t o as the 1-electrodes) were connect ed
t hrough a Kei t hl ey Model 485 pi coammet er. A sat urat ed cal omel el ect r ode ( SCE) was al so
i ncl uded in t he cel l for measur ement of t he corrosi on pot ent i al (Eco~r)- A pi ece of pl at i num
mesh was used as an auxi l i ary el ect rode.
The t hree i dent i cal el ect rodes wer e connect ed to t wo ampl i fi er ci rcui t s based on Anal og
Devi ces Model AD524BD operat i onal ampl i fi ers shown in Fi g. 2. Thi s al l owed smal l de-
vi at i ons in pot ent i al bet ween the E- el ect r ode and I-el ect rodes to be moni t or ed at a hi gh
resol ut i on. For the 12-bit anal og- t o- di gi t al ( A/ D) convert er used, the 100 ampl i fi er resul t ed
in an i nst rument at i on resol ut i on of 2.4 I~V. The negat i ve i nput channel s on t he ampl i fi ers
were connect ed to t he el ect r ode that hol ds t he ground i nput for t he pi coammet er. The posi t i ve
i nput channel was connect ed to the E-el ect rode. The common out put channel was used as
the gr ound signal for t he dat a acqui si t i on board. It was found that i t was i mport ant t hat this
signal was connect ed to the ground i nput on the Kei t hl ey Met r abyt e Model DAS- 16 dat a
Terminal
box
Ampl i f
Data acquisition s ys t em l
aal
3
ithley 485
oammeter
Identical electrodes
FIG. 2- - El ect roni cs o f data acquisition with details of connections. Amplifiers were f or measurement
of EPN whereas the pi coammet er was used f or measurement of ECN.
acqui si t i on syst em (DAS) board, not t he l ow input. The Vou , channel was connect ed to the
hi gh-i nput channel on the DAS board.
The pi coammet er ground i nput was connect ed to t he sampl e that hel d the ground i nput
for the ampl i fi er as shown in Fi g. 2. The hi gh-i nput channel was connect ed t o t he sampl e
used onl y for current measurement . The pi coammet er was connect ed to the DAS boar d wi t h
the ground output from the pi coammet er connect ed to gr ound i nput on the DAS board. The
hi gh out put from t he ammet er was connect ed to the hi gh i nput on t he DAS board.
Measur ement s were per f or med t hree t i mes a day at 6-h i nt erval s for seven days. A single
measur ement consi st ed of moni t ori ng t he current bet ween t wo of t he el ect rodes (the I-
el ect rodes) and the pot ent i al di fference bet ween this coupl e and t he t hi rd SS410 el ect rode
(the E-el ect rode) at 20 Hz for 30 min. The col l ect i on frequency of 20 Hz was chosen to
det ect fast er transients t han are nor mal l y consi der ed in ENM. No frequency dependence was
found for t he el ect r ochemi cal noi se par amet er s report ed here over a frequency range of 1 to
1000 Hz. Resul t s from ot her anal yses of t hese dat a wi l l be report ed later.
Af t er the measur ement of the EPN and ECN (for use in the det er mi nat i on of R, and PI),
four ot her paramet ers were measured. The measur ed par amet er s i ncl ude Eco ~, whi ch we
define as the pot ent i al of t he I-el ect rodes versus a sat urat ed cal omel reference (SCE); E,vg,
whi ch we define as the average pot ent i al di fference bet ween the E- el ect r ode and the
1-electrodes for a gi ven t i me peri od; and the average coupl i ng current, lavg, bet ween the I-
el ect rodes over the same t i me peri od. Not e that EPN refers to the fluctuations in the pot ent i al
about some average val ue bet ween t wo nomi nal l y i dent i cal el ect rodes, whereas E, vg is the
average value. Wher eas for t wo t rul y i dent i cal el ect rodes Eavg woul d be zero, for passi ve
mat eri al s undergoi ng l ocal i zed cor r osi on l arge di fferences in pot ent i al can devel op bet ween
t wo i sol at ed, nomi nal l y i dent i cal el ect rodes. The average current has the same magni t ude as
the r oot mean square of the current, but can be of ei t her pol ari t y. Thi s was used to al l ow us
to moni t or whi ch of t he I-el ect rodes was the net anode at any poi nt duri ng an experi ment .
In addi t i on, in some tests, the pol ar i zat i on resi st ance of the E- el ect r ode was measured ac-
cordi ng to t he ASTM Pract i ce for Conduct i ng Pot ent i odynami c Pol ari zat i on Resi st ance Mea-
surement s (G 59) usi ng an SCE as a reference el ect r ode and a pl at i num count er el ect rode.
Three test sol ut i ons were used: 0. 1M hydr ogen chl or i de (HC1), phosphat e buffer at pH 7
wi t h addi t i on of 0. 5M sodi um chl ori de (NaCI) and 0. 01M hydrogen per oxi de (H20/ ) aft er
four days of i mmersi on, and 1M NaC1 at pH 3. Al l chemi cal s were reagent grade. Al l
measurement s were made at r oom t emperat ure.
Res ul t s
Results in Acid
The use of 0. 1M HCI sol ut i on al l owed the st udy of uni form at t ack of the SS410. Because
of t he l ow chr omi um cont ent of this mat eri al , as shown in Table 2, it cannot spont aneousl y
passi vat e in this solution. Instead, the mat eri al undergoes active di ssol ut i on at a hi gh rate
(about 600 ixA/cm2). Al t hough the l arge surfaces of the sheet speci men underwent uni form
corrosi on, some pi t t i ng was obser ved on the exposed edges, most l i kel y a result of a pref-
erent i al attack of i ncl usi on stringers. In the seven-day tests, mass l osses of appr oxi mat el y
TABLE 2--Composition of SS410 stainless steel (all in wt %).
Fe Cr Ni Mo Cu C AI Mn P S Si
Balance 11.73 0.09 0.0l 0.05 0.12 0.007 0. 41 0.015 0.005 0.34
100 mg / c m 2 were observed, whi ch cor r esponded to t hi ckness l osses on the or der of 230
la.m.
The corrosi on pot ent i al (Ecor~) of the SS410 duri ng exposure to 0. 1M HC1 was - 0 . 4 9 V
(SCE) and fai rl y const ant ( + 2 mV) aft er the first 40 h. The Ear g was al so st eady and less
than 1 mV. The pol ari zat i on resi st ance was st eady at appr oxi mat el y 15 f~ (195 f~-cm2). The
noi se resi st ance was not qui t e as st abl e as Rp, as shown in Fi g. 3, and was gener al l y hi gher
than the pol ari zat i on resi st ance by appr oxi mat el y a fact or of 3, al t hough in rare i nst ances
R n was less than Rp. The lavg reached a st eady state of appr oxi mat el y 5 ~A. The pi t t i ng
i ndex vari ed bet ween 0.069 and 0.87 as shown in Fi g. 4.
The addi t i on of 0. 2M sodi um hydr oxi de (NaOH) (vi a t wo separat e addi t i ons, each of
whi ch i ncreased the concent rat i on by 0. 1M) was used to passi vat e the el ect r ode and to
det ermi ne i f the vari ous el ect rochemi cal paramet ers coul d fol l ow such a change. Af t er the
addi t i on of the NaOH, t he open ci rcui t pot ent i al first fel l and then i ncreased dramat i cal l y.
Bot h the pol ari zat i on resi st ance and the noi se resi st ance i ncreased dr amat i cal l y as wel l , from
values on the order of 15 11 to values on the order of 10 to 12 kD, The pi t t i ng i ndex fell
aft er the addi t i on of NaOH t o val ues of bet ween 0.1 and 0.3.
The wei ght loss of the E- el ect r ode was found to be 0. 6806 g, whereas the t wo I-el ect rodes
l ost 0.4803 and 0. 5510 g.
Results in pH 7 Phosphate Buffer with Added Chloride and Peroxide
SS410 spont aneousl y passi vat es in neutral phosphat e buffer solutions. In t hese solutions,
a prot ect i ve oxi de forms, whi ch subst ant i al l y di mi ni shes uni form corrosi on. The addi t i on of
chl ori de i ons and per oxi de (to rai se the pot ent i al ) can di srupt the fi l m and l ead to pitting.
Thi s envi ronment was chosen to st udy the el ect rochemi cal noi se from a passi ve el ect r ode as
wel l to serve as a test vehi cl e for a st udy of t he t ransi t i on t o pitting. The speci mens exposed
2 0 0
Rp
R.
150 --
~ 1 0 0 -
9 - - _ - _ - _ - _ - = = -
O - l i F - I I i
0 2 0 4 0 60 80 100 120 140
Ti me / h
FIG. 3- - Rp and R.f or SS410 in O.1M HCI as function of exposure time. Note that effect of addition
of NaOH at 135 h is not shown.
.8 -
~
0 . 6
e ~
~ 0 . 4 4
0 . 2 -
0
0
I I i I I 1
25 50 125 150
1
75 100 175
T i me / h
FIG. 4- - Pi t t i ng index f or SS410 in O. 1M HCl as f unct i on o f time. Arrows indicate addition o f O. 1M
NaOH.
--]~l. 0.5 M NaC1 and - I - E~o
0 ' 0 . 0 1 MH2 0 2 a d d e d I I ~ E , ,
- 50
- 100 t
i ; i ~ L
- - 2 0
- - 2 2
- - 24
- - 2 6
- - 2 8
- - 3 0
0 25 50 75 100 125 150
T i me / h
FIG. 5 - - E . , r ~ a n d E.,,g versus time f or SS410 in borate buffer. E~orr was measured v e r s u s a saturated
cal omel electrode, whereas E , ~ , , g was the average pot ent i al difference between the E- and 1-electrodes.
to this envi ronment showed no measur abl e uni form corrosi on, but each el ect rode devel oped
pi t s aft er the sol ut i on addi t i ons.
The t i me dependenci es of t he t wo pot ent i al s measured (Eco, and E a v g ) a r e shown in Fig.
5, al ong wi t h an i ndi cat i on of the t i me at whi ch the sol ut i on addi t i ons were made. The
corrosi on pot ent i al of the speci mens r ose sl owl y before t he sol ut i on addi t i ons. The Eavg
fl uct uat ed bet ween - 2 2 and - 2 9 mV. Af t er addi t i on of the chl ori de and per oxi de, t he Eco ~
fel l dramat i cal l y, i ndi cat i ng the i ni t i at i on of a stable pit on one of the I-el ect rodes. The
pol ari t y of Eavg was such that a posi t i ve val ue of the open ci rcui t pot ent i al cor r esponded to
the E- el ect r ode bei ng at a hi gher pot ent i al than the I-el ect rodes.
The coupl i ng current was ext r emel y smal l (on the or der of l 0 hA) before the addi t i on of
chl ori de. Af t er addi t i on of t he chl ori de and peroxi de, a large, l ong- l i ved t ransi ent was mea-
sured, wi t h a peak val ue of over I l 0 txA as shown in Fi g. 6, i ndi cat i ng that one of t he I-
el ect rodes had i ni t i at ed a pi t and a subst ant i al amount of the cat hodi c react i on support i ng
pi t growt h was occurri ng on t he ot her I-el ect rode. Thi s current decr eased over 24 h to 60
ixA at the t ermi nat i on of the experi ment . Smal l pits, confined most l y to the edges of the
coupons, were obser ved on bot h I-el ect rodes. A few large pits were found on the flat surface
of the c oupons - - one was a hemi spher i cal pi t roughl y 300 ixm in di amet er, the others were
el ongat ed pi t s rangi ng from 0.7 to 2 mm in length and 0.2 to 0.7 mm in width.
The noi se resi st ance and the PI decr eased dr amat i cal l y aft er the i ni t i at i on of pi t t i ng as
shown in Fi g. 7. The PI decr eased dr amat i cal l y and fell from a val ue of 0.5 to 0.015 aft er
the i ni t i at i on of pitting, al t hough it l at er i ncreased to 0.15 before t he t ermi nat i on of the
experi ment . The noi se resi st ance decreased from appr oxi mat el y 1.1 Ml-I to appr oxi mat el y 2
kD.
Results from 1M NaCl at pH 3
In some instances, subst ant i al pi t t i ng can occur in the presence of si gni fi cant uni form
corrosi on. Thi s is the case for SS410 in 1M NaC1 aci di fi ed to pH 3. Af t er the test, sampl e
<
J
120
100
8 0 -
60
4 0 -
20
o r
-20 -
0
0.5 M NaCI and I
Y 0.01 M H:O2 added /
. J
! t
75 100 125
T i me / h
25 50 150
FIG. 6--Average current as a function of time for SS410 in borate buffer. Arrow indicates addition
of O.5M CI- and O.01M H202 before measurement.
o ~
10000 -
1000 J
1 o o - '
1 0 -
1 -
4
0.5 M NaC1 and 1
0 . 0 1 M H2 0 2 a d d e d
0.1 I ~ I
0 25 50 75
Time / h
i
- 0.1
P I
i
~ - 0.01
F j - - 0.001
100 125 150
FIG. 7- - R, and pitting index as a function of time for SS410 in borate buffer. Arrow indicates addition
of O.5M CI- and O.01M HeO 2 before measurement.
surfaces showed some uniform corrosion, although the weight loss was t oo small to be
measured ( <0. 2 mg) after onl y seven days of exposure. A large number of small pits were
found on all exposed surfaces.
The corrosion potential of the I-electrodes rose over the first 30 h from - 0. 55 V (SCE)
to - 0. 325 V (SCE) before falling slowly to - 0 . 4 4 V (SCE) over the next 100 h as shown
in Fig. 8. The magnitude of E, vg slowly increased from less than 5 mV at the start of the
test to approximately 300 mV. The polarization resistance increased from 150 to 2800 f l as
Ecor~ increased as shown in Fig. 9. As the corrosion potential fell slowly, so did the polari-
zation resistance. The noise resistance generally tracked the polarization resistance. However,
the R,, values were again consistently higher than the R, values by approximately a factor
of two, as shown in Fig. 10 for a portion of the test.
The mean current varied sporadically during most of the test period, although its magni-
tude increased significantly after approximately 100 h as shown in Fig. 11. The pitting index
was high (close to 1) early, but then fell to approximately 0.1 after 25 h before oscillating
between 0.1 and 0.8 as shown in Fig. 11.
D i s c u s s i o n
Type 410 stainless steel has been used to investigate the correlation between a variety of
electrochemical parameters and the nature of the physical attack that occurs when it is
exposed to a variety of solutions. Reasonable correlation was found between the degree of
the uniform corrosion and the values of the polarization and noise resistances over a broad
range of solutions in which R, varied from 15 I I to 1 MD. However, the noise resistance
was consistently higher than the polarization resistance. Al t hough generally R, was approx-
imately three times greater than Rp, R, was sometimes more than an order of magnitude
larger, and occasionally slightly less than Rp. The noise resistance also appeared to be more
volatile in situations in which general corrosion was accompani ed by pitting, as in the 1M
-300 [- - - I - F_ , ! 0
- 5 5 0 , , , x /
-600 r i t ~ [
0 25 50 75 100 125 150
Ti me / h
FIG. 8- - E .... and Ea,,g venus time f or 1M NaCl at pH 3.
-50
I
~ - 1 5 0 ~
J ~
-250
r
~ - 3 0 0
NaC1 solution at pH 3 (see Fig. 10). Nonetheless, both the noise resistance and the polari-
zation resistance were able to detect the effects of a large change in the corrosivity of the
environment. For example, when the pH of the acid solutions was raised to 10, both the
polarization and noise resistances increased by three orders of magnitude.
The weight loss measured for the E-electrode exposed to acid (on which the polarization
resistance measurements were performed) corresponds to a corrosion current of 4.57 mA
3000
2500 -
200O
1500
1000
50O
1 I I 1 I I
0 20 40 60 80 100 120 140
Time / h
FIG. 9--Rp versus time f or 1M NaCl at pH 3.
10000
--I I -- R,
8000 -
6000 -
4000
2000
I 7 - - 7 - k ~ - I
70 80 90 100 110 120 130
Time / h
FIG. 10--Rp and R, versus time f or 1M NaCl at pH 3.
140
(340 ixA/cm2). This woul d agree well with the polarization resistance values i f both the
anodic and cathodic Tafel slopes were 120 mV/ decade, that is, for a Stern-Geary B coeffi-
cient of 0. 026 V. Good agreement with the noise resistance woul d occur if the B coefficient
were 0. 052 V. This woul d require an extremely high anodic Tafel slope (implying passivity),
because the expected Tafel slope for hydrogen evolution is 120 mV/ decade. Polarization
- 2 - ~
<
:::L
- 6 - -
- 8 ~ ~
0 25 50 75
T i me / h
P , 1
i
I- 0.8
i 0.6
- 0 . 4
- 0 . 2
I
100 125 150
FIG. 11--Average current and pitting index f or I M NaCl at pH 3.
~f
fro
curves generated for SS410 in 0. 1M HCI exhibited an anodic Tafel slope of 109 mV/ decade
and a cathodic Tafel slope of 105 mV/ decade. The importance of these results lies in the
use of ENM for corrosion rate monitoring. Al t hough R, can be used for monitoring changes
in corrosivity, these results indicate that it will generally overestimate the polarization resis-
tance, leading to an underestimation of the corrosion rate.
An electrochemically measurable parameter that characterizes the degree of localized cor-
rosion would be of great practical use. The PI has been proposed [9] to be that parameter,
with higher values indicating localized corrosion and lower values indicating uniform cor-
rosion. This classification has been developed based on measurements in complicated sys-
tems in which post-test verification of the type of attack was difficult, and the determination
of when pitting initiated was impossible. By choosi ng a simple system, a critical test of the
PI has been performed. SS410 is spontaneously passive in phosphate buffer solutions. In
quiescent solutions, as the passive film grows, the anodic reaction slows, leading to a rise
in the corrosion potential. In the absence of an aggressive species, the material will remain
passive. However, for the tests reported here, the pitting index ranged in value from 0.2 to
0.9, whereas the SS410 was exposed onl y to phosphate buffer. This would normal l y be
interpreted as indicative of localized corrosion. Clearly, this would be an erroneous
interpretation.
After the addition of 0. 5M chloride ion and 0. 01M peroxide, SS410 will undergo pitting
in phosphate buffer. When a material begins to pit, the corrosion potential falls dramatically.
This can be rationalized based on mixed potential theory. When a small, high-rate dissolution
site such as a pit is produced, the remainder of the surface acts as the cathode. Because
oxygen reduction is sluggish on the oxide-covered surface and is diffusion limited, the po-
tential of the pit and the passive surface falls, Figure 5 shows this effect. Not e that the Eavg
was not affected by the solution addition (see Fig. 5), but there was a large increase in the
Iavg (see Fig. 6). The most likely explanation of this is that pitting occurred on one of the I-
electrodes and the E-electrode.
The PI fell to very low levels during the pitting (0.015), which would indicate predomi-
nantly uniform corrosion. However, this was not the case. On each electrode, one or two
large pits and a number of smaller pits were observed in the otherwise passive surface.
These results have implications for corrosion monitoring via ENM. Clearly, the Ecor~ of
test specimens appears to be more sensitive to changes in the corrosivity than was either the
Eavg or PI. This is unfortunate, because the maintenance of reliable reference electrodes is
difficult in many industrial applications that require corrosion monitoring. Of particular con-
cern is the possibility of misinterpretation of the ENM. The pitting index was found to be
unreliable as presently constituted. During the period when the SS410 was clearly passive,
the PI indicated that localized corrosion was occurring. In addition, when localized corrosion
was occurring, the PI indicated that the predominantly uniform corrosion was taking place.
The development of pitting on the E-electrode prevented it from following the course of the
pitting process on one of the I-electrodes. This would complicate its use in the monitoring
of localized corrosion as well.
Although the reasons behind the lack of correlation between the PI and the observed attack
are still unclear, these results cast doubt on its use for the detection of the onset, propagation,
and cessation of localized corrosion. Mathematically, the PI is a relative standard deviation,
indicating the size of the current fluctuations relative to the average coupling current. In the
case of SS410 in phosphate, the very small values of I , ~ when the system is passive drive
the index to values indicative of localized corrosion, as the measured fluctuations (th) are of
the same magnitude. Because both I~n s and tr~ are an order of magnitude above the electrical
noise of the instruments used, it appears that the values reported reflect the electrochemical
processes under study. During the propagation of localized corrosion, the I, , s rises more than
does the Orl, which causes the PI t o fall to low values indicative of uniform corrosion.
Unfortunately, the PI, as presently constituted, is not able to differentiate localized and uni-
form corrosion for this system.
The system studied was specifically chosen to provide an unambi guous test of the various
parameters derived from ENM. The noise resistance shows promise for monitoring changes
in corrosivity. While the fundamental basis for noise resistance remains a topic of debate
[10-12], this is an important practical application of electrochemical techniques to corrosion
engineering. The pitting index, as presently constituted, shows much less promise as a tool
to differentiate localized and uniform corrosion.
Co nc l us i o ns
1. The polarization resistance of SS410 in solutions ranging from pH 1 to 7 increases by
five orders of magnitude. Over this range of solution composition, the noise resistance
generally tracks the polarization resistance. Hence, R, can be used t o moni t or changes
in solution corrosivity.
2. The noise resistance was found to be consistently higher than the polarization resis-
tance. The use of R, in the Stern-Geary relation woul d lead to an underestimation of
the corrosion rate. In general, the ratio of R, to Rp was usually t wo t o three for the
results reported here, although values for this ratio ranged from less than one to
fourteen.
3. The pitting index did not correlate to the occurrence of pitting. For SS410 in a phos-
phate buffer solution, the PI indicated that localized corrosion was occurring. After the
addition of 0. 5M CI - and 0. 01M H202, the P! indicated that the SS410 was undergoing
predominantly uniform corrosion when post-test examination showed that pitting was
the sole mode of attack.
Acknowl edgment s
The technical assistance of N. M. Brush in the performance of the experiments is gratefully
acknowledged. The authors would like to acknowledge the financial support of Mobil Ex-
ploration and Production Technol ogy Company (Dr. C. Kroen).
Re f e r e nc e s
[1] Iverson, W. E, Journal of the Electrochemical Society, Vol. 115, 1968, pp. 617-618.
[2] Dawson, J. L., Farrell, D. M., Aylott, E J., and Hladky, K., Paper 31, Corrosion/89 Conference,
NACE International, Houston, TX, 1989.
[4] Magaino, S., Kawaguchi, A., Hirata, A., and Osaka, T., Journal of the Electrochemical Society,
Vol. 134, 1987, p. 2993.
[5] Stolica, N., Corrosion Science, Vol. 9, 1969, p. 205.
[6] Schwenk, W, Corrosion, Vol. 20, 1964, p. 129t.
[7] Magaino, S., Boshoku Gijutsu, Vol. 32, 1983, p. 712.
[8] Magaino, S., Yasuda, M., and Yamada, H., Boshoku Gijutsu, Vol. 34, 1985, p. 157.
[9] Eden, D. A., John, D. G., and Dawson, J. L., International Patent WO 87107022, World Intellectual
Property Organization, 1987.
[10] Mansfeld, E and Xiao, H., Journal of the Electrochemical Society, Vol. 141, 1994, pp. 1403-1404.
[11] Eden, D. A., Journal of the Electrochemical Society, Vol. 141, 1994, pp. 1402-1403.
[12] Bierwagen, G. P., Journal of the Electrochemical Society, Vol. 141, 1994, pp. L155-L157.
L u c Be a u n i e r , t Jo#' l F r y d ma n , 1 C l a u d e Ga b r i e l l i , ~ F r a n g o i s Hu e t , J
a n d Mi c h e l K e d d a m ~
Comparison of Spectral Analysis with Fast
Fourier Transform and Maximum Entropy
Method. Application to the Role of
Molybdenum Implantation on Localized
Corrosion of Type 304 Stainless Steel
REFERENCE: Beaunier, L., Frydman, J . , Gabrielli, C., Huet, E, and Keddam, M., "Com-
parison of Spectral Analysis with Fast Fourier Transform and Maximum Entropy
Method. Application to the Role of Molybdenum Implantation on Localized Corrosion of
Type 304 Stainless St eel , " Electrochemical Noise Measurement f or Corrosion Applications,
ASTM STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and
John L. Dawson, Eds., American Society for Testing and Materials, 1996, pp. 114-128.
ABSTRACT: A comparison of a spectral analysis using the fast Fourier transform (FFT) and
the maximum entropy method (MEM) was carded out in the case in which both methods can
be performed, that is, when several time acquisitions can be recorded. A summary of the
principles of the MEM is given. Then the main properties of this method are investigated, that
is, influence of the MEM order on the spectrum accuracy, validity of the low-frequency plateau
usually given by this technique, overlapping of spectra measured for different frequency band-
widths, and influence of a slow evolution of the amplitude of the signal fluctuations.
The susceptibility to pitting corrosion of type 304 stainless steel and type 304 modified by
molybdenum (Mo) by means of ion implantation was studied. The power spectral densities
(PSD) measured with the FFT and MEM techniques are in reasonable agreement, except for
low electrochemical current noises (ECN) buried in the parasitic noise generated by the power
supply. In that case, the FFT technique is more appropriate than the MEM, which gave qual-
itative results only. The type 304 stainless steel showed a large metastable pitting leading to
only a few macroscopic pits, whereas the type 304 Mo-implanted specimen showed a very low
metastable pitting leading to many hemispheric pits covered by the Mo-implanted layer, under
which localized corrosion occurred.
KEYWORDS: potentiostatic electrochemical noise measurement, fast Fourier transform, max-
imum entropy method, localized corrosion, molybdenum implantation, stainless steel, data
analysis techniques
The i nvest i gat i on o f l ocal i zed cor r os i on of t en l eads t o t he anal ysi s o f r a ndom cur r ent
f l uct uat i ons r el at ed t o t he r a ndom bi rt h, gr owt h, and r epassi vat i on o f pi t s at an el ect r ode
surface. It is gener al l y t hought that t he anal ysi s o f t he t i me seri es o f el ement ar y event s
occur r i ng at pot ent i al s bel ow t he pi t t i ng pot ent i al al l ows t he suscept i bi l i t y o f an al l oy or
met al t o l ocal i zed cor r os i on t o be as s es s ed [1,2].
i Physique des Liquides et Electrochimie, UPR15 CNRS, Universit6 Pierre et Marie Curie, Tour 22,
4 place Jussieu, 75252 Paris Codex 05 France.
Copyrighl 9 1996 by ASTM International
114
www.astm.org
BEAUNIER ET AL. ON COMPARISON OF SPECTRAL ANALYSIS 115
During the prepitting stage, the usual approach for characterizing such a random signal is
to estimate its power spectral density (PSD) or spectrum, that is, the distribution of the power
of the signal in the frequency domain.
Usually the PSD of a random signal is obtained through a fast Fourier transform (FFT)
algorithm. However, especially when onl y one experiment is available, or when the signal
drifts t oo much and therefore limits the measurement time, the maxi mum entropy method
(MEM) was proposed to obtain the PSD [ 3 , 4 ] . This method was first applied in geophysics,
more generally in earth sciences, and from 1967 many papers have been published on this
topic (see Ref 5 and references t h e r e i n ) . The proponents of the MEM claimed that it had
some advantages:
1. It needed only one time acquisition.
2. It gave smooth spectra.
3. It led to the values of the spectrum at frequencies lower than the inverse of the acqui-
sition time.
This method has already been used in corrosion investigation for studying pitting of alu-
mi num [6], mild steel [7], and pure iron [8], to obtain data at frequencies much lower than
with the FFT technique while keeping reasonable acquisition times.
In this paper, a compari son of a spectral analysis with the FFT and the MEM was at-
tempted on systems where the t wo methods can be carried out, that is, when several time
acquisitions can be recorded, to assess their relative efficiencies. This compari son was con-
ducted by processing signals delivered, first, by electronic devices, then by type 304 stainless
steel electrodes. I n that case, the effect of mol ybdenum (Mo) implantation on the localized
corrosion susceptibility in a chloride-containing acidic medi um was studied by using Mo-
implanted and unimplanted specimens.
Principles of the Analysis Methods
The PSD can be obtained through the peri odogram method based on the Cool ey Tuckey
FFT algorithm [9]. Here, the spectrum is estimated by:
~b(f) = T. t*j~-"7~ IlJ(f)P (1)
where
f = the frequency,
T = the acquisition time,
l j ( f ) = the Fourier transform of the elementary time recording l j ( t ) ,
9 I = the number of time recordings.
This method has the advantages of being simple, easily implementable on a computer, and,
above all, applicable to a large class of random signals.
However, despite these advantages, the FFT needs, to obtain accurate spectra, t o average
ove r . l" squares of the modul us of the Fourier transforms of I j ( t ) (see Eq l); therefore, the
peri odogram method will be designated as FFT(. I ). This leads to the following drawbacks:
1. The time to acquire the data is multiplied by 9 ~ compared to a method that would
need only one acquisition.
1 1 6 ELECTROCHEMICAL NOISE MEASUREMENT
2. It is appropri at e onl y i f the t i me si gnal s are reproduci bl e, that is, i f several acqui si t i ons
can be recorded duri ng the same experi ment .
Therefore, this met hod is i ncompat i bl e wi t h experi ment s that can be carri ed out onl y once
or that do not l ast a suffi ci ent l y l ong t i me. For this reason, t he MEM was devel oped.
Si mi l ar to the FFT anal ysi s, there are t wo ways for est i mat i ng t he PSD by t he MEM,
ei t her a di r ect met hod, in whi ch the spect ral est i mat i on is made on t he signal sampl es, or
an i ndi rect met hod, in whi ch t he PSD is est i mat ed t hrough the aut ocorrel at i on funct i on [5].
We have tested bot h met hods and, for our condi t i ons, t hey gave si mi l ar results. Therefore,
we use, in this work, t he second met hod (Levi nson al gori t hm), whi ch l eads to faster
cal cul at i ons.
The sampl i ng duri ng a t ot al t i me T of the t i me series x(t) of N dat apoi nt s separat ed by
At = T/ N l eads to a di scret e set of dat a x(n) t aken at t i me nAt (in our case N = 2048).
The MEM is an est i mat i on of the PSD suggest ed by the i nformat i on theory. It was first
assumed that the sampl ed data, x(k), can be descr i bed by an aut oregressi ve model :
y(k) =x ( k ) - a , y ( k - 1 ) - a 2 y ( k - 2 ) - . . . - a My ( k - M) (2)
where y(k) is the est i mat ed val ue and M is the or der of the model. Then it was assumed that
the est i mat i on of the PSD + ( f ) was:
1. Coherent wi t h the N known val ues of the aut ocorrel at i on function R~(m) defi ned at
t i me mAt by
1 u m-I
R~(m) = ~ ~ x(n) x(n + m)
,~=o
(3)
Hence the Wi ener - Khi nt chi ne t heorem gi ves
f [
m.~ e z' ~a' d~(f ) df = R~(k)
Fmax
O<- k <- N - 1 (4)
where Fm,x is the Nyqui st frequency, that is, the maxi mum anal yzed frequency Fmax =
1 ~2At.
2. Independent of any hypot heses on t he unknown values of Rx~(m) for m -> N.
This last poi nt is equi val ent to i mposi ng maxi mum ent ropy to the PSD versus the values
R~(m), m >- N, hence the name of the method. Not e that t he per i odogr am met hod assumes
that R,~(m) = 0 for m -> N.
An al gori t hm was deri ved to est i mat e the PSD that can be i mpl ement ed on a comput er
[5]. Cont rary to the FFI" technique, whi ch gi ves a spect rum in the range [ 1/ T = 2Fm,x/N,
Fmax], the PSD is est i mat ed by the MEM at any frequency f - < Fm,x, wi t h
2 tr 2 At
(5)
BEAUNIER ET AL. ON COMPARISON OF SPECTRAL ANALYSIS 1 17
where o ~, a I . . . . , a M are M + 1 coefficients dependent on M, which are calculated from
the (M + 1) (M + 1) matrix equation
[
R~(O) R=( I )
, %. 0) , %(0)
R=iM) Rxx(M- 1)
R x ~ ( M - l ) a I [ o l
a2
9 - . R~(O)
The maj or parameter of this algorithm is the order M o f the model. Therefore, the MEM
will be called MEM(M).
Properti es o f t he MEM
The MEM properties of interest to electrochemists will be reported below by processing
either a white noise signal generated by a Solartron JM 1861 or a signal generated by a
corrodi ng electrode. The signals were digitized with a real-time comput er (Concurrent Com-
puter RTU 6600). No drift was observed on the analyzed signals; therefore, the onl y oper-
ation on the time recordings was the elimination of their mean value before comput i ng the
PSD.
Influence of the Order of the MEM on the Accuracy of the Spectra
To examine the influence o f the order of the MEM on the accuracy of the estimated
spectra, the spectrum of a white noise was calculated for various orders 10, 30, 100, and
300 [MEM(10), MEM(30), MEM(100), MEM(300)] and compared with a F F r processing
averaged over 20 elementary spectra [FFT(20)]. The MEM spectra were calculated with the
same time record, and, for a better reading of Fig. 1, the MEM(10), MEM(30), MEM(100),
and MEM(300) spectra were divided by 10, 102, 10 3, and 104, respectively. The comparisons
plotted in Fig. 1 show that the levels of all spectra are the same, and that the opt i mum order
of the MEM is a trade-off: an order that is too low leads to poor frequency resolution (smooth
spectrum) with a few wiggles in the high-frequency range, whereas an order that is too high
leads to a finely resolved spectrum with many spurious oscillations. In Figs. 1 and 4, the
decrease of the spectra at frequencies higher than 0.67 Fro, x is due to the anti-aliasing low-
pass filter.
Performance of the MEM for Signals Without a Low-Frequency Plateau in the Analyzed
Frequency Bandwidth
The signals whose spectra are plotted in Fig. 2 were generated by filtering a white noise
signal by an electronic circuit in which the characteristic frequency of the RC circuit is lower
than the inverse of the time record duration 1/T, whi ch is the mi ni mum frequency 2Fm~x/N
available with the FFr . In this experiment, the FFI" was chosen as a standard, although it
needed measurement times 20 times longer than the MEM to be estimated. Here, the
MEM(10) spectrum was calculated with a logarithmic frequency distribution with 20 fre-
quencies per decade between 1 Hz and 50 kHz to save calculation time. The curves in Fig.
2 show that the MEM leads to spectra whose low-frequency parts [ f -< 41T] are not in
good agreement with those obtained through FFr . Therefore, the validity of the low-
t
N
r
>
I0--~
i O - s
I 0 -6
I 0 -~ '
1 0 - 8 .
i 0 - 9
lo_iO i
i O - u
iO - m
i i
il
b
c
d
e
i i i i t i
i i ! i i
lO 2 l O s
F REQUENCY
i g ! 1
i t ! i
/ Hz
i i t i , ~ 1
i i i !
5
FIG. 1- - PSD of white noise analyzed by means of an FFT algorithm (a : FFT(20)) and an MEM of
different orders (b : MEM(IO); c : MEM(30); d : MEM(IO0); e : MEM(300)). The curves b, c, d, and
e were divided by 10, 103, 103, and 104, respectively.
frequency plateau obtained by the MEM is often questionable. Not e that Eq 5 always leads
to a finite value +(0).
Overl appi ng o f t he Meas ur ed Spect ra
The MEM measurement can be carried out accurately over three decades (because the
number of samples in one time recording is usually N = 2048). For broadband random
signals, as the spectrum changes over more than three decades, it is necessary to perform
measurements on several overlapping bandwidths to analyze the whole useful frequency
range. In Fig. 3, these measurements were carried out for filtered white noise (Curve a) and
unfiltered white noise (Curve b). For the high-frequency measurement with Fma x = 50 kHz,
the same probl em as ment i oned previously arises for the filtered signal: curve a shows that,
in the considered bandwidth (2Fmax/N, Fmax), there is no low-frequency plateau, so the low-
frequency part of the calculated spectrum is wrong. However, by carrying out a low-fre-
quency measurement (Fm,~ = 500 Hz), the whole spectrum is accurately obtained. For white
noise, onl y one high-frequency measurement is sufficient because, in this case, data can be
accurately obtained below 1/T. For both cases, the overlap of the two measured spectra is
reasonably good.
PS D o f Poor St at i onari t y Si gnal s
When the analyzed signal changes slowly with time, the spectrum estimated by the MEM
depends on the time record chosen. As an example, the random current generated by a type
BEAUNIER ET AL. ON COMPARISON OF SPECTRAL ANALYSIS 1 19
"7,
N
r
r
9,
10L
10 -s_
l0 -t~
t0 -~_
i0 -13_
i o -
i0 -~
!
a
b
i i i i i i i i i i i
, \
[ W h it e n ~ t . ~ V ~ , i
- - g e n e r a t o r ~ )
_ _
A,
I I
i i i i i i i i i i i i
\
I ] I [ I I I I i i i i
FREQUENCY / Hz
FIG. 2 - - PS D o f f i l t ered white noise by an electronic circuit given in the inset. (a) FFT(20) measured
in two overlapping bandwidths [0.5 to 500 Hz] and [50 Hz to 50 kHz]. (b) MEM(IO) measured f rom a
time record obtainecl f or F ~ = 50 kHz (logarithmic f requency distribution).
304 stainless steel corroding electrode was recorded over a time 204.8 s, giving then ten
recordings, each lasting T = 20.48 s. From the ten time T-recordings, the FFT(10) spectrum
was estimated, and each time T-recording was processed by an MEM of order 10, which
produced ten estimated spectra MEM(10). In Fig. 4a, the estimated spectrum FFI~(10) is
plotted with two estimated spectra MEM(10). It can be observed that the level of the low-
frequency plateau of the spectra MEM(10) (Curves a and b) changes widely and depends
on the time record chosen.
In Fig. 4b, the estimated spectra MEM(10) given in Fig. 4a are compared to the estimated
spectra FFT(1) obtained by processing the considered time record by FFI ~ without averaging
(that is, the acquisition time of the processed signal is the same for FFT(1) and MEM(10)
in each case). It can be seen that MEM(10) gave a smooth average of FFT(1) in each case.
In particular, the mean low-frequency plateau given by FFF(1) depended, as for MEM(10),
on the considered time recording, that is, depended on the pitting activity. Of course, the
average of the ten FFT(1) led to the spectrum FVF(10), which gave the averaged low-
frequency plateau measured over a time 10T.
Role of Mol ybdenum on Localized Corrosion of Type 304 Stainless Steel
To investigate the influence of molybdenum ion implantation on the susceptibility of a
type 304L stainless steel to localized corrosion, the ECN induced by the birth, growth, and
repassivation of pits at potentials in the prepitting range was analyzed for two different
specimens of type 304 steel (75% Fe, 17% Cr, 8% Ni in approximate weight percentages);
the surface of one of them (called type 304 Mo steel in the following) was implanted with
=~
i
N
: =
>
t 0 - ' ~
1 0 - s _ :
1 0 - 6 _
t 0 -7 -
1 0 4 -
I 0 -s_
1 0 -l~
1 0 - u _
1 0 - ~ _
io-~_:
io-._!
i i ! I
b
a ~
I I I I I I l I
! I I [
I I I I
i
T I
i i I i ~ i
' ' " 1
|
io-' I b ~ i o ~ I b " i o 3 I b ' I b 5
F R E Q U E N C Y / H z
FIG. 3- - Overl appi ng of MEM(IO) spectra measured f rom a 20.48 ms ( F . . . . = 50 kHz) and a
2.048 s ( F , , ~ = 500 Hz) time record. ( a ) Filtered white noise. ( b ) White noise.
|
r
r
<
I E a
i 0 - s _
io-,O_
1 o - " _
I o - ~ _
Io-,3_
Io-"_
!
i 0 - ~ -
i !
a
l I
c ' - ~
b - - I
I I
! i i i
. T7
I I I [ I I I I I I I
l o - ' t b ~ l o ' l o ~
F RE QUE NCY / Hz
FIG. 4a- - Sl owl y time-varying random signals. Comparison of FFT(10) (Curve c) and two MEM(10)
(Curves a and b) obtained f rom t wo different elementary time records used to determine the FFT(10).
i
N
r
<
~
9 ,
10 4
1 0 _ 9 '
10
| ! | !
a
b _ _
. . . . . . . . . . . . I I , ~,
' l l . . . . I
, , ,
, 4 mL -
t l f ' , l -
i , I ' F I -
,, J '11 t
F RE QUE NCY / Hz
FIG. 4b- - Sl owl y time-varying random signals. Comparison of MEM(IO) (Curves a and b, same as
in Fig. 4a) and FFT(1) (Curves c and d) obtained f rom the same time records.
mol ybdenum ions (Mo+). Mol ybdenum was chosen for its beneficial role against corrosion,
especially pitting.
Ma t e r i a l s
The electrode surface was a disk of 0. 5-cm diameter (area 0.2 cm2). The lateral surface
was covered with an insulating electrophoretic coating (cataphoretic paint used in car in-
dustries, Corona EW 2258 and EW 2269). The implantation process was performed at room
temperature with a beam of 100 keV and a fluence of 2.5 x l016 ions/cmL The structure
was characterized by transmission electron mi croscopy (TEM) at 100 keV. The mi crochem-
ical analysis was performed on a 200-keV TEM- STEM equipped with an X-ray energy
dispersive spectrometer (EDS analysis). The implantation profile was measured by Ruther-
ford backscattering analysis (RBS).
For interpretation of electrochemical noise results, the structural description of the im-
planted film can be summarized as follows: the RBS profile of the thin implanted film was
pseudo-gaussian with a maxi mum at a 25-rim depth and a maxi mum implantation depth of
60 nm shown in Fig. 5. By TEM, we could observe an austenitic-ferritic transformation
induced by the implantation process. Correlatively, the grain size was decreased from 5 to
12 i~m in the initial austenitic phase to 0.1 to 0.3 ixm in the ferritic phase. No growi ng of
martensite was observed by TEM at the surface region. X-ray analysis revealed a large
enrichment up to a mean value of 15% in weight in mol ybdenum in the transformed film.
However, the local composition measured with a 4-nm beam showed important fluctuations
in the distribution of the elemental concentrations. The structural description of the implanted
film is further detailed by Beaunier et ai. [10].
FIG. 5--Gaussian distribution of the Mo implantation and associated microstructural changes versus
depth below the surface.
The electrochemical investigations were carried out at room temperature in an aqueous
solution (volume 300 cm 3) of 0.5M sulfuric acid with 0.05M sodium chloride (NaCI) for the
type 304 stainless specimen at potential 0.3 V versus a saturated sulfate electrode (SSE).
For the type 304 Mo steel specimen, the conditions were more aggressive (0.3M NaCI,
potential 0.55 V/SSE) for testing protection against pitting corrosion. The counter-electrode
was a large surface platinum grid. The experimental setup is based on homemade low-noise
potentiostat and amplifiers; the ECN was recorded with an audiotape recorder (Biologic DTR
1200) for more convenient signal processing after the experiment. Later, the signal was
digitized and the PSD was calculated with the real-time computer.
The intrinsic noise of the instrumentation was modeled in [11]. The PSD of the parasitic
current noise superimposed to the ECN is the ratio of the PSD of the voltage noise measured
between the reference electrode and the working electrode, and the square of the modulus
of the working electrode impedance. Therefore,
1. It depends not only on the instrumentation used, but also on the system under study.
2. In the high-frequency range, it increases with frequency because the impedance mod-
ulus decreases with frequency (Figs. 6a and b).
3. It can be neglected in the low-frequency range where the impedance modulus is
important.
BEAUNIER ET AL. ON COMPARISON OF SPECTRAL ANALYSIS 1 2 3
I N
104 -
10-9-
10_1o_."
10-"_
10 -m_
l 0 -'+_
1 0 - :
10 -m_
1 0 - ` 7 -
to-dO_
i O - ' s _
1 i 1
a ~
hi . ,
i i i i i i i i
1
I
b
I I I I I I I I I I I I i i i i
I
i i i i
l.J
t
i i i i
! i i i -
i i i
l 0 - 2 1 0 " l 1 3 ~ 1 0 1 1 0 2 l 0 a 1 0 + i 0
F REQUENCY / Hz
FIG. 6 a - - PS D of the ECN measured with the FFT technique in prepitting conditions. (a) Type 304
stainless steel electrode, 0. 5M H2S04 + 0. 05M NaCl at pot ent i al 0.3 V/ SSE. (b) Molybdenum-implanted
type 304 steel electrode, 0. 5M H2SO 4 + 0. 3M NaCl at potential 0.55 V/ SSE.
Resul t s and Di s cus s i on
Fi gur e 6 shows t he PSD o f t he ECN f or the i mpl a nt e d and uni mpl ant ed s peci mens , me a -
sur ed wi t h t he ~ t echni que (see Fi g. 6a) , and wi t h t he MEM ( see Fi g. 6b) f or compar i s on.
I n each case, t he me a s ur e me nt was pe r f or me d on t hr ee over l appi ng bandwi dt hs (Fmax, = 50
Hz, Fmax2 = 500 Hz, Fmax3 = 20 k Hz f or t he t ype 304 s pe c i me n and 5 k Hz f or t he ot her
one f or l i mi t i ng t he hi gh- f r equency r i si ng par t o f t he s pect r um as a r esul t o f t he pot ent i ost at
noi se) . I n Fi g. 6a, t he over l appi ng o f t he me a s ur e d s pect r a is f ai r l y good; f or t he t ype 304
Mo s pe c i me n (Fig. 6a, Cur ve b), t he l evel o f t he ECN wa s so l ow t hat we had t o use
Ha nni ng wi ndowi ng t o r educe t he wi dt h o f t he spect r al l i nes i nduced by t he p o we r s uppl y
( 50 Hz and har moni cs ) [9]. Wi t h t he MEM, t he over l appi ng o f t he me a s ur e d s pect r a ( see
Fi g. 6b) is accur at e f or a hi gh l evel o f ECN si gnal (t hat is, t ype 304 s peci men) but is
i naccur at e f or a l ow l evel o f ECN, wi t h as s oci at ed hi gh- ampl i t ude par asi t i c l i nes (t hat is,
t ype 304 Mo s peci men) , be c a us e o f t he i nabi l i t y o f t hi s t echni que t o r educe t he wi dt h o f
spect r al l i nes. Once mor e, Fig. 6b shows t hat t he ext r apol at i on o f t he s pect r um at f r equenci es
l owe r t han t he i nver se o f t he me a s u r e me n t t i me can be danger ous. The l ow- f r equency pl a-
t eaus obt ai ned wi t h t he t i me r ecor di ngs cor r es pondi ng t o Fma~ = 500 Hz and Fm,x = 5 k Hz
ar e dr amat i cal l y di f f er ent .
Whe n t he r a n d o m t i mes o f pi t gener at i on are a s s ume d t o be i ndependent ( Poi sson pr ocess) ,
t he PSD l evel is pr opor t i onal t o t he pi t gener at i on r at e [1]. Hence, t he l arge di f f er ence o f
t he PSD l evel , seen wi t h bot h FFF and MEM anal ysi s, f or t he t wo s pe c i me ns ( seven decades
at l ow f r equenci es ) r eveal s an i nt ense pr epi t t i ng act i vi t y f or the t ype 304 el ect r ode and a
ver y l ow act i vi t y f or t he t ype 304 Mo el ect r ode. However , it is not i ceabl e t hat t he t i me
m
( ' ~
<
1 0 - a
! i ! t
1 0 - 9 _ : . - - _ _
1 0 - t 0 _ ! a
10
1 0 -t3 _ :.
10-t~_:
i o - :
i o - " l
1 o - t ! b
1 0 - t _ :
1 0 - t !
1 I 1 1
! ! ! !
1 1 1 1 l 1 I I
' ' " l
"q
1
J
I l I I
I 17
) ) i i t ~ ) T
1 0 - z t O - t i 3 0 1 0 t i 0 2 1 0 3 1 0 4 t 0 5
F RE QUE NCY / Hz
FIG. 6b- - PSD of the ECN measured with the MEM in the same conditions as in Fig. 6a; three
overlapping bandwidths were successively analyzed (0.05 Hz, 50 Hz), (0.5 Hz, 500 Hz), and (20 Hz, 20
kHz) (Curve a) or (0.05 Hz, 50 Hz), (0.5 Hz, 500 Hz), and (5 Hz, 5 kHz) (Curve b).
constants of the repassivation process are very similar (about 0.5 s). The typical time re-
cordings given in Fig. 7 confirm the presence of
1. Numerous depassivation-repassivation current transients (about a hundred per second)
for the unimplanted specimen with an average electrical charge of 1 I~C (see Fig. 7a).
2. Very few transients for the Mo-implanted specimen (about 0.02 per second) with an
average charge of 0.1 ixC (see Fig. 7b).
After the experiment, we observed considerable differences in the pitting state of the
unimplanted and implanted specimens: the type 304 stainless steel exhibited three or four
pits per square centimeter. A single pit with classic features is represented in Fig. 8, with
20 to 100 v.m in width. By comparison, the mol ybdenum implantation induced the formation
of numerous pits in the implanted layer (up to 30 times more than for the type 304 steel)
(Fig. 9). These effects were attributed to Mo because of its well-known role in the passive
film during pitting corrosion. Moreover, a classical pitting process was observed for speci-
mens implanted with nonchemical sensitive species such as argon, krypton, and neon, which
were used for testing the physical effect of implantation.
Second, pits in the Mo-implanted ferritic film had a dramatically smaller area compared
to the unimplanted specimen. We observed a very special feature. After initiation, the pits
developed as holes about 50 nm in width in the ferritic layer at points corresponding to
physical or chemical defects introduced by the implantation process [12]. After this initial
pitting process, the dissolution occurred under the implanted ferritic film in the austenitic
matrix, which gave rise to hemispheric pits of about 50 v.m in diameter. The cap on the pit
<
:=J..
600
500
400
300
200
100
%
' I ' I ' I , I , I , I , I , i , i , i , i , I , i , [ , i , i , i , i , i ,
0 20 40 60 80 iO0 120 i40 180 i80 200
t i me / ms
FIG. 7a--Typical time recording of ECN corresponding to experimental conditions given in Fig. 6a
for type 304 stainless steel electrode.
1 , Z r m
1,2
1,0
.8 _
<
=I. .6
<1
. 2
0,0 ..~ . . . . . . A. , . ~ . . . . . . . ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . t, . . . . ~ . . . . . . .
/
0 1 2 3 4 5 6 7 8 9 lO
t i m e / s
FIG. 7b--Typical time recording of ECN corresponding to experimental conditions given in Fig. 6a
for Molybdenum-implanted type 304 steel electrode.
FIG. 8--Pi t observed on the type 304 stainless steel specimen.
was identified as the ferritic-implanted layer by TEM and EDS analysis. Figure 10 shows
that a confined corrosion process occurred in the pit covered by the implanted film, and the
corrosion products, issued from the occluded cell, which have crystallized over the primary
50-nm hole.
This study shows that the pit initiation process is very different after surface modification
by molybdenum ion implantation:
FIG. 9--Pits distributed on the Mo-implanted type 304 stainless steel specimen.
FIG. lO--Photograph of surface (top) and schematic illustration of cross section (bottom) of the pit
observed on the Mo-implanted type 304 stainless steel specimen.
1. For type 304 stainless steel with an austenitic matrix, the pit initiation occurs at chem-
ical defects, such as sulfate inclusions, and, immediately after, an important anodic
dissolution event takes place. This process leads to an open pit.
2. For Mo-implanted type 304 stainless steel, the pit initiation occurs at physical and
chemical defects. This process leads to a covered hemispheric pit, which gives rise to
confined corrosion with low current density followed by fracture of the implanted layer
and normal anodic dissolution.
Conclusion
1. The MEM and the FPT methods give similar results for calculating power spectral
densities, with a shorter measurement time for the first method. However, the advan-
t ages cl ai med by the proponent s of the MEM are not al ways cl ear in corrosi on
i nvest i gat i ons.
2. Smoot h MEM spect ra are often rel at ed to a poor frequency resol ut i on. In addition, i f
a spectral line exi st s in the PSD, the frequency resol ut i on has to be i mproved by
i ncreasi ng the order of the MEM, whi ch det eri orat es the smoot hness.
3. Measurement s in t he very l ow-frequency range shoul d be made prudent l y because t he
MEM al ways l eads to a l ow-frequency pl at eau for suffi ci ent l y l ow frequencies.
4. The over l appi ng of MEM spect ra for several frequency bandwi dt hs can be difficult
wi t h sharp, st ruct ured spectra.
5. In some cases, the MEM is the onl y appl i cabl e met hod when onl y one t i me record is
avai l abl e, but, the result has to be careful l y anal yzed, especi al l y in the case of an
unst abl e corrosi on process. The resul t can depend on the specific t i me record used to
cal cul at e the PSD.
6. Concerni ng the corrosi on of mol ybdenum i mpl ant ed stainless steel:
a. a prot ect i ve surface l ayer was f or med as a result of ferritic t ransformat i on and mo-
l ybdenum enri chment , whi ch is di fferent from the mechani sm for prot ect i on obt ai ned
wi t h bul k al l oyed mol ybdenum- bear i ng stainless steels.
b. The i mpl ant at i on decr eased the prepi t t i ng activity, but, nevert hel ess, a number of
pi t s devel oped that perforat ed the prot ect i ve layer, whi ch was in cont rast wi t h the
t ype 304 st ai nl ess steel.
c. It seems that a syst emat i c rel at i onshi p bet ween the l evel of the prepi t t i ng act i vi t y
and the pi t densi t y observed aft er some t i me per i od is quest i onabl e. A l i mi t ed num-
ber of severe pi t s may somet i mes coexi st with an al most noi sel ess passi ve sampl e.
Re f e r e nc e s
[1] Gabrielli, C., Huet, F., Keddam, M., and Oltra, R., Corrosion, Vol. 46, 1990, p. 266.
[2] Gabrielli, C., Huet, E, Keddam, M., Oltra, R., and Pallotta, C., "Stochastic Aspects of Mechanical
and Chemical Breakdown of Passivity," in Passivity of Metals and Semiconductors, M. Froment,
Ed., Elsevier Science Publication, Amsterdam, 1983, p. 293.
[3] Burg, J. P., "Maximum Entropy Spectral Analysis," in Proceedings of the 37th Meeting of the
Society of Exploration Geophysicists, Oklahoma City, Oct. 1967.
[4] Andersen, N. O., Geophysics, Vol. 39, 1974, p. 69.
[5] Kay, S. M. and Marple, S. L., "Spectrum Analysis, a Modem Perspective," Proceedings of the
IEEE, Vol. 69, 1981, p. 1380.
[6] Uruchurtu, J. C. and Dawson, J. L., Corrosion, Vol. 43, 1987, p. 19.
[7] Searson, P. C. and Dawson, J. L, Journal of the Electrochemical Society, Vol. 135, 1988, p. 1908.
[8] Mansfeld, E and Xiao, H., Journal of the Electrochemical Society, Vol. 140, 1993, p. 2205.
[9] Bendat, J. S. and Piersol, A. G., Engineering Applications of Correlation and Spectral Analysis,
John Wiley and Sons, New York, 1980.
[10] Beaunier, L., Pillier, E, and Beaunier, R, "Phase Transformation in Molybdenum Surface Implanted
Stainless Steel: Microstructural Corrosion Characteristics," in Proceedings of the 6th International
Congress on Intergranular and Interphase Boundaries in Materials, Vol. 126-128, Ph. Komninou
and A. Rocher, Eds., Thessaloniki (Greece), Materials Science Forum, Trans Tech Publications,
Switzerland, 1993, p. 507.
[ll] Gabrielli, C., Huet, E, and Keddam, M., Electrochimica Acta, Vol. 31, 1986, p. 1025.
[12] Beaunier, L., "Surface Modification by Molybdenum Ions for Corrosion Protection," in Proceedings
of the 3rd Euromat European Conference on Advanced Materials and Processes, Paris (France),
1993, p. 356.
Andr a~ L egat ~ and E dvar d Govekar ~
A Comparison of Spectral and Chaotic
Analysis of Electrochemical Noise
REFERENCE: Legat, A. and Govekar, E., "A Comparison of Spectral and Chaotic Anal-
ysis of Electrochemical Noise," Electrochemical Noise Measurement f or Corrosion Applica-
tions, ASTMSTP 1277, Jeffery R. Kearns, John R. Scutly, Pierre R. Roberge, David L. Reichert,
and John L. Dawson, Eds., American Society for Testing and Materials, 1996, pp. 129-141.
ABSTRACT: Potential and current fluctuations spontaneously generated by corrosion reactions
are known as electrochemical noise. In certain cases, good correlation can be obtained between
the results of the spectral analysis of electrochemical noise and corrosion rate and type. How-
ever, because of the chaotic nature of corrosion processes, a special mathematical treatment
may be needed. In the present study, the electrochemical noise measured on various metals
was treated by methods known from the theory of chaos, and the results were compared with
the results of spectral analysis. It has been shown that the chaotic characteristics of electro-
chemical noise are related to corrosion type, whereas the rate of corrosion has no influence on
the fractal dimensions of the noise.
KEYWORDS: electrochemical noise measurement, power-spectrum density, chaos, fractal
analysis
Of all t he met hods of cor r osi on measurement , onl y a few are abl e to di st i ngui sh di fferent
t ypes of corrosi on. Most of t hem (pol ari zat i on curves, el ect r ochemi cal i mpedance spect ros-
copy) use an ext ernal vol t age or current source; for this reason, corrosi on processes can be
di st urbed, and the resul t s may not be perfect l y rel i abl e. On t he ot her hand, el ect rochemi cal
noi se consi st s of spont aneousl y generat ed pot ent i al and current fluctuations, whi ch can be
measur ed in freel y cor r odi ng syst ems.
The phenomenon of el ect r ochemi cal noise, part i cul arl y its measur ement as a possi bl e
par amet er for a cor r osi on- moni t or i ng met hod, has recei ved consi der abl e at t ent i on over t he
l ast 20 years. In earl y exami nat i ons of el ect r ochemi cal noi se measur ement ( ENM) at open
ci rcui t pot ent i al , onl y one el ect rochemi cal quant i t y was measur ed and anal yzed [1- 3],
whereas most l at er st udi es st ri ct l y di st i ngui shed bet ween el ect r ochemi cal pot ent i al and cur-
rent noi se [4,5]. Anal yses of ENM wer e per f or med not onl y in t he i nvest i gat i ons of vari ous
t ypes of corrosi on (uni form [41, pi t t i ng [61, and crevi ce corrosi on [7]), but al so in the eval -
uat i on of corrosi on i nhi bi t ors [8] and organi c coat i ngs [9]. In several studies, t he ENM resul t s
were compar ed t o t he resul t s of pol ari zat i on curves, l i near pol ari zat i on resi st ance (LPRM),
and el ect r ochemi cal i mpedance spect r oscopy (ELM). It has been confi rmed that ENM enabl es
t he det er mi nat i on of t he rat e of cor r osi on [10-12] and t he r ecogni t i on of the t ype of corrosi on
[5,13]. Two mai n met hods of anal ysi s of measured el ect r ochemi cal noi se were i mpl ement ed:
Researcher, Institute for Testing and Research in Materials and Structures, Dimi~eva 12, 61000
Ljubljana, Slovenia.
2 Researcher, Faculty of Mechanical Engineering University of Ljubljana, Agker~eva 6, 61000 Lju-
bljana, Slovenia.
129
www.astm.org
statistical (root mean square) and spectral (power-spectrum density). Over the last five years,
ENM has been used for corrosion monitoring in various industrial systems, especially in
electric power plants, both in situ [14-16] and under simulated conditions [17-20]. Although
several studies have been carried out, as yet, no unified theory exists for the sources of ENM.
Over the last 25 years, in nonlinear dynami c theory, some new mathematical parameters
have been developed to characterize nonperiodic and chaotic systems [21], such as: the
reconstruction of attractors [22,23], fractal dimensions [24-26], and Lyapunov exponents
[27,28]. The theory of chaos has been also used in chemistry [29], particularly to analyze
electrochemical processes [30-35]. Various chaotic parameters of current oscillations have
been estimated to describe the electrodissolution of copper [30,31] and iron [32], and the
initiation of localized corrosion [33], as well as to simulate the evolution of pit on silver
[34]. An excellent review of the applications of deterministic chaos theory to corrosion was
presented by Stringer and Markworth [35].
It was established by Mandelbrot that the power law ( l / f " ) of power spectrum may in-
dicate the chaotic nature of a time series, where the exponent c~ is considered to be an index
of its irregularity [36]. The results of the spectral analysis of measured electrochemical noise
usually indicate the continuous broadband nature of fluctuations. Whereas this t ype of spec-
t rum is characteristic for random and chaotic signals, rescaled range analysis has been used
to extend the statistical approach of electrochemical voltage noise [37,38]. Fractal dimensions
of voltage and current noise measured on stainless steel have been calculated to estimate the
dimensionality of the phase space of different types of corrosion [39]. The aim of the present
study has been to apply the theory of chaos to ENM for various metals to improve corrosion-
monitoring techniques based on the spectral analysis.
Electrochemical potential and current noise were measured in a freely corrodi ng system.
The probe contained three identical metal rods encapsulated in an epoxy tube so that onl y
the transverse surface of each was exposed t o the electrolyte. The first pair of electrodes
formed a voltage source, and the second pair a current source, with one electrode in common.
The measuri ng system consisted of two multimeters (HP 3457A) connect ed via an I EEE 488
bus to a personal computer. The input impedances were 100 ~ for current input and 109 1~
for voltage input. Resolution was 1 nA for current and 1 i~V for voltage measurements. The
sampling rate was 500 mHz. In 1 test record, 4096 voltage and current values were recorded.
Measurements of electrochemical noise were made on various metals (carbon steel AI SI
C1008, stainless steel AI SI 302, and pure aluminum 99.99%) in aqueous solutions of various
pH and conductivity values (deionized water, 0.1% sodium hydroxide [NaOH], 0.1% sodium
chloride [NaC1], 0.5% NaCI, 3.5% NaCI, 0.1% HCI, 5% HC1, 0.1% sulfuric acid [H2SO4],
5% H2SO~) to generate a wide spectrum of corrosion rates and types. All tests were per-
formed at constant temperature (25~ and mixing of the electrolyte, so that the level of
dissolved oxygen remained nearly unchanged. Electrode surface areas varied from 7.1 to
50.2 mm 2. To determine the corrosion type and rate, various reference methods were used:
visual inspection, scanning electron mi croscope (SEM) analysis (JEOL 840A), and polari-
zation curves (EG&G PARC 273).
Results and Discussion
It has been shown in previous studies [12,13] that the spectral analysis of electrochemical
noise may indicate the rate and type of corrosion. The power-spectrum density of electro-
chemical current noise (PSD(1) in the frequency interval from 10 to 500 mHz) can be related
LEGAT AND GOVEKAR ON SPECTRAL AND CHAOTIC ANALYSIS 131
to the general corrosion rate, whereas the slope of the power-spectrum density of electro-
chemical voltage noise on a log versus l og scale (the parameter et being obtained from the
1/ ff function) has been recognized as a significant parameter for distinguishing among dif-
ferent types of corrosion. To improve the pattern recognition met hod for distinguishing dif-
ferent types of corrosion, the attractors of potential and current noise were reconstructed and
their fractal dimensions were estimated.
Three typical forms of electrochemical voltage and current fluctuations were generated by
the various types of metal corrosion in the chosen electrolytes. The passivation process was
observed on carbon steel and stainless steel in 0.1% NaOH and on aluminum in deionized
water (Fig. 1). With the exception of the high initial values of voltage and current as a result
of immersion, the values of measured noise were very low (Fig. 2.). In some cases, the
current noise was below measurement limits, which was defined by instrumental noise (see
Fig. 2).
Uni form corrosion was detected on the stainless steel in 5% H2SO4 (Figs. 3 and 4),
whereas the aluminum corroded uni forml y and intensively in 0.1% NaOH (see Fig. 4). The
electrochemical noise generated by uniform corrosion consisted of very frequent voltage and
current transients appearing in the frequency domai n much like white noise (Fig. 5). The
mean values of measured voltage and current were close to zero, but the amplitude of
fluctuations was much higher than during the passivation process.
Pitting corrosion was observed on the stainless steel and aluminum in 3.5% NaC1 (Figs.
6 and 7). The fluctuations of voltage and current were less frequent than during uni form
corrosion. As can also be seen in Fig. 8, the rise time of voltage fluctuations was, in general,
shorter than the descent time; however, for current transients the situation was the opposite.
The power-spectrum densities of potential and current noise could be interpolated by a 1/ ff
function on a log versus l og scale. The voltage and current transients often occurred
simultaneously.
The electrochemical noise records measured during the different types of corrosion were
split into four shorter time series, transformed to the frequency domain, and averaged (see
Figs. 2, 5, and 8). The parameter (x was obtained by linear interpolation of the power-
spectrum densities on a l og versus log scale (Table 1). Additionally, the fractal dimensions
of the attractors of electrochemical noise were estimated and compared with the results of
the spectral analysis.
The behavior of a dynami c system is best described in its phase space, a coordinate system
whose coordinates are the variables necessary to describe completely the state of the system
0 , 6 J i I I ) I H I i h l l l r l l J ~ ~ ' ~ ] H I H J J ' ~ - - T i ~ ] T F 0 ' I ] I T H 1 ] T " ~ ~ I H I T 1 F T T T T i l ~ r r J u m 1 T F r T n ~
|
0. 4 Q ) ~ J - ~ . . . . . . q -0.2 I | b )
- 0 . 4 /
-0. 2
~0~6
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
10-2 10-1 101 10 2 )-3 10-2 10-1 10 o 101 0 2
i / laA c m -2 i / p A c m - 2
FIG. l--Polarization curves measured on: (a) stainless steel AISI 302 (area = 19.6 mm 2) in 0.1%
NaOH and (b) pure aluminum 99.99% (area = 50.1 mm 2) in deionized water.
-20
-60
2 ' o 4 0
. . . . . L . ~ j
80 I{D 120
0 . . . . r - - i , i J , i i i ~ r , l , . ~ T - l ~ 1 1 q T i I ' T
-20" a
' ~
-8 0 i
1 [ a J _ LJ- t \
20 d
0 ~ -80
-100
<= -zo - ~' -azo
-40 b b
-140
-60 d ta
-80 -150 c ~ .
-1000 20 40 60 80 100 120 - 1% _z , , 10 ~ 101 102 , ~rl03
TIME/min log FREQUENCY/mHz
FIG. 2--Electrochemical noise generated by an alloy in a passive condition: (a) stainless steel AISI
302 (area = 19.6 mm 2) in 0. 1% NaOH, (b) pure al umi num 99. 99% (area = 50.1 mm 2) in dei oni zed
water, (c) pure al umi num 99. 99% (area = 7.1 mm 2) in dei oni zed water, and (d) i nst rument al noise.
at any moment . To each possi bl e state of t he syst em a poi nt corresponds in the phase syst em,
whereas the evol ut i on of states is r epr esent ed by a trajectory. A phase port rai t is a graph
depi ct i ng the evol ut i on of the syst em from di fferent i ni t i al condi t i ons. The final state or the
equi l i bri um state of the syst em is model ed by l i mi t sets al so cal l ed attractors.
It has been shown by Packar d et al. [22] and Takens [23] that the phase space can be
appr oxi mat ed by usi ng a r ecor d of a si ngl e observabl e. Thi s procedure, known as the t i me
del ay met hod, has been used by the authors to reconst ruct the attractors of t he measured
el ect rochemi cal noise. The poi nt s of at t ract or of a scal ar t i me series X ( t 3 [in our case E( t )
and l(t)] in D E di mensi onal phase space were deri ved by Eq 1. 9 is the t i me del ay mul t i pl e
of the sampl i ng t i me, and DE is t he embeddi ng di mensi on of the reconst ruct ed phase space,
whi ch shoul d be pr oper l y chosen. The values of x used in reconst ruct i ng the at t ract ors were
det er mi ned by the i nt egral l ocal def or mat i on met hod based on the condi t i on that t wo di st i nct
t raj ect ori es shoul d not i nt ersect [40].
X( t i ) = { [X(t), X(t~ + -r)] . . . X[t~ + ( D E - 1) 9 "r]} ( l )
For a graphi c present at i on of attractors, D E is usual l y chosen to be 2. In this case, Eq 1
is si mpl i fi ed, and the phase- space pl ot s are reconst ruct ed as X( t i ) versus X( t i - "0. The t wo-
di mensi onal phase space pl ot s of the el ect rochemi cal noi se generat ed by di fferent t ypes of
corrosi on can be seen in Fi g. 9. The at t ract or of pot ent i al noi se measured duri ng the passi -
FIG. 3- - SEM micrograph of stainless steel AISI 302 after exposure to 5% H2SO 4.
vation process is nearly a straight line (see Fig. 9a-I), whereas the phase-space plots of
current are dispersed as a result of instrumental noise (see Fig. 9a-II). The attractors of
electrochemical noise generated by uniform corrosion formed disordered sets of points (see
Fig. 9b). The two-dimensional phase space plots of electrochemical noise measured during
pitting corrosion consisted of multiple loops (see Fig. 9c).
From Fig. 9 it is evident that different types of electrochemical noise form different types
of attractors. However, for the characterization of the structure of these attractors, the fractal
dimensions have to be estimated. The dimensionality of an attractor also has an important
physical meani ng- - i t is equal t o the minimum number of variables present in the evolution
of a corresponding dynamic system (degree of freedom). Various types of fractal dimensions
o
> -0.2
-0.4
-0.6
0. 4 ~ 1 1 i i i i i , J ~ ~ 1 i i i i i i i i r ~ rrerT - ~r Tl ~l l 1
a) / ~\ \
0.2 f
-0.8
10-1 10 o
-0.6
b)
101 102 103 104 105 10-1 10 o 101 102 103 104 105
i / FA cm "2 i / pA cm -2
FIG. 4--Polarization curves measured on: (a) stainless steel AISI 302 (area = I9. 6 mm 2) in 5%
1-12804 and (b) pure aluminum 99.99% (area = 50.1 mm 2) in 0.1% NaOH.
>
20
10
-10
0 20 40 60 80 100 120
0 ~ - i i i i , l l l l i - ~ r T x z r ~ i l l l l l ~ - - , r E I p l I ,
J
-20 i o
I
~ 8 f
-100
- I - - i i i i u 2 z J _ ~ _ _ l i i i l l ' J J ~ _ ~ I i I i i [ i i _ l i i l i l
100 l0 t 102 103
3 ~ I
2
1
<
- 1
-2
-80
-100
<
-120
t2
-140
-3 -160
-4u 0 " 1~ ~' ~u- I 100 ' ~ J - ~ J ' ~
20 40 60 80 100 120 101 102 103
T I M E / m i n FREQUENCY/mHz
FIG. 5--Electrochemical noise generated by uniform corrosion: (a) stainless steel AISI 302 (area =
19.6 mm 2) in 5% H2SO 4 and (b) pure aluminum 99.99% (area = 50.1 mm 2) in 0.1% NaOH.
are known, but for application to real data, particularly for hi gher-di mensi onal phase spaces,
the so- cal l ed correlation di mensi on is wi del y used. The procedure for cal cul ati ng the cor-
relation di mensi on (descri bed in detail in Re f 24) was used. Gi ven the vector ti me series
X(t3, the correlation functi on Co~ is defined as:
1 ~ 0{ r - IlX(ti) - X(t)H} (2)
C~ = M 2 - M , , /
where 0 is the Heavi si de step function, M is the number o f poi nts in the vector ti me series
X(tl ), and the vertical bars indicate the norm o f the vector. The summat i on counts the number
o f pairs o f points in the attractor for whi ch the di stance IPf(ti) - X(t)lP is l ess than r. The
correlation di mensi on D2 at various embeddi ng di mensi ons DE can be obtai ned from the
expressi on:
D 2 = l i m l n C~ (3)
,.~o l n r
The correlation di mensi on D 2 is actual l y a measure o f the extent to whi ch the presence
o f a data poi nt affects the posi t i on o f other poi nts l yi ng on the attractor ("spatial correla-
ti on"). It can be estimated onl y i f Eq 3 has a val ue that i s limited by i ncreasi ng the embed-
FIG. 6- - SEM micrograph of stainless steel AISI 302 after exposure to 3.5% NaCI.
ding di mensi on D E of the reconst ruct ed phase space. The correl at i on funct i ons Co~ and the
correlation di mensi ons D2, cal cul at ed for attractors of el ect rochemi cal noise at di fferent em-
beddi ng di mensi ons D e, can be seen in Figs. 10, 11, and 12.
It is evi dent that the correl at i on di mensi ons D 2 of el ect rochemi cal noise measured during
pitting corrosi on converge by i ncreasi ng De (see Fig. 11), whereas for uni form corrosi on no
saturation is observed in D 2 (see Fig. 12). It can be concl uded that the el ect rochemi cal noise
generat ed by uni form corrosi on is random noise. The plot lnCD~ versus l nr for el ect rochem-
ical noi se in the passivation process has two scaling regions, whi ch are also reflected in the
cal cul at i on of D2 (see Fig. 10). Such characteristics of CD~ are typical for l ow-di mensi onal
>
0.6
0.4
0.2
0
-0.2
-0.4
10-1
i i i i i i i i J ~ i i i i l f l I
10 ~ 10 ] I(P 103 104 l0 s
i / pA cm -2
0 ~ ~ i i i , t l ,
-o.2 b )
-0.4
;>
-0.6
-0.8
-1
E , r ~ r r r ~ l l . . , , , , i Ll . ~ , , H, I . , l i Hi n
. ~ [ i l l l l i
1~0.1 10 ~ t~.L.~_~.,,,,,.lO 1 10 a ,, ,,,,,,,10 3 ,, ,,J,,.lO 4 , , ,,~0 s
i / pA cm -2
FIG. 7--Polarization curves measured on: (a) stainless steel AISI 302 (area = 19.6 mm 2) in 3.5%
NaCl and (b) pure aluminum 99.99% (area = 50.1 mm 2) in 3.5% NaCL
100
50
> -50
E
-aso L I
-250 20 40 60 80 10O 120
~ a
- 4 0 ~ - - ~
-60 ] ~ ~ ' ~
-80
l
.lOO ~
I
-t 10 o 101 10 2 10 3
10
200
100
0
<
-100
-20O
-30O 0
i L
20
r . . . . . . i i - - 7
!
J
4'0 f~0 8'0 100 1 89
TIME/min
t
-80 }
-100 ~-
-120 1
FREQUENCY/mHz
FIG. 8--El ect rochemi cal noise generated by pitting corrosion: ( a) stainless steel AI SI 302 (area =
19.6 mm 2) in 3.5% NaCI and ( b ) pure aluminum 99.99% (area = 50.1 mm 2) in 3.5% NaCl.
syst ems wi th an external noi s e that di ffuses the structure o f the attractor [21]. It can be
recogni zed, in general, that D2 o f current noi se s l owl y reaches a l i mi ted val ue than D2 o f
potential noi se (see Fig. 11). However, it is not known whether this i s i nfl uenced by the
different nature o f potential and current noi se, or by instrumental noi s e (a l ower s i gnal / noi s e
ratio for current ( see Fig. 2).
The correlation and embeddi ng di mensi ons o f el ect rochemi cal vol t age and current noi se
generated by different t ypes and rates o f corrosi on is summari zed in Table 2. For each
combi nat i on o f metal and sol uti on, ten pol ari zati on curves were recorded. The val ue o f icor~
was obtai ned as the average o f current densi ti es calculated by Tafel extrapolation. It i s evi dent
that the general corrosi on rate did not affect the fractal di mensi ons.
T A B L E l - - Sl ope s of power-spectrum densities and capacity f ract al dimensions of electrochemical
noise in different types of corrosion (minimum and maximum values).
e t E/ d BV % / d B A
Ty p e of Corros i on decade -~ decade J Do( E) Do( / )
Passi ve - 2 0 - 15 - 1 1 1. 09 1. 22 l . 10 1. 30
Pi tti ng - 3 0 - 2 0 - 15 - 10 1. 35 1. 45 1. 24 1. 38
Uni f o r m - 7 2 - 6 1 1. 68 1. 83 1. 69 1. 79
L E G A T A N D G O V E K A R O N S P E C T R A L A N D C H A O T I C A N A L Y S I S 137
9 L ~ i l
" , . , . . , ' . < , ~
. , . , , . , , + : ~
\ ;? + : j
L L , , ~ L L
0 0 0 0
t I
( ~ - - + 1 3
9 , . " 7 ; ~ : ~ "
, " .'":".C ~" ' ~i , ~" ~' -"
t I [ J
0 ~ 0
I
( 1 - ~ ) 3
- - T ~ I I - -
I _ _ i i I
0 cO ~ ~'
( : ~ - ~ ) 3
o
I
0
C~
I
0
o . I
o ~,
C~
o
0
I . ' C )
9
I
0 4
0
C~
I 1 ~ I ]
. ' j . + .
: , . . : : . ; . ~ . ~ : L . r . , . . . . . . . . . . . .
l
" i + 9
I ,
2
0 0 0 0
0 0 0
I I
(3. -), ) I
I I
r , , ,
. / . . , . ' + + 9 .
L 1 I
0 0 0 0
I I
( i - ~) i
I
"G
I
0 0
8
I
A
t ~
Oi
03
I
0 ~
o I
I
, + ~
~, tr
v N . , , ~
II
" e ~
b
2 ~
- 5 '
} , , .
0
- 5
- q - 1 0
- 1 5
- 1 0
1 0 - -
8
6
S
a)
i i i I
- 8 - 6 - 4
I n r
0 . . . .
- 2
- 4
m - 6
-8 1
- 1 0 . . . . ~ . . . . 9 . . . . ~ - L __ _
- - 4 - 3 - 2 - 1 0
I n r
c}
"Z"
cY
J
- 8 - 6 - 4 - 2 0 5
I n r
d)
~3
- 4 - 3 - 2 - 1
I n r
FIG. lO---Correlation functions and correlation dimensions of electrochemical noise (measured on
alloy in a passive condition--pure aluminum 99.99% in deionized water) at various embedding dimen-
sions (DE from 2 to 10, step 1): (a) CI~ (r) of potential noise, (b) CD~ (r) of current noise, (c) D 2 (r) of
potential noise, and (d) D 2 (r) of current noise.
The met hod of estimating the correlation dimension of measured electrochemical noise
can be a reliable basis for the determination of corrosion type. Unfortunately, the procedure
is very t i me-consumi ng [41], so it is unsuitable for corrosion-monitoring systems. To reduce
the complexity of the calculations, a simpler met hod has been implemented. The box-count-
ing procedure was applied to the measured signals, presented as two-dimensional geometrical
objects, t o estimate the capacity fractal dimension [42].
Let N(~) be the mi ni mum number of 8-mesh squares needed to cover the graph [in this
ease E(t) or I(0]. The capacity fractal dimension, denoted by Do, can be obtained by taking
the limit as 8 approaches zero:
Do = lim l nN(8) (4)
~. o I n( l ~8)
A comparison between the slopes of the power-spectrum densities on a l og versus log
scale, and the estimated capacity fractal dimensions of the measured electrochemical noise,
can be seen in Table 1. The parameters a and D O were calculated for different types of
corrosion of the metals (carbon steel AI SI C1008, stainless steel AI SI 302, and pure alu-
mi num 99. 99%) and onl y mi ni mum and maxi mum values of estimate values are presented.
It is evident that capacity fractal di mensi on Do is related t o the parameter a obtained by the
0
-5
U
dO
-15
o) T
D E = 2 ~ /
-10 -8 -6 -4 -2
In r
U
f
b) T O ~
In r
5 1 i i T
c)
4 \ ~
1 DE= 2 ~ ~ _ z
d)
DE = 2
~ 0 . . . . . . . . . . . . . .
-8 -6 -4 -2 0
In r In r
FI G. 1 1 - - C o r r e l a t i o n functions and correlation dimensions of electrochemical noise (measured during
uniform corrosion--pure aluminum 99.99% in 0.1% NaOH) at various embedding dimensions (DE from
6 to 24, step 2): ( a) C ~ (r) of potential noise, ( b) CDE (r) of current noise, ( c) D2 (r) of potential noise,
and ( d) D 2 ( r ) of current noisel
spectral analysis; moreover, the fractal dimension was recognized as an even more accurate
parameter distinguishing among different types of corrosion. It can also be seen from Table
1 that Do, when estimated from potential noise, enables the classification of the different
types of corrosion without the overlapping of intervals, as opposed to current noise in which
some overlapping occurs.
Conc l us i ons
The analysis of electrochemical noise by mathematical tools known from the theory of
chaos enables the distinction of different types of corrosion. The correlation dimension in-
dicates that the dimensionality of the phase space of electrochemical noise increases with
the mode of corrosion from passivation, pitting, to uniform corrosion. From the chaotic
analysis of electrochemical noise, it can be assumed that potential noise contains more in-
formation about the form of corrosion than current noise.
The capacity dimension of measured electrochemical noise was also estimated and has
been recognized as a reliable parameter for the determination of the type of corrosion. The
corrosion rate can be estimated by the spectral analysis, but it has no influence on the fractal
dimension of electrochemical noise. Thus, spectral and chaotic treatment can be used as
compl ement ary methods in the analysis of electrochemical noise for corrosion monitoring.
S
n
u [ O ) . . . . . . . l - - -
!
-5 j DE:
i
-10)
r
) // / / / /
V , / ,
/ / / /
5 / /
L _ _ t 9
-10 -8 -6 -4 -2 0
- ' ~ ":)
- l o - 8 - 6 4 - i
In r In r
] 5 c) ' /\ 24 15i d) '
!
10 10
5 - ~ 0 5
DE: 6
0-10 -6 -4 -2 -01O -~8 & -4 -2 0
In r In r
FIG. 12--Correlation function and correlation dimension of electrochemical noise (measured during
pitting corrosion--pure aluminum 99.99% in 3.5% NaCl) at various embedding dimensions (DE from 2
to 10, step 1): (a) CD~ (r) of potential noise, (b) Ct~ (r) of current noise, (c) D 2 (r) of potential noise,
and (d) D2 (r) of current noise.
TABLE 2--Correlation and embedding dimensions of electrochemical noise in different types
of corrosion.
Type of Corrosion Metal ico~/~A cm -: D2(E) De(E) D2(/) De(/)
Passive stainl ess steel AI SI 302 0.4 1.35 8 >10 >26
Passive al uminum ( 99.99%) 0.4 1.15 4 >10 >10
Pitting stainl ess steel AI SI 302 1 1.8 7 2.5 10
Pitting al uminum (99.99%) 2 1.8 5 4.2 9
Unif orm stainl ess steel AI SI 302 40 >12 >26 >9 >26
Unif orm stainl ess steel AI SI 302 80 >12 >26 >10 >26
Unif orm al uminum (99.99%) 100 >12 >24 >14 >24
Unif orm carbon steel AI SI C1008 >1000 >11 >26 >12 >24
Acknowledgment
The au t hors t hank al l r evi ewer s f or t hei r hel p f u l comment s, w hi ch have enabl ed t he au t hors
to l ook at t he ex p er i ment al resu l t s wi t h a mor e cri t i cal ey e and to cl ari f y t he concl u si ons.
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[18] Brennestuhl, A. M., in Proceedings of the 12 th International Corrosion Congress, Vol. 6, NACE
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[20] Liu, C., Macdonald, D. D., Medina, E., Villa, J. J., and Bueno, J. M., Corrosion, Vol. 50, 1994, p.
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[21] Tsonis, A. A., Chaos--From Theory to Applications, Plenum Press, New York, 1992.
[22] Packard, N. H., Crutchfield, J. P., Farmer, J. D., and Shaw, R. S., Physical Review Letters, Vol. 45,
1980, p. 712.
[23] Takens, F., in Dynamical Systems and Turbulence, Warwick 1980, D. A. Rand and L. S. Young,
Eds., Lecture Notes in Mathematics, Vol. 898, Springer-Verlag, New York, 1981, p. 366.
[24] Grassberger, P. and Procaccia, I., Physica D, Vol. 9, 1983, p. 189.
[25] Higuchi, T., Physica D, Vol. 31, 1988, p. 277.
[26] Theiler, J., Journal of the Optical Society of America, Vol. 7, 1990, p. 1055.
[27] Eckmann J.-P. and Ruelle, D., Reviews of Modern Physics, Vol. 57, 1985, p. 617.
[28] Broomhead, D. S. and King, G. P., Physica D, Vol. 20, 1986, p. 217.
[29] D. Avnir, Ed., The Fractal Approach to Heterogeneous Chemistry: Surfaces, Colloids, Polymers,
John Wiley & Sons, Chichester, Great Britain, 1989.
[30] Basset, M. R. and Hudson, J. L., Journal of Physical Chemistry, Vol. 93, 1989, p. 1989.
[31] Dewald, H. D,, Parmananda, P., and Rollins, R. W., Journal of the Electrochemical Society, Vol.
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721.
[33] Sharland, S. M., Bishop, C. M., Balkwill, P. H., and Stewart, J., in Advances in Localized Corrosion,
H. S. Isaacs, U. Bertocci, J. Kruger, and S. Smialovska, Eds., NACE International, Orlando, 1987,
p. 109.
[34] Corcoran, S. and Sieradzki K., Journal of the Electrochemical Society, Vol. 139, 1992, p. 1568.
[35] Stringer, J. and Markworth, A. J., Corrosion Science, Vol. 35, 1993, p. 751.
[36] Mandelbrot, B. and van Ness, J. W., SlAM Review, Vol. 10, 1968, p. 422.
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[38] Roberge, P. R., Corrosion, Vol. 50, 1994, p. 502.
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[40] Buzug, T. and Pfister, G., Physical Review A, Vol. 45, 1992, p. 7073.
[41] Parker, T. S. and Chua, L. O., Practical Numerical Alghorithms f or Chaotic Systems, Springer-
Verlag, New York, 1989.
[42] Falconer, K., Fractal Geometry: Mathematical Foundations and Applications, John Wiley & Sons,
Chichester, Great Britain, 1990.
Pi erre R. Rober ge I
Quantifying the Stochastic Behavior of
Electrochemical Noise Measurement During
the Corrosion of Aluminum
REFERENCE: Roberge, R R., "Quantifying the Stochastic Behavior of Electrochemical
Noise Measurement During the Corrosion of Aluminum," Electrochemical Noise Measure-
ment f or Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R. Scully, Pierre
R. Roberge, David L. Reichert, and John L. Dawson, Eds., American Society for Testing and
Materials, 1996, pp. 142-156.
ABSTRACT: This paper describes a study of electrochemical measurements that included the
analysis of potential noise fluctuations recorded during the free corrosion of a strain-hardened
aluminum alloy exposed to an aerated saline solution. The analysis of spontaneous electro-
chemical noise (EN) generated during these experiments was made by various analysis tech-
niques specifically designed to reveal the stochastic and fractal nature of signals and shapes.
The paper demonstrates how rescaled range analysis and stochastic process detector techniques
can serve to highlight features present in the frequency domain of transformed data records.
It is also shown that the corrosion cell made with aluminum exposed to an aqueous aerated
saline solution is an excellent source of noise, which can be easily varied by changing the pH
of the solution to force depassivation phenomena. The analysis of spontaneous EN by com-
plementary methods is demonstrated to be a practical approach for the identification of the
physical phenomena causing the EN. It is also demonstrated that monitoring the electrochem-
ical impedance spectroscopy behavior in parallel to EN can be valuable because it helps to
establish some fundamental correlations in real time and define the sensitivity of each technique
under similar conditions. In the present study, the drastic changes recorded by EN measure-
ments when the solution pH was slightly reduced are indicative of the tremendous sensitivity
of EN monitoring to changes in the corroding environment.
KEYWORDS: electrochemical noise, stochastic, chaos, depassivation, aluminum corrosion,
analysis methods
Many biological, chemical, and physical systems have been found to exhibit chaotic be-
havior [1-5]. The extensive development of techniques for studying electrochemical reactions
has similarly stimulated the study of fluctuating electrochemical processes that translate into
electrochemical noise (EN) [6]. In this context, the study of spontaneous current or potential
fluctuations for the characterization of corrosion processes has also received considerable
attention in recent years. The study of corrosion potential fluctuations was applied, for ex-
ample, to monitor the onset of events characterizing pitting [7-10] and stress corrosion
cracking corrosion [11-13]. During localized corrosion, EN seems to be generated by both
stochastic processes typically present during passivation breakdown and repassivation events
and deterministic processes such as film formation or pit propagation. In this paper, fluctu-
ations of the corrosion potential observed on freely corroding aluminum material exposed
Professor, Department of Chemistry and Chemical Engineering, Royal Military College, Kingston,
Ontario, Canada, K7K 5L0.
142
www.astm.org
ROBERGE ON QUANTIFYING STOCHASTIC BEHAVIOR OF ENM 143
to aerated saline solutions will be analyzed with techniques specifically designed to reveal
the stochastic and chaotic features that are present in EN signatures.
Noise and Chaos Analysis
The most common way to analyze EN data has been to transform time records in the
frequency domain to obtain power spectral density (PSD) plots. PSD plots can typically be
computed using fast Fourier transforms (FFT) [14] or other algorithms such as the maximum
entropy method (MEM) [15,16]. But quite a few other analytical tools have been developed
to detect and characterize hidden deterministic or chaotic features in seemingly random data
and reveal the properties of the equations that could represent fluctuating behavior. These
tools include calculations of the probability distribution, Lyapunov exponent, and various
measures of the fractal dimension. Many of these tools have recently become commercially
available [17]. Two other techniques, rescaled range scale (R/ S) analysis and stochastic
process detector (SPD), which are not yet available in software form, are included in the
present study because they have already been applied by the author in different corrosion
studies [18-21].
Chaos Dat a An a l y z e r
Although the concepts and models necessary to characterize chaotic behavior can be com-
plex, the association of low-dimensional chaotic dynamics with the presence of strange at-
tractors has permitted the quantification of chaos. Various methods provide the estimation
of properties of strange attractors. These attractors have been characterized, for example, for
their fractal presence in a spatial representation or for the degree of divergence of repeated
patterns using Lyapunov exponents. Owing to the ingenuity of many experimenters, the study
of deterministic chaos has undergone a transition from the derivation of purely mathematical
and theoretical results to the quantitative identification of chaotic features in experimental
data.
Re s c a l e d Range An a l y s i s
This approach, which is relatively new in electrochemistry, was derived from one of the
most useful mathematical models for analyzing time-series data that was proposed by Man-
delbrot and van Ness [22]. Although the fractional Brownian motion (fBm) model can help
to describe very complex geometries or time series, its analysis can be made relatively simply
by using the rescaled range analysis technique originally proposed by Hurst [23] and applied
by Mandelbrot and Wallis to the determination of the fractal characteristics of a time series
[24]. A detailed description of the R/ S technique (where R or R(t , s) stands for the sequential
range of the data points increments for a given lag s and time t, and S or S(t , s) for the square
root of the sample sequential variance) can be found in Fan et al. [25]. Hurst [23] and later
Mandelbrot and Wallis [24] proposed that the ratio R( t , s ) l ( t , s ) , also called the rescaled range,
is itself a random function with a scaling property described by Eq 1 in which the scaling
behavior of a signal is characterized by the Hurst exponent (H), which can vary between
0 < H< I .
R~,.,) ~ S H ( 1)
S ( t , s )
It has additionally been shown [26] that the local fractal dimension dFi of a fBm noise
trace is related to H through Eq 2, which makes it possible to characterize the fractal di-
mension of given time series by simply calculating the slope of a R/ S plot.
d F ~ = 2 - H 0 < H< 1 (2)
Stochastic Process Detector
The SPD technique was designed to quantify the stochasticity of EN records as a function
of frequency. In the present study, this frequency was the sampling frequency, that is, 2 Hz.
The main idea behind the SPD technique is that specific corrosion modes, such as pitting or
other forms of localized corrosion, will potentially generate EN containing deterministic
features. It was hoped that by focusing on the stochasticity of EN records the technique
would be highly sensitive to any feature falling out of such category and reveal some infor-
mation not visible by any other analysis technique. The SPD technique, which has been
explained in details elsewhere [19], consists in two levels of EN transformation. First, EN
records are transformed into a series of singular events, that is, each point of a time series
is examined for its appurtenance to either positive or negative noise peaks. In the second
level of transformation, the distribution of peak lengths f ( t ) is examined and compared to
the theoretical exponential decay distribution, represented by Eq 3 where ),, is the mean
value and t is the peak length (time), that would characterize a series of stochastic events
[27]. The goodness-of-fit (GF) of real data by the exponential function is then calculated to
serve as a measure of stochasticity of the time records.
f ( t ) = X," e -a' (3)
The slope of the basic events (AV/ At ) is also comput ed by the SPD technique because
this parameter is thought to be an important characteristic of the electrochemical systems
being studied.
The specimens were cut from a block of strain-hardened 5083-H131 aluminum alloy armor
material (thickness 5.0 cm; analyzed composition chromi um: 0.19, copper: 0.06, iron: 0.53,
magnesium: 4.1, manganese: 1.3, silicon: 0.50, zinc: 0.21) t o appropriate sizes for mount i ng
in epoxy according t o metallographic techniques. A pair of identical aluminum specimens
exposing their short transverse face was immersed in a 2-L beaker containing a solution of
3% sodium chloride. Before mounting, provisions were made for electrical connection to the
unexposed back of the samples and the unexposed edges were coated with an aluminum-
vinyl anticorrosive paint to prevent crevice corrosion between the epoxy mount and the
aluminum electrodes. After mounting, the specimens were polished up to a 600-grit finish
and cleaned with acetone and dichloromethane. The cell was equipped with an air purge and
a saturated calomel electrode (SCE) brought into close proximity with one electrode by a
Luggi n probe. The mount ed specimens were separated by 2.5 mm and kept in a stable
parallel position with plastic holders. The samples were exposed to the neutral aerated saline
solution for three days before the solution was acidified to a pH of ~4. 8 by adding small
increments of a 0.1 N hydrochloric (HC1) solution.
The reference electrode (SCE) served to measure the corrosion potential and its fluctua-
tions. The fluctuations were monitored through a high-pass filter (resistance (R) = 1 m~ in
series with a capacitor (C) -- 50 p,F and a lower frequency cutoff (f~) = 1/(2~rRC) that is,
3.2 mHz) to increase the sensitivity of the measurements. The high-sensitivity multimeter
used in these studies (Hewlett Packard Model 3457A) has a resolution of l 0 nV on its most
sensitive scale (30 mV). A sampling interval (At) of 0.5 s and a number of consecutive data
points (N) of 1800 were chosen because this gives a factual measuring frequency window
in which corrosion processes are dominant [28]. The frequency domain corresponding to
these sampling conditions can be evaluated to be between 1 Hz (fmax) and 1 mHz (fmi,) with
the help of Eqs 4 and 5 [29].
1
f"~' = 2A---t (4)
1
fmin = NAt (5)
The electrochemical impedance spectroscopy (EIS) measurements were performed with a
commercial generator/analyzer (Solartron Model 1255) at the corrosion potential (Eco~r), and
each measurement was repeated five times to ascertain the stability of the system being
evaluated. A frequency range of 100 to 0.1 Hz was selected for its sensitivity to corrosion
resistance. A potentiostat was not used in these measurements. The alternating current was
applied directly between the two aluminum electrodes and kept at a value that would not
FIG. 1--pH and parameters calculated from E1S data (corrosion rates, V, and Cdl , [~) during the
exposure of alloy 5083 specimens to an aerated 3% NaCl solution.
cause more than lO-mV difference (peak to peak) across the cell. The polarization resistance
(Rp) values were determined with the projection of centers analysis technique described
elsewhere [30-32].
Results and Di scussi on
The corrosion rates (CR) and the double-layer capacitance (Cdl) values calculated from
the EIS results obtained during the twelve-day experiment are presented in Fig. 1. The
transformation of EIS Rp values into corrosion rates was possible by using Eq 6, after cor-
recting for the two-electrode configuration (each electrode = Rp/2). In Eq 6, EW is the
equivalent weight of the corroding metal (8.99 g eq -t for aluminum alloys), d is the metal
density (2.7 g cm-3), A is the exposed surface area (cm2), and K is a constant that has a
value of 3.3 if Rp is in kft and the polarization resistance constant (B) is in mV. A B value
of 24 mV has been reported as an average value for aluminum alloys exposed to chloride
solutions [33].
K.EW.B
Corr. rate (p.m/y) = d- Rp 9 A (6)
The initial low corrosion rates of the aluminum specimens immersed in a neutral 3%
sodium chloride (NaCI) solution increased markedly when the pH was lowered during the
fourth day of the experiment. Lowering the pH is known to accelerate the breakdown of the
FIG. 2--E-pH diagram of the chemical species involved in the system O-H-AI with concentration of
soluble species set at 10 -5 M.
protective film on aluminum and prevent self-repairing before finally leading to an acceler-
ation of localized corrosion [34]. Figure 2 illustrates the passive/corroding frontier of alu-
minum in the traditional form of a E-pH diagram computed from available thermodynamic
data [35] and with the concentrations of soluble species set at 10 -5 M. Note that the presence
of chloride has no effect on the predominance diagram of Fig. 2, but that the presence of
chlorides greatly accelerates the kinetics of the reactions involved [35].
When the solution pH was adjusted to 4.8, the corrosion potential temporarily moved to
slightly more anodic values (Fig. 3). Although the corrosion rates and double-layer capaci-
tance values calculated from the EIS results increased notably when the environment was
acidified, three times for CR and two times for Cdt, note that the average Eco~ values, expect
for the temporary anodic excursion after acidification, remained stable. But lowering the pH
dramatically increased the EN recorded at Er and even favored the production of potential
oscillations that could last for many hours. The oscillations encountered when the pH was
lowered were difficult to reproduce and could hardly be used for monitoring. But their
presence, even temporary, is indicative of the complexity of the competing corrosion pro-
cesses occurring at such metallic/environment interface.
Examples
Three EN records have been chosen to illustrate the different noise characteristics observed
during that experiment. The first file (Fig. 4) was sampled a few hours after immersion of
FIG. 3--Eco,-, and pH measured during the exposure of 5083 specimens to an aerated 3%
NaCl solution.
0.4
>
E
5n
O
r
II)
O)
O
0. 3
0. 2
0.1
0
-0.1
-0. 2
-0. 3 [ ' ~
-0.4 =
-0.5
0 100 200 300 460 500 6 ( ~ 0 700 860 900
Ti me/ s
FIG. 4 - - EN recorded during 15 min of the first day of the experiment with 5083 exposed to an aerated
3% NaCI solution.
the freshly polished specimens into the aerated saline solution. The level of noise activity at
that point was relatively small, the fluctuations slow or sluggish, and without specific fea-
tures. The PSD plot (Fig. 5) corresponding to this noise record shows a rapid decline of the
power density in the low-frequency portion of the PSD plot (between 10 3 and 10 -2 Hz)
and very small energy attributable to higher frequency values. The second example chosen
(Fig. 6) was sampled during the day that followed the pH adjustment. The tremendous level
of potential activity, which is visible by considering the scale of the potential fluctuations
recorded (10 mV peak to peak), translated into very high values on the corresponding PSD
plot (Fig. 5). The level of electrochemical activity was, in this second case, prevalent right
to the frequency domain corresponding to fmi, (10 2.5 HZ). The final example (Fig. 7) was
sampled on Day 9 of the experiment, at which point the EN was apparently dominated by
chaotic features. The PSD plot (Fig. 5) of the noise file indicated that a dominant frequency
component existed at approximately 0.016 Hz (10 -18 Hz) with a period around 1 min or
63 s.
The results obtained by analyzing the EN of the first example (see Fig. 4) with the SPD
method (Fig. 8) indicated a very poor fit (82%) of the exponential decay model at the
sampling frequency (2 Hz), whereas the R/ S analysis revealed a fractal dimension (D =
1.37) indicative of a small degree of persistence (or regularity). The fit (Fig. 9) made by the
SPD method was excellent (96.7%) for the example presented in Fig. 6, and the R/ S analysis
showed a fractal dimension (D = 1.65) indicative of antipersistence [25].
Although the results obtained with the SPD method (Fig. 10) applied to the third example
(see Fig. 7) appeared to fit the distribution of peaks tightly (GF of 95.7%), the distribution
of positive potential slopes presented an important anisotropy that was not paralleled on the
FIG. 5--Results of analysis by FFT of EN recorded during: Day 1 of experiment (Fig. 4); Day 4
(Fig. 6); and Day 9 (Fig. 7).
15-
~ I . . . . . . . . . . . . . . . . . . . . . . ~ I
> -10
-15 . . . . . . . . . . . . . . . . . . . . . . . . . . .
-20 j ~- - - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
-250 100 260 3( ) 0 460 560 600 700 860 900
Time/s
FIG. 6--EN recorded during 15 min of Day 4 of the experiment with 5083 exposed to an aerated 3%
NaCI solution.
>
E
.oo
o
m
0
2
0.5
0-
-0.5
-1-
-1.5-
-2
0 160 200 300 400 5( ) 0 600 760 860 900
Time/s
FIG. 7- - EN recorded during 15 min of Day 9 of the experiment with 5083 exposed to an aerated 3%
NaCl solution.
FIG. 8--Resul t s of analysis by SPD of EN recorded during Day 1 of experiment (Fig. 4); histogram =
real distribution, line = calculated distribution, and hatched surface = potential slopes.
350
300
O.
50
250
t -
O
"5 200
0
Q..
~ 150
|
Q..
100
0
.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
3, 500
3,000
2, 500 m
>
2, 000
O.
O
1,500 a~
1,000 :~
5O0
Peak durat i on/ s
[ I I F i t t e d model [~Observed peaks [~Observed slopes 1
FIG. 9--Resul t s of analysis by SPD of EN recorded during Day 4 of experiment (Fig. 6): histogram =
real distribution, line = calculated distribution, and hatched surface = potential slopes.
negative side. This can be explained by the sharpness of the positive or anodic potential
excursions, visible in Fig. 7, symptomatic of a fast repassivation process following the much
slower depassivation of the partially protective surface. The R/S analysis performed on these
data clearly indicated the presence of persistence (D = 1.33), which is characteristic of the
presence of deterministic features.
Correl at i ons
The analysis of spontaneous EN by different and complementary methods, illustrated by
the previous examples, can serve to quantify the visible differences present in noise records.
In the present study, the drastic changes recorded by EN measurements, when the solution
pH was slightly reduced, are indicative of the tremendous sensitivity of noise monitoring to
changes in the corroding environment.
The data generated by the various techniques used in this experiment were analyzed for
the presence of correlations between the numerous parameters involved. For example, the
results obtained by monitoring the system with EIS seemed to correlate fairly well with the
pH measurements. The correlation coefficient calculated between CR and pH values was, in
fact, excellent (-0.96), indicating a simple inverse relation existed between pH values and
the corrosion rate. The Cat values also followed an inverse relation with the pH, but the fit
was slightly less, that is, correlation coefficient = -0.84. But, not surprisingly, the Eco =
250
200
o3
o~
Q .
~_ 100
50
.5 1 .5 2 2.5 3 3.5 4 4.5 5 5.5
300
300
! 2 0
200 >
"-i
150 o
c r )
1 0 0 o
>
50
Peak durat i on/ s
I IIFi tted model [ ] Observed peaks [ ~ Observed slopes I
FIG. lO--Results of analysis by SPD of EN recorded during Day 9 of experiment (Fig. 7):
histogram = real distribution, line = calculated distribution, and hatched surface = potential slopes.
me a s ur e me nt s di d not cor r el at e wel l wi t h any of t hese par amet er s ( - 0 . 1 9 wi t h CR, - 0 . 3 4
wi t h Cdt, and 0. 18 wi t h t he pH).
The cor r el at i on coef f i ci ent s cal cul at ed be t we e n pH, CR, Ddt, and Eco,~ and s ome o f t he
par amet er s obt ai ned by anal yzi ng EN r ecor ds wi t h var i ous t echni ques ar e pr es ent ed i n Tabl e
1. Amo n g t he par amet er s eval uat ed by t he SPD met hod (GF, l / h , and pot ent i al sl opes) ,
none s e e me d t o cor r el at e ver y wel l wi t h any o f t he f our st andard el ect r ochemi cal par amet er s.
Thi s was not a bi g sur pr i se becaus e t he SPD was known t o be mos t l y sensi t i ve t o t r ansi t i ons
TABLE 1--Correlation coefficients calculated between standard electrochemical measurements and
parameters estimated from EN records.
Correlation Coefficient
Parameter GF a 1 / h a Slop@ dFi b CapD c Lyap d
pH - 0.17 0.03 0.45 - 0. 84 - 0. 44 - 0. 65
CR - 0. 20 - 0. 03 0.55 0.85 0.49 0.71
C~ - 0. 20 0.45 0.25 0.82 0.57 0.82
Eco ~ 0.17 - 0. 09 0.40 - 0. 21 - 0. 09 - 0. 17
Goodness-of-fit, mean, and potential slopes measured by SPD.
b Fractal dimension calculated by R/ S analysis (Eq 2).
c Capacity dimension calculated, with the Chaos Data Analyzer [17].
d Lyapunov exponent calculated with the Chaos Data Analyzer.
between stochastic and deterministic processes that are themselves related to localized cor-
rosion problems [18,19]. Figure 11 illustrates the sensitivity of the potential slopes, for
example, to the modification of the pH done on Day 4.
Another feature revealed by the SPD method is the presence of anisotropy between the
anodic and cathodic potential excursions and between short and long duration peaks. This
phenomenon appears as differences in the calculated values presented in Fig. 11. It can be
seen that there existed some differences between the positive and negative potential slopes
before the pH was modified and that these differences disappeared, from that point onward,
from the negative excursions and became variable for the positive excursions. These subtle-
ties are also more characteristic of localized corrosion phenomena.
But the analysis for correlations revealed that an interesting relation seemed to exist be-
tween the fractal dimension that can be evaluated by the R/ S technique and three of the
four electrochemical parameters, that is, CR, Cat, and pH. This is illustrated in Fig. 12, in
which the Hurst exponent that leads to the fractal dimension through Eq 2 is seen to change
from values indicating persistence (~0.6) to values indicative of antipersistence (~0.4) after
the pH was modified. Both the capacity dimension and the Lyapunov exponents calculated
with the Chaos Data Analyzer also seemed to follow these three electrochemical parameters,
although with much more scatter than dn, indicating that the chaotic nature of the EN records
is also linked, at least in this experiment, to the corrosion kinetics (CR) measured indepen-
dently by EIS and the corrosivity of the solution (pH). Once sound correlations are estab-
lished, the advantages of any of the transforms examined in this study become obvious: the
FIG. 11--Positive (black symbols) and negative (white symbols) potential slopes corresponding to
short ([[] and U) and long (A and ~r) duration peaks measured during the experiment with 5083
aluminum.
FIG. 12--Lyapunov (A) and Hurst (~) exponents calculated during the experiment with 5083
aluminum.
patterns or absence of patterns could give immediate indications concerning the state of a
corrosion situation. By looking at various aspects of the EN signatures, it may become
possible to relate specific combination of characteristic features to the corrosion processes
themselves.
Summary
This paper has described a study of electrochemical measurements that included the anal-
ysis of potential noise fluctuations recorded during the free corrosion of a strain-hardened
aluminum alloy used for armor applications exposed to an aerated saline solution. The anal-
ysis of spontaneous electrochemical noise generated during this experiment was made by
various analysis techniques specifically designed to reveal the stochastic and fractal nature
of signals and shapes. It was found that the corrosion cell made with aluminum exposed to
an aqueous aerated saline solution is an excellent source of noise which can be easily varied
by lowering the pH of the solution to force depassivation phenomena. If this pH is adjusted
to 4.8, it is even possible to initiate the production of oscillations that can last for many
hours and be a vivid demonstration of the complexity of the processes that can occur at a
corroding interface.
But to make sense of these features and reveal their essential components, it is important
to consider appropriate signal-processing techniques. In the present paper, the fractal dimen-
sion estimated by R/S analysis seemed to fit the trends observed independently by measuring
the corrosion rates with EIS and the corrosivity as it relates to the pH of the solution. These
findings, if they are confirmed for other systems, would indicate that the potential fluctuations
can be used to monitor the corrosion rates.
Acknowl edgment
The aut hor is grat eful to t he Def ence Resear ch Es t abl i s hment Paci fi c, and par t i cul ar l y t o
Dr. Der ek Lenar d, wi t hout whose suppor t this wor k woul d not have been done.
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Thomas E Barton, Davi d L. Tuck, and D. Brett Wells ~
The Identification of Pitting and Crevi ce
Corrosion Spect r a in Electrochemical Noi se
Using an Artificial Neural Net work
REFERENCE: Barton, T. E, Tuck, D. L., and Wells, D. B., "The Identification of Pitting
and Crevice Corrosion Spectra in Electrochemical Noise Using an Artificial Neural Net-
work," Electrochemical Noise Measurement f or Corrosion Applications, ASTM STP 1277,
Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson,
Eds., American Society for Testing and Materials, 1996, pp. 157-169.
ABSTRACT: An artificial neural network has been developed to identify the onset and classify
the type of localized corrosion from electrochemical noise spectra. The multilayer feedforward
(MLF) network was trained by classical back-propagation to identify corrosion from the char-
acteristics of the initial current ramp. Using 50 training files and 39 test files taken from
measurements on Type 304 stainless steel in a dilute chloride electrolyte, the network accurately
detected and classified 96% of the data and reported no misclassifications. Experiments with
high levels of adventitious noise superimposed on the original data have been carried out to
examine the noise tolerance of the network.
KEYWORDS: artificial neural networks, pitting corrosion, crevice corrosion, electrochemical
noise, stainless steel
El ect rochemi cal Noi s e and Loc al i z e d Corros i on
Electrochemical noise associated with corrosion processes is readily detected on passive
or coated surfaces as low-frequency current or potential fluctuations. Previous analysis of
electrochemical noise has concentrated on two broad treatments: under steady-state condi-
tions, small fluctuations in potential and current have been correlated to produce measure-
ments of low-frequency impedance allowing estimation of corrosion rate [1,2]. Second, under
stationary conditions, the stochastic nature of localized corrosion processes has been inves-
tigated by spectral analysis in the frequency domain or statistical counting in the time domain
[3-10]. In the latter treatment, stochastic models have been explored yielding parameters
such as intensity or rates of pit generation [6,7], and criteria for sustained localized disso-
lution based on a critical pit age have been developed [8,9]. Within the framework of these
localized corrosion models and with the recognition of electrochemical noise signatures as-
sociated with specific corrosion processes, particularly metastable or incipient localized cor-
rosion processes [It)I, an opportunity exists to develop monitors for localized corrosion. The
objective was to develop and test an artificial neural network to identify the onset of localized
corrosion from el ect rochemi cal noise spectra.
The practical interest in neural networks as a detection and classification tool lies in the
analysis of field-generated electrochemical noise spectra. Fluctuations in the environmental
conditions found in industrial plants frequently represent a larger source of uncertainty than
Research scientists, Industrial Research Ltd., EO. Box 2225, Auckland, New Zealand.
157
www.astm.org
the random variation associated with the initiation of localized corrosion in laboratory ex-
periments. The assumption of a stationary state is often invalid. The successful identification
of precursors to localized corrosion using neural networks may reduce the risk of corrosion
failure for plant conditions that are not adequately defined.
A fundamental requirement for direct monitoring of corrosion activity is the efficient
interpretation of spectral characteristics. Criteria for identifying localized corrosion have been
proposed based on changes in the noise resistance R, = V / I (where V and 1 are root mean
square [rms] values of potential and current) [2] or the characteristic shape of the power
spectral density curve [3, 4]. The averaging procedures associated with these techniques are
expected to limit the sensitivity to infrequent corrosion activity, and this study concentrates
on the direct analysis of data in the time domain only. A neural network has been designed
to operate as a decision-making filter, to distinguish the onset of pitting or crevice corrosion
based on the characteristics of the current spectra. Onl y the initial current ramp has been
used to identify between corrosion processes. The advantage of using a neural net work for
identification is that the network establishes its own "noi se-t ol erant " criteria for classification
and offers the potential for on-line operation and actual field training.
Electrochemical data have been collected for the initiation of pitting and crevice corrosion
on AISI Type 304 stainless steel in a dilute chloride environment (1000 mg 9 L 1 C1-) to
enable training and testing of the network.
Neural Networks and Learning
The architecture of an artificial neural network consists of highly interconnected processor
elements with groups of elements operating in parallel. Because of the distributed nature and
interconnectivity of the network, large amounts of input activity converge on each of these
processor elements, which operate as simple summers. Weights exist on the processor inter-
connections, which proportion the flow of data through the network. Nonlinear transfer func-
tions operate on the summed converging data at each processor element. The outputs of the
network therefore depend on the
9 Input data,
9 Net work architecture,
9 Weights of the network interconnections, and
9 Form of the transfer functions.
The choice of the size and type of architecture and the form of the transfer functions
depend on the type of input data and the problem to be solved [11,12]. The type of training
algorithm is usually determined by the architecture chosen. A multilayered feedfoward
(MLF) network [13,14] was chosen for this pattern detection and classification problem.
Weights on the processor interconnections of the MLF network were developed by a back-
propagation training algorithm [15].
Multilayered Feedforward Network
The MLF network is the most widely applied artificial neural network. This network has
input and output layers of processors and one or more hidden layers of processors. (Hidden
refers to those that are not directly accessible by, or to, external manipulation.) Each layer,
beginning at the input layer, connects to the next layer ahead of it in a feedforward manner
(Fig. 1). Using the classical back-propagation training algorithm, this type of net work has
BARTON ET AL. ON ARTIFICIAL NEURAL NETWORK 159
D ~ W O R K
I N ~ PUTS
HIDDEN HIDDEN
LAYER LAYER
FIG. 1--A schematic of a simple multilayer feedforward network with two hidden layers.
been shown to be able to solve most neural network applicable problems [12,13,16]. Some
solutions take considerable computing time and do not always provide the best possible
solutions. However, successful application areas include modeling or mapping data and sys-
tems, pattern recognition, classification, optimization and time series prediction, a special
case of modeling.
Net work Size~Generalization
The optimal size of the MLF neural network can be roughly defined by the size of the
problem set, but significant controversy remains regarding the minimum number of layers
and processors per layer [17,18]. In general, the larger the network, the longer computational
time required for training. A practical solution to most problems can be found using MLF
networks with ideally one [12] or, generally, two "hidden layers" of processors; two hidden
layers were used in this study. The size of the network following training must be able to
generalize, that is, map appropriate input values to the correct output pattern result. The
number of weights should be kept to less than the number of training data samples to prohibit
the network from learning that data explicitly (assuming each weight has the potential to
store one piece of training data). The validity of this rule depends on the complexity of the
underlying information content in the data and does not allow for redundancy as a result of
repetition in the data set. Too few weights can provide insufficient freedom for the network
to produce a good model of the information implicit in the training data set or result in no
training at all. Generalization of a network can be a difficult goal to accomplish, and ex-
perimentation with alternate network architectures is one way to verify that a satisfactory
solution has been determined.
Transfer Functions
Within any single processor, the summation of the incoming connection activity is per-
formed by calculating the sum of the products of the respective weight and input activity
Xj : ~ i Wj i * Y i
( 1 )
where
j = the i ndex number for the pr ocessor in the l ayer under consi derat i on,
y, = the output level of the ith pr ocessor in the previ ous layer, and
wjl = the wei ght for the connect i on bet ween the ith and j t h processors.
The resul t of this wei ght ed summed process is the act i vat i on level, xj, whi ch is then operat ed
on by the t ransfer function, f i x ) , to pr oduce the new output for that processor, z~ = f ( x ~ ) . The
t ransfer funct i on is usual l y chosen to be nonl i near to assi st in the f or mat i on of a compl ex
represent at i ve space. As the out put s must be const rai ned in magni t ude and be di fferent i abl e
for the i mpl ement at i on of back- pr opagat i on t rai ni ng, t he most commonl y used t ransfer func-
tion t ypes are si gmoi dal or hyper bol i c functions. These l i mi t the out put s to bet ween 0 and
+ 1 for l ogi st i c functions, and - 1 and + 1 for hyperbol i c functions. The fol l owi ng l ogi st i c
t ransfer function was chosen for this st udy:
f(x) = (1 - e x)-, (2)
L e a r n i n g / T r a i n i n g
The MLF net work is t rai ned by back- pr opagat i on, whi ch is a t wo-pass supervi sed pr o-
cedure. Fi rst , successi ve i nput sets of the t rai ni ng dat a are operat ed on by the net work in a
feedforward manner to pr oduce cor r espondi ng out put dat a sets. The net work out put dur i ng
t rai ni ng is compar ed with target out put sets, known t ransformat i on resul t s bet ween i nput and
out put dat a sets. The initial wei ght s are usual l y preset to smal l r andom values. Errors bet ween
the actual and target out put dat a sets are cal cul at ed and accumul at ed for the whol e t rai ni ng
set. In the second pass, the i nt erconnect i ve wei ght s are syst emat i cal l y changed by appl yi ng
t rai ni ng rules that first reduce the output l ayer errors and then subsequent l ayer errors, movi ng
backwar d ( back- pr opagat ed) t hrough the net wor k to the input. An i t erat i ve pr ocedur e is
fol l owed to r educe the out put error until
9 the mean (output) squared error (MSE) is suffi ci ent l y low,
9 the t i me deri vat i ve of the MSE is suffi ci ent l y low, or
9 a sufficient percent age of the l earni ng and test set are correct l y cl assi fi ed.
where
MSE = 0. 5N Ec EjN (zj.,. - d j . , . ) :
MSE = the mean out put l ayer squared error,
c = the case bei ng anal yzed,
Zj,c = the actual out put val ue of t he j t h output l ayer pr ocessor for case c,
dzc = its desi red output, and
N = the total number of cases used to train or test the net work.
( 3 )
Thi s mi ni mi zat i on rul e gi ves a maxi mum est i mat e for the wei ght adj ust ment s necessary
to cancel the out put errors. General l y, smal l i ncrement al adj ust ment s proport i onal to a learn-
ing rate coeffi ci ent (usual l y < < 1.0) are made. Often ot her t echni ques are used to assi st wi t h
the convergence to near opt i mal sol ut i ons; one common met hod al so uses the second deri v-
ative of the training rate and the product of an exponential decay or moment um coefficient
( < 1.0) to contribute to the weight adjustments.
The correctness of the solution is evaluated and confirmed by testing with an independent
data set. Once a suitable solution is determined, the weights can then be fixed and new data
processed in a feedforward manner so the network output provides the appropriate answers.
The information stored by the network in its internal representational space during training
is clearly related to the weight values. However, the complexity of the weight values and
network structure mask the underlying logic rules used to solve the problem. Onl y with
extensive testing can confidence be gained in this "bl ack box" model i ng approach. It is usual
practice to use t wo independent sets of data: one for training the network and the second
for testing the resultant solution determined.
Data Collection
Pitting and crevice experiments were performed on AI SI Type 304 stainless steel in a
deaerated, 1000-mg 9 L ~ chloride electrolyte. Electrodes were prepared from solution-
annealed Type 304 stainless steel disks with a 1.5-cm 2 surface area. The electrodes were
mount ed flush in epoxy. Electrochemical data were gathered using a multispecimen cell and
an eight-channel potentiostat with data collected simultaneously on all eight channels with
a comput er system. The counter-electrode was a large platinum foil. The cell was placed
inside a Faraday cage to minimize external noise, although adventitious noise was super-
imposed on the data during testing of the network.
To initiate localized corrosion, the potential of each electrode was slowly ramped from
- 3 0 0 to +700 mV (versus a saturated calomel reference electrode) at 0.1 mV/ s , and the
current was recorded at one data point per second. The level of the baseline current was
typically 0.1 txA at the onset of localized corrosion. The full-scale current limit was set at
30 ~A at which point the working electrode was isolated from the potentiostat t o prevent
excessive corrosion damage.
Because of the mount i ng geomet ry of the electrodes, localized corrosion could occur via
two mechanisms: pit formation on the face of the electrode or crevice formation at the edge
of the electrode between the stainless steel and the epoxy mount. The potential ramp and
electrolyte conditions were such that there was an equal likelihood of pitting corrosion or
crevice corrosion.
After each experiment, the electrodes were examined by optical mi croscopy to identify
the t ype o f corrosion that had occurred. Files containing up to I 0 000 data points were
examined and then shortened so that they contained the pit or crevice corrosion initiation
data, plus some additional leading data points to establish the baseline level of current. When
training the network, the start of the corrosion event was arbitrarily assigned as the first of
at least three consecutive data points above the mean baseline plus two standard deviations
calculated from local baseline noise. Fifty training files were produced, 25 pitting and 25
crevice corrosion data files. An additional 39 files were prepared for testing, 21 pitting and
18 crevice corrosion data files. Typical current / t i me data files showing the onset of corrosion
can be seen graphically in Fig. 2.
The Artificial Neural Network
The network initially had two outputs for classifying corrosion events, that is, pits or
crevices. Using this network, the number of processors in the hidden layers was optimized
' . D
rr
u
t~ . . ' ' 2
~ g J - - -
Z
r
i
0 4 8 12 16
Ti me i n Se c onds
pi t s
cr evi ces . . . .
FIG. 2--Typical current/time spectra of the initiation of pitting and crevice corrosion.
wi t h the first hi dden l ayer requi ri ng seven processors and the second hi dden l ayer requi ri ng
five. Af t er this pr el i mi nar y study, a t hi rd out put was added in the t rai ni ng phase to rei nforce
the basel i ne- dat a- onl y si t uat i on before corrosi on was i ni t i at ed to avoi d fal se det ect i on of
corrosi on events. A sl i di ng wi ndow el even dat a poi nt s wi de (Fig. 3) was used to i nput the
cur r ent / t i me dat a (that is, a net work i nput of el even consecut i ve dat a poi nt s). Duri ng t rai ni ng
and testing, the wi ndow was scanned al ong the dat a poi nt s for ei ght or ten shifts to si mul at e
dat a i nput from a corrosi on monitor, each shift pr oduci ng a mat hemat i cal l y i ndependent dat a
set of el even points. Therefore, the t ot al number of i ndependent dat a sets was the number
of dat a files t i mes the dat a sets per file, or a mi ni mum of 400 t rai ni ng dat a sets and 312
testing sets. The t rai ni ng pr ocess was desi gned to rei nforce the net work out put cl assi fi cat i on
aft er t he present at i on of the i nput dat a set, such that
9 i f t he i nput val ue in t he mi ddl e of the sl i di ng wi ndow i ncreased consi st ent l y above the
mean basel i ne pl us t wo st andard devi at i ons for at l east three consecut i ve shifts of the
BARTON E'F AL. ON ARTIFICIAL NEURAL NETWORK 163
a) Detection t l I - " "
Level =0. 1 l / 9 9 I 9 9
9 . . . . . ' - . . . . . . . I" . . . . . . . . . . . . . . . . . . . . Baseline Mean
2 shifts f ur t her on:
b) Detecti~ i . . . . . . ' I 9
Level = 0.5[ ~ 9 9 "
. . . . . . . . . . . . . . . . . . . . . . . I ] [ 9 9 9 ~
Mean
' " 9 1 7 6 1 4 9 . . . . 1 " 1 . . . . . . . ..i . . . . . . 1 . 7 . . - . - . . 7 7 . 2 a s e l i n e M e a n
d) LDeetelc ti Oo7 [ I I 9 ~- 9 9 9
FIG. 3--Schematic operation of the eleven-poim sliding window.
Baseline Mean
input window along the data points, then the output value should increase from 0.1 to
0.5 for the correct corrosion mechani sm (either pitting or crevice corrosion) and
9 Each additional shift of the sliding window, which was above the threshold level (mean
plus two standard deviations), should provide a further increase in the correct output
value by 0.1 to a maxi mum of 0.90.
Figure 3 illustrates the sliding window process, and Table 1 shows how the pitting and
crevice corrosion output values develop after training as the sliding window is shifted over
a typical pitting corrosion data file. I f the data set did not exhibit evidence of either type of
TABLE l--Output levels during operation of the sliding window.
Sliding Window Pitting Corrosion Crevice Corrosion
Shift Number Detection Level Detection Level Baseline Detection Level
1 0.10 0.10 0.90
2 0.10 0.10 0.90
3 0.12 0.08 0.88
4 0.50 0.15 0.45
5 0.62 0.10 0.31
6 0.71 0.13 0.23
7 0.73 0.07 0.24
8 0.81 0.10 0.18
9 0.85 0.09 0.13
10 0.89 0.11 0.10
corrosion initiation, then the corrosion type outputs were trained to give a detection level of
0.1 and the output for the baseline presence trained to 0.90.
Each of the 50 training files was processed through the network multiple times during the
training period with each full set of training data considered as one cycle. The net error was
monitored during the training cycles, and, when the rate of change of the error value was
sufficiently low, the test data files were run through the network (typically after 15 000 and
30 000 training cycles) to confirm a valid solution.
Resul t s
Initially, only a two-output network was used with outputs for indicating pitting corrosion
and crevice corrosion, but no output to reinforce the presence of baseline data. The criteria
for acceptable identification were three consecutive output values above 0.45 of the correct
corrosion process and increasing confidence in the output values such that the sum of the
three consecutive values was above 1.65. These criteria were arbitrary but offered a relatively
stringent measure of acceptable classification. After 15 000 cycles of the training data, using
eight shifts of the sliding window, the network was able to identify successfully 100% of
the pitting corrosion training files and 76% of the crevice corrosion training files (Table 2).
When the test files were run through the network, 95% of the pitting corrosion files and
TABLE 2--Percentage of accurate classification by the neural network.
2 Output, a 3 Output, b 3 Output, b
15 000 Cycles, 30 000 Cycles, 30 000 Cycles,
8 Shifts, % 8 Shifts, % 10 Shifts, %
Training: Total 88 96 96
Pitting 100 96 100
Crevicing 76 96 92
Testing: Total 85 90 95
Pitting 95 95 100
Crevicing 72 83 90
Baseline false detections <5 0 0
a Two outputs: pitting, crevicing.
b Three outputs: pitting, crevicing, baseline.
72% of the crevi ce corrosi on files, were identified. There were 5% fal se det ect i ons in whi ch
t he net wor k recorded a crevi ce corrosi on i ni t i at i on in whi ch t here was onl y basel i ne data.
A t hi rd out put to the net work to di st i ngui sh sect i ons of the dat a files that cont ai ned onl y
basel i ne l evel current was added to mi ni mi ze t he occurrence of fal se det ect i ons. By t rai ni ng
this new net wor k to 30 000 cycl es wi t h t he t hi rd output, the correct det ect i ons i ncreased to
96% for bot h the pi t t i ng and crevi ce corrosi on t rai ni ng files, wi t h no fal se det ect i ons. The
t hree-out put net work had sl i ght l y mor e di ffi cul t y i dent i fyi ng the t est files correct l y wi t h 95%
of t he pi t t i ng corrosi on t est files and 83% of the crevi ce corrosi on t est files correct l y i den-
tified. There were, however, no fal se det ect i ons in the basel i ne data.
By i ncreasi ng t he number of shifts of the sl i di ng wi ndow f r om ei ght to t en in t rai ni ng of
anot her t hree-out put net work (for 14 500 cycl es), t he percent age of correct det ect i ons in-
creased to 100% for pi t t i ng corrosi on t rai ni ng files and 92% for the crevi ce corrosi on t rai ni ng
files. Resul t s for the test files al so i mpr oved with 100% of the pi t t i ng corrosi on t est files and
90% of t he crevi ce corrosi on test files correct l y i dent i fi ed and no fal se det ect i ons.
As t he ori gi nal dat a files wer e col l ect ed wi t h a l ow level of advent i t i ous noise, furt her
exper i ment s were carri ed out to t est the net wor k' s noi se t ol erance by art i fi ci al l y superi m-
posi ng advent i t i ous noi se on the signal. The levels of noi se in the ori gi nal dat a were anal yzed,
and files cont ai ni ng an addi t i onal 2.0, 4.0, and 5.0 st andard devi at i ons of basel i ne noi se were
produced. The results are l i st ed in Tabl e 3 for a net work t rai ned wi t hi n the ori gi nal dat a files
but t est ed wi t h addi t i onal advent i t i ous noi se added. Two st andard devi at i ons of noi se r educed
the correct i dent i fi cat i on rates onl y sl i ght l y to 96% of t he pi t t i ng corrosi on t rai ni ng files and
90% of t he crevi ce corrosi on t rai ni ng files, wi t h no fal se det ect i ons. Of the test data, 100%
of t he pi t t i ng corrosi on files and 88% of the crevi ce corrosi on files were correct l y identified.
The addi t i on of 4. 0 and 5.0 st andard devi at i ons of noi se r educed t he correct i dent i fi cat i on
of crevi ce corrosi on onset but di d not great l y affect the accuracy of the net work for pi t t i ng
corrosi on identification. Exampl es of files wi t h advent i t i ous noi se super i mposed on the ex-
peri ment al dat a are present ed in Fi g. 4.
Di s c us s i on
The results i ndi cat e t he neural net work coul d successful l y i dent i fy the onset and t ype of
l ocal i zed corrosi on usi ng a narrow wi ndow and few dat a poi nt s. Accept abl e i dent i fi cat i on
levels of >95% are encour agi ng wi t hi n the stringent defi ni t i on of success, that is, gi ven t hat
a posi t i ve cl assi fi cat i on is expect ed at or soon aft er the fourth shi ft and requi res t hree con-
secut i ve val ues of >0. 45 to be obt ai ned within the four or six shifts used. Vari abi l i t y is
observed in the number of shifts requi red to first i dent i fy the onset of pi t t i ng corrosi on and
mor e so for crevi ce corrosi on. The scat t er appears to cor r espond to the arbi t rary defi ni t i on
of i ni t i at i on used wi t h the t rai ni ng and test data. The l ower per cent age of correct classifi-
TABLE 3--Percentage of accurate classification by the neural network with noise-added spectra.
No Noise, %" 2~ Noise, %~ 4tr Noise, %~ 5cr Noise, %~
Training: Pitting 100 96 88 92
Crevicing 96 90 64 36
Testing: Pitting 100 100 100 100
Crevicing 90 88 61 55
Baseline false detections 0 0 0 5
Q Refers to noise added to spectra.
o ' 3
~
.- = / ,
c ' - I
L)
t ~
C' 4
i
0 4 8 12 16
Ti me in Seconds
pits
crevices . . . .
FIG. 4--Current~time spectra with adventitious noise added.
cations found for the eight-shift procedure is believed to result from this constraint because
three consecutive correct values must be established in only five shifts.
The onset of pitting corrosion was identified under all test conditions with considerable
certainty despite the overlap in ramp rate of some crevice and pit data. Detection or classi-
fication errors were usually associated with crevice corrosion measurements, and this was
not substantially improved by the addition of a third output to reinforce the baseline data,
although false detections were eliminated by the presence of the third output during training.
As the adventitious noise was increased to five standard deviations above the baseline level,
the output values for crevice corrosion were subject to greater variability and errors arose
from the failure to measure three consecutive values above 0.45 in seven window shifts.
Only a small percentage of the test results indicated no increase in crevice output values as
the data were shifted through the window. The number of shifts required to classify both
pitting and crevice corrosion systematically increased with increasing adventitious noise.
Refinement of the classification criteria and an increase in the number of shifts of data
through the network are expected to assist in increasing noise tolerance, although it is not
possible to quantitatively predict the level of improvement. Preliminary results for networks
that have been trained with adventitious noise have not revealed substantial improvements
in the noise tolerance. Other networks may offer better discrimination for very noisy data
sets (for example, adaptive resonance theory network [19]) or more efficient transformation
mapping processes (for example, Kohonen networks [20] or recurrent networks [16]). No
attempt was made to evaluate the efficiency of our network architecture against other
possibilities.
Although it may be cited as a strength that the MLF neural network requires no author-
imposed classification model, the inability to identify the criteria used for classification leads
to lengthy development and training times to optimize the technique. It is speculated that
the network classifies pitting and crevice corrosion primarily by the variation in current ramp
rate above the baseline value. A larger window size should provide greater confidence in
classifying crevice corrosion because the value of the current over time progressively rises
above the baseline. It is impractical to increase the input data set substantially as the number
of weights, and therefore the complexity of the network, rises rapidly.
Although fast Fourier transform (FFT) and maximum entropy techniques are normally
valid as steady-state operations, they can act like this neural network as a window analysis
on a snapshot of real-time data. For comparison, the results of FFT and noise resistance (rms
V/ 1) techniques using pitting and crevice test data with the original level of baseline noise
are presented in Fig. 5. The FFF analysis was based on a 16-point window; the resistance
noise method used an 11-point running mean. Figure 5 shows that, although the onset of
pitting corrosion can be recognized by both techniques, only FFF can easily distinguish
crevice corrosion under these condi t i ons. More work is required to provide an adequate
comparison between the performance of these networks simply trained to operate in the time
domain, and a neural network that uses maximum entropy methods or FF1 r techniques to
preprocess the data before interpretation.
The next step in the development of the neural network system is to make alterations to
allow continuous signal analysis for on-line monitoring. This development would allow field
study of localized corrosion. Additional developments will include producing a hybrid system
incorporating an expert system to allow rule-based judgments from neural network outputs.
This approach will allow other more logical criteria to be added to classification analysis
including prepitting or repassivation behavior. Multiple neural networks could also be linked,
in which each network is trained for an individual classification, and the combined system
produces multiple output for decision making.
Although it has been demonstrated in this work that neural networks are successful clas-
sifiers of electrochemical noise spectra, there are other applications in the area of corrosion
and electrochemical noise where neural networks might be valuable. Smets and Bogaerts
used a neural network to forecast chloride-induced stress corrosion cracking based on tem-
perature, chloride, and oxygen concentrations [21]. Rosen and Silverman successfully used
a neural network to link potentiodynamic polarization scans with prediction of pitting, crev-
ice, and general corrosion probabilities [22], although Silverman generally used experimental
values as inputs rather than spectral data [23,24]. Ben-Haim and MacDonald did similar
predictive work by modeling chemical characteristics of salt brines using neural networks
[25]. Other areas that show potential include modeling AC impedance spectra and classifi-
cation of multivariable solution conditions with the characteristics of corrosion initiation.
2 0 0 0 0
1 5 0 0 0 ~
C
D \
i 0 0 0 0 ~
"~ 5 0 0 0 ~
< " ._.
0
0 1 2
Pi t t i ng
Cr e v i c i ng . . . . . . . .
Bas e l i ne
Fas t Fo ur i e r Tr a n s f o r m
3 4
n
5 6 7
Fr e q u e n c y Ha r mo n i c
>
N o i s e Re s i s t a n c e
o
E
"6
>
2800
1400
\
\
4 6 8
n
! 0
Wi n d o w s hi f t s
Pi t t i ng
Cr e v i c i n g . . . . . . . .
FI G. 5--F ast Fourier transform and resistance noise analysis of data files.
Summary
A multilayer feedfoward neural network has been used to identify the onset of localized
corrosion by the analysis of electrochemical noise data. The advantage of using a neural
network for this identification is that the network appears to be able to generalize and choose
its own optimal criteria for classification. The network was able to detect and classify cor-
rectly 96% of the data within seven to ten data points (recorded at one sample per second).
It is concluded that neural networks in conjunction with electrochemical noise could offer a
robust, nondestructive monitoring technique for the detection of localized corrosion.
Acknowl edgment
This research was funded by the New Zealand Foundation for Research, Science, and
Technology under Contract CO8216.
References
[1] Gabrielli, C. and Keddam, M., Corrosion, Vol. 48, 1992, p. 794.
[2] Rothwell, A. N. and Eden, D. A., Corrosion~92, No. 223, NACE, Houston, TX, 1992.
[3] Gabrielli, C., Huet, E, Keddam, M., and Oltra, R., in Advances in Localised Corrosion, NACE 9,
H. Isaacs, et al, Eds., NACE, Houston, TX, 1990, p. 93.
[4] Umchurtu, J. C. and Dawson, J. L., Corrosion, Vol. 43, 1987, p. 19.
[51 Bertocci, U. and Yang-Xiang, Y., Journal of the Electrochemical Society, Vol. 131, 1984, p. 1011.
[6] Shibata, T. and Takeyama, T., Corrosion, Vol. 33, 1977, p. 243.
[7] Baroux, B., Corrosion Science, Vol. 28, 1988, p, 969.
132, 1985, p. 1796.
[9] Williams, D. E., Westcon, C., and Fleischmann, M., Journal of the Electrochemical Society, Vol.
132, 1985, p. 1804.
[10] Stewart, J., "Pit Initiation on Austenitic Stainless Steels," Ph.D. thesis, University of Southampton,
UK, 1990.
[11] Barton, T. E, Tuck, D. L., and Wells, D. B., in Proceedings of the 93 ANNES Conference, IEEE
Computer Society Press, Los Alamitos, CA, 1993, p. 325.
[12] Lippmann, R., IEEE ASSP Magazine, Vol. 4, 1987, p. 4.
[13] Rumelhart, D. E., McClelland, J. L., et al., Parallel Distributed Processing, Vols. I and II, MIT
Press, Cambridge, MA, 1986.
[14] McClelland, J. L. and Rumelhart, D. E., Explorations in Parallel Distributed Processing, MIT Press,
Cambridge, MA, 1988.
[15] Hinton, G. E., Scientific American, Vol. 267, No. 3, 1992, p. 105.
[16] Bressloff, P. C. and Weir, D. J., GECJournal of Research, Vol. 8, No. 3, 1991, p. 151.
[17] Albertson, E C. and Sontag, E. D., Neural Networks, Vol. 6, 1993, p. 975.
[18] Bulsari, A., Neural Networks, Vol. 6, 1993, p. 991.
[19] Carpenter, G., Grossberg, S., and Reynolds, J., Neural Networks, Vol. 4, 1991, p. 565.
[20] Kohonen, T., Self-Organization & Associative Memory, Springer-Verlag, Berlin, 1987.
[21] Smets, H. M. and Bogaerts, W. F., Materials Performance, Vol. 31, No. 9, 1992, p. 64.
[22] Rosen, E. M. and Silverman,D. C., Corrosion, Vol. 48, 1992, p. 734.
[23] Silverman, D. C., Corrosion, Vol. 50, 1994, p. 411.
[24] Silverman, D. C., in Application of Accelerated Corrosion Tests to Service Life Prediction of Ma-
terials, ASTM STP 1194, G. Cragnolino and N. Sridhar, Eds., American Society for Testing and
Materials, West Conshohocken, PA, 1994, pp. 43-64.
[25] Ben-Haim, M. and MacDonald, D. D., Corrosion Science, Vol. 36, 1994, p. 385.
Industrial Applications
Bar r y C. Syrei~,t ) and Wi l l i am M. Cox 2
A Review of EPRI Projects Since 1984 that
Used Electrochemical Noise Measurement
Instrumentation
RE F E RE NCE : Syrett, B. C. and Cox, W. M., "A Review of EPRI Projects Since 1984 t hat
Used Electrochemical Noise Instrumentation," Electrochemical Noise Measurement f or Cor-
rosion Applications, STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David
L. Reichert, and John L. Dawson, Eds., American Society for Testing and Materials, 1996, pp.
173-185.
ABS TRACT: This review paper documents the development of a modem approach to online
corrosion evaluation: the origins of the approach, configuring multiple techniques to maximize
data retrieval, and taking the instrumentation out of the laboratory and into the field. Several
Electric Power Research Institute (EPRI) projects conducted over the past decade have used
this approach. This paper describes how with the use of modem corrosion surveillance instru-
mentation the objectives of each of these EPRI projects were achieved and an appropriate
corrosion management strategy was developed. The final section includes a discussion of the
future of corrosion management systems, and their relation to, and dependence on, electro-
chemical noise (EN) instrumentation.
KEYWORI)S: technology demonstrations, electrochemical noise, real time, Electric Power
Research Institute (EPRI), online, surveillance, process control, instrumentation
In the late 1970s, it was recognized that considerable fuel cost savings were possible if
the outlet gas temperature on large power generation boilers could be reduced. It was cal-
culated that a small (approximately 17~ or 31~ reduction in outlet flue gas temperature
would yield annual savings of approximately $3 million in a single 2000-MW power station
[1]. However, a reduced outlet gas temperature increases the risk of condensation of aggres-
sive acids on the walls of the outlet duct and stack, and the onset of so called dewpoint
corrosion. An investigation was launched in 1978 at the University of Manchester Institute
of Science and Technology (UMIST), along with two parallel studies, to examine the mech-
anism of acid dewpoint corrosion in combustion systems. In one study, the electrochemical
impedance spectroscopy technique of corrosion rate evaluation was used [2]. In one of the
other studies, Hladky, working on electrochemical noise evaluations, established that a non-
perturbative approach to the examination of electrochemical response from corroding systems
had considerable advantages over the more widely accepted linear polarization techniques
[3]. The onset and propagation of localized corrosion, such as pitting, were clearly identified
using the electrochemical noise approach.
Subsequent work for the nuclear industry investigated localized corrosion in condensing
nitric acid systems. A multitechnique approach was used in which linear polarization, elec-
Manager, Corrosion Science and Technology, Strategic Research and Development, Electric Power
Research Institute, Palo Alto, CA 94303.
2 Director, Corrosion Management Ltd., Hyde, Cheshire, UK, SK14 5LT.
173
www.astm.org
trical resistance, electrochemical impedance, zero resistance ammetry, and electrochemical
noise techniques were used simultaneously to maximize data retrieval. 3 The advantages of
combi ni ng several methods were recognized, and sensor configurations that had been de-
veloped for impedance studies in condensing conditions were adapted to permit measure-
ments, using several electrochemical techniques simultaneously, under essentially identical
environmental conditions. These compact multielement sensors allowed electrochemical
measurements to be conduct ed conveniently in the laboratory and operating plants.
In late 1979, impedance equipment was transported to the Drax Power Station in York-
shire, England, and tests were conducted in the flue gas system of a 660- MW coal-fired
power generation boiler. This and similar work undertaken in the outlet duct of oil-fired
boilers at the Esso Oil Terminal at Trafford Park, Manchester, England, marked the entry of
modem corrosion instrumentation into online corrosion monitoring and opened the way for
a new approach to corrosion control.
Commenci ng in 1981, electrochemical noise instrumentation was used on site in the sec-
ond phase of the dewpoint investigation. In this investigation, the instrumentation demon-
strated that few materials could withstand operation at temperatures just below the dewpoint
temperature. Aggl omerat i ons of ash, bound together by condensed sulfuric acid, could form
causing fouling and bl ockage of the air heaters. Heat recovery could be optimized by mon-
itoring the corrosion rate, establishing an acceptable maxi mum corrosion rate, and reducing
the exhaust gas temperature as much as possible without exceeding the corrosion rate
maximum.
Electrochemical Techniques
Electrochemical Impedance Spectroscopy
This technique is an i mprovement over the conventional linear polarization method of
corrosion rate determination. A small alternating signal, typically of 20 or 40 mV peak to
peak, is applied to the corrosion cell. The frequency of the signal is varied, usually between
10 kHz and 100 mHz for metallic systems, and impedance measurements are plotted in a
Nyqui st or Bode format. From these data, a value of the charge transfer resistance can be
estimated, and a corrosion rate can be deduced via the Stern Geary relationship and Faraday' s
law [4,5].
The technique is especially useful to evaluate changes in solution resistance (or conduc-
tivity), specimen charge transfer resistance, and diffusion behavior. It works well in activa-
tion-controlled corrosion systems but is less effective where systems are entirely diffusion
controlled. When used in combination with the electrochemical noise analysis, it can verify
general corrosion rate estimates obtained from the noise analysis.
Electrochemical Noise Measurement
The electrochemical noise (EN) analysis techniques are based on the evaluation of spon-
taneous current and voltage transients and low level signals. These fluctuations and transients
can be used to characterize the electrochemical condition at a corroding interface.
In its simplest application, the data may be analyzed using an approach analogous to
Ohm' s law ( V/ I = R). For linear polarization, Av/ Ai = Rp would be used (where Av is the
3 D. A. Eden, "Pitting of Stainless Steels in Iodide Solution," CAPC1S Internal Report (private com-
mercial communication), 1981.
SYRETT AND COX ON ELECTROCHEMICAL NOISE INSTRUMENTATION 175
i ncr ement al c ha nge in vol t age, Ai is t he as s oci at ed i ncr ement al c ha nge in cur r ent , and Rp i s
t he cons equent pol ar i zat i on r esi st ance) , and f or noi se gener at ed by uni f or m cor r os i on, t he
st andar d devi at i on o f t he si gnal s i s ~rv/cr i = R, ( wher e tro is t he ma gni t ude o f t he vol t age
noi se si gnal , tr, is t he ma gni t ude o f t he cur r ent noi se si gnal , and R, i s t he cons equent " n o i s e
r e s i s t a nc e " val ue, whi ch i s anal ogous t o t he pol ar i zat i on r esi st ance) . Be f or e t he UMI S T
pat ent s wer e i ssued [6,7], nume r ous st udi es ma de r ef er ence t o el ect r ochemi cal noi se, but t he
dat a wer e not conver t i bl e i nt o cor r os i on r at es unt i l i t wa s r ecogni zed t hat (i n es s ence) it wa s
ne c e s s a r y t o c ombi ne t he pot ent i al noi se and cur r ent noi se c o mp o n e n t t o obt ai n t he r at i o
val ue or " r e s i s t a nc e noi s e " ( al t hough in par t i cul ar c i r c ums t a nc e s ei t her c o mp o n e n t c a n be
a s s ume d t o be essent i al l y cons t ant be t we e n def i ned l i mi t s). I t i s t her ef or e ar guabl e t hat
el ect r ochemi cal noi se t heor y can be cons i der ed t o be t he gener al case, obt ai ned wi t hout
ext er nal pol ar i zat i on, wher eas convent i onal l i near pol ar i zat i on t heor y is a speci al case, whi ch
e na bl e d pol ar i zat i on t heor y t o b e f or mul at ed, and whi c h ha ppe ne d t o b e di s c ove r e d first.
Noi s e anal ysi s is es peci al l y usef ul f or t hr ee r easons:
1. Cur r ent and vol t age t r ansi ent s r esul t i ng f r om el ect r ochemi cal pr oces s es as s oci at ed wi t h
t he ons et o f cor r os i on act i vi t y ar e det ect abl e l ong be f or e any vi s i bl e d a ma g e i s evi dent
at a me t a l / e n v i r o n me n t i nt er f ace, a l l owi ng t he r i sk o f at t ack t o be i dent i fi ed, and en-
abl i ng t i mel y and ef f ect i ve r e me di a l act i on t o mi ni mi z e cor r os i on d a ma g e t o t he pl ant .
2. The cur r ent and vol t age noi se t r ansi ent s can be eval uat ed t o char act er i ze and quant i f y
l ocal i zed cor r os i on be ha vi or (pi t t i ng cor r osi on, cr evi ce at t ack, st r ess cor r os i on cr acki ng,
cavi t at i on, and under - depos i t at t ack) .
3. El e c t r oc he mi c a l vol t age and cur r ent noi se si gnal s are obt ai ned i n r eal t i me.
The i mpor t ance o f r eal - t i me i nf or mat i on has been ove r l ooke d i n convent i onal me t hods o f
cor r os i on cont r ol , whi ch i nst ead e mpha s i z e d a ma g e l i mi t at i on. The avai l abi l i t y o f accur at e
and r epr esent at i ve r eal - t i me cor r os i on i nf or mat i on f aci l i t at es pr eci s e onl i ne pr oc e s s cont r ol ,
whi c h was di ffi cul t or i mpos s i bl e t o achi eve by i nf er r i ng cor r os i on st at us b y eval uat i on o f
cumul at i ve cor r os i on r at es; or moni t or i ng o f i ndi r ect pa r a me t e r s as t emper at ur e, pr essur e,
pH, or cor r os i on pot ent i al moni t or i ng; or even onl i ne c he mi c a l anal yses. I mp r o v e d cont r ol
is t he mos t cos t - ef f ect i ve a ppr oa c h b y whi c h t o r educe oper at i ng and ma i nt e na nc e cost s,
mi ni mi z e downt i me, i ncr eas e pr oduct i vi t y, i mp r o v e pr oduct qual i t y, and i ncr eas e safety.
EPRI Project Revi ew
I n 1984, t he El ect r i c Powe r Re s e a r c h I nst i t ut e ( EPRI ) b e c a me i nt er est ed in t he c o mb i n e d
el ect r ochemi cal i mpe da nc e and el ect r ochemi cal noi se i nst r ument at i on. Ini t i al l y, EPRI us ed
t he i ns t r ument at i on t o i dent i f y whe n and why condens at e cor r os i on t ook pl ace in fl ue ga s
des ul f ur i zat i on ( FGD) s ys t ems . I t s successf ul us e al l owed oper at i ng cost s t o be r educed b y
s peedi ng t he de ve l opme nt o f ef f ect i ve r emedi al st r at egi es and al l owi ng t hei r ef f ect i venes s t o
be ver i f i ed whi l e t he pl ant wa s onl i ne. Lat er, EPRI us ed s i mi l ar i ns t r ument at i on i n ot her
p o we r pl ant appl i cat i ons. The s e pr oj ect s ar e des cr i bed bel ow.
LaQue Center for Corrosion Technology/R. M. Schahfer Generating Station
Be f or e a f ul l - scal e pl ant trial, t he f easi bi l i t y o f onl i ne cor r os i on moni t or i ng in condens i ng
fl ue ga s condi t i ons wa s de mons t r a t e d at t he La Que Ce nt e r f or Cor r os i on Technol ogy, i n
Wr i ght s vi l l e Beach, Nor t h Car ol i na, usi ng a pi l ot - s cal e we t l i mes t one F GD s ys t e m t hat had
been bui l t f or mat er i al s t est i ng.
The instrumentation was commissioned in February 1985. The sensor, manufactured from
Type 316L stainless steel, was located immediately downstream of the absorber column. It
operated in a continuously wetted condition and was occasionally partially covered with
deposits, comprising ash (introduced deliberately to simulate plant slurries) and limestone
dust particles. Electrochemical noise transients typical of the onset of pitting corrosion were
observed, and the extent of corrosion was seen to depend on operating variables, such as
flue gas temperature.
After a three-month exposure, the sensor was removed for inspection by project staff who,
on the basis of electrochemical noise data, had been confidently predicting the onset of pitting
corrosion, but no pitting was evident! The sensor was disconnected from the rig and taken
to the laboratory for more detailed inspection. Examination on a stereo optical microscope
at 100 magnification revealed that pitting had, in fact, occurred. This was the first success
on the EPRI online monitoring program, and a second stage of work for plant investigation
was authorized [8,9].
The instrumentation was relocated on a dual alkali FGD unit at the R. M. Schahfer Gen-
erating Station, operated by the Northern Indiana Public Service Company (NIPSCO). Con-
siderable corrosion damage was being sustained by the outlet flue gas ducting on the FGD
system. The ducting was constructed from Type 317LM stainless steel, and substantial pitting
attack had been observed after nine months of operation. Station engineers wished to un-
derstand the underlying cause of attack and formulate effective remedial measures.
The location of the damage was unexpected. It was most marked just downstream of the
reheater, where the gas stream should have been dry. It was important to establish when
these duct surfaces became wetted with condensate, so a duct wall sensor was installed to
provide a continuous indication of the corrosion status. It was located immediately down-
stream of the reheater approximately 4 ft (1 m) above the duct floor (Fig. 1). It was soon
FIG. 1--External view of corrosion-monitoring probes located in duct at R. M. Schahfer Generating
Station.
confirmed that the exhaust flue gas, although reheated to the target outlet temperature, was
not dry during much of the operating time. An example of the traces provided by the in-
strumentation at this installation is shown in Fig. 2. The outlet duct, on this occasion, sus-
tained damage for almost a complete 8-h night shift, even t hough the outlet gas temperature
was considerably higher than should have been necessary to dry it [10]. Calculations revealed
that, i f the flue gas could be discharged in the unreheated state, corrosion rates were actually
much lower and cost savings approaching $8 million could be achieved over a ten-year
operating period by the use of lower cost construction materials and improved thermal
efficiency.
S c h o l z Ge n e r a t i n g C e n t e r
In October 1986, EPRI adopted the online monitoring concept to assist in the investigation
of corrosion phenomena in cyclic reheater systems for FGD plants. Using two inline, tube-
type heat exchangers, a cyclic reheat system extracts heat from hot flue gas before the gas
enters a wet sulfur dioxide (SO2) scrubber and returns the heat to the cooler clean gas after
the FGD system. This process increases gas buoyancy and prevents condensation. The service
environment of the first-stage heat exchanger (heat extractor) is harsh, and a materials in-
vestigation was in progress in a pilot cyclic reheat unit, installed at Gul f Power Company' s
Scholz Generating Center, to identify candidate alloys and coatings for this application.
Over the course of the trials, it has been reported that many alloys sustained "localized
corrosion. " This finding was unexpected on Alloy 276, which in other trials had exhibited
r
i g ~ D ~
r
l ~ _ !
i , r ~l v
_ I M _ u
I - - M - - ~ M
!
I~ % , i | ~11* t , # ~ . "
- ~ 1 - - t l l
_ u _ |
. . . . . . . . . . . . . . . ' . . ' : - " " . t . . . . . . . . . . . . . . . .
m . . q m . . I
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I
I
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I
FIG. 2 - - S u b s t a n t i a l i ncrease in corrosi on act i vi t y c aus e d by a decr eas e in t he reheat t empera-
t ure ri se f r o m 25 to 14~ i dent i f i ed by al l corrosi on moni t ors. ECN = el ect rochemi cal cur r ent noi se,
EPN = el ect rochemi cal pot ent i al noi se, ZRA = zero resi st ance ammet ry, and El M = el ect rochemi cal
i mpedance measurement .
sat i sfact ory performance. It was deci ded that a real -t i me i ndi cat i on of corrosi on act i vi t y
woul d be helpful, and t wo of the 1-in. (25. 4-mm) di amet er test heat exchanger t ubes were
repl aced by sensor assembl i es of si mi l ar di mensi ons. The t ubes were modi fi ed to enabl e t he
sensi ng el ement s to be reposi t i oned at di fferent l ocat i ons across the gas st ream (Fig. 3).
It was qui ckl y evi dent that the unexpect ed damage resul t ed from low gas-fl ow r egi mes
adj acent to the t ube sheets, whi ch al l owed ash deposi t s to accumul at e. The deposi t s i nsul at ed
the tube sheets, pr omot i ng sulfuric aci d condensat i on. The sulfuric aci d caused r api d general
corrosi on attack beneat h the deposi t . The at t ack was uni form in nature but was onl y sust ai ned
over a l i mi t ed ar ea [11]. The di fferences in corrosi on performance bet ween seam- wel ded and
unwel ded Al l oy 625 mat eri al were then eval uat ed [12].
The Hi gh Sul f ur Test Cent er
In a cont i nuat i on of t he R. M. Schahfer program, a series of compar at i ve trials commenced
in 1988 at the EPRI Hi gh Sul fur Test Cent er near Buffalo, New York. The pur pose of t hese
trials was to eval uat e candi dat e al l oy mat eri al s for cost -effect i ve retrofit in FGD out l et flue
gas duct i ng. A t wel ve- sensor compound exposur e assembl y was i nst al l ed i mmedi at el y down-
st ream of the mi st el i mi nat or in the outlet sect i on of the 4- MW pi l ot FGD syst em (Fi g. 4).
The scrubber was not fitted wi t h a gas-reheat i ng facility, so the sensors were t emper at ur e
cont rol l ed to al l ow cool i ng and heat i ng of the sensor el ement s. The t i me for t he onset of
at t ack on each of the exposed al l oys and t he degree to whi ch t hey repassi vat ed aft er a change
in the servi ce envi ronment were investigated. In a second phase of the work, smal l quant i t i es
of chemi cal s were added to the scrubber l i quor to i ncrease scrubbi ng efficiency or cont rol
scal i ng charact eri st i cs. Because car r yover of the scrubber l i quor into the outlet duct was
possi bl e, t he effects of the addi t i ves on t he rat e and mor phol ogy of at t ack were al so inves-
t i gat ed. These results were report ed in 1993 [13,14].
An i mport ant finding of the EPRI tests di scussed so far was that corrosi on damage oft en
occurs in operat i ng pl ant s because actual servi ce condi t i ons depar t si gni fi cant l y f r om desi gn-
Watar
J J
I rm'rf'rrm'rrrrrrm'rMl i I
/ / - - "
adi~.m~)
d P i l o t S c a l e \
I C y c l i c R e h e a t
U n i t
I = H o, .I
, I I , ~
t k~. ~
FIG. 3--General layout of the corrosion-monitoring installation in the pilot-scale cyclic reheat unit
at Scholz Generating Center.
SYRETF AND COX ON ELECTROCHEMICAL NOISE INSTRUMENTATION 179
FIG. 4--Corrosion probes installed in the FRP duct in the 4-MW pilot scrubber at EPRI's High Sulfur
Test Center near Buffalo, New York.
operating conditions. Ducts can be operated satisfactorily with low-cost materials, such as
plain carbon steel, if adequate reheat is provided at all times and the outlet ductwork and
stack always operate hot and dry. Systems constructed from the lower-grade stainless steels
can operate satisfactorily if the system is operated wet, without reheat, provided they are
adequately drained. Ducts operated under alternating wet and dry conditions accumulate acid,
which, in combination with dissolved salts, is highly corrosive. Highly corrosion-resistant
alloys can be used to minimize unplanned down time, but the cost for this insurance is high.
Indianapolis Power and Light Company
Indianapolis Power and Light Company' s (IPL's) Petersburg Generating Station Unit 3
participated in a trial. The station uses fossil fuels, and the unit is fitted with a limestone
slurry FGD system. In 1988, there was concern that an organic lining on the chimney stack
had sustained damage. Budget provision had been made to reline it with a corrosion-resistant
nickel base alloy or titanium alloy. A monitoring investigation was funded by EPRI to
establish if the relining was necessary. Instrumentation from the cyclic reheater program at
Gulf Power in Florida was transferred to IPL.
Preliminary trials demonstrated that corrosion could be avoided provided the gas reheater
systems were online and mist eliminators operated satisfactorily. A permanent surveillance
system was installed in 1990. The system was comprised of six sensors (see Fig. 5 to review
sensor layout). An online control room display informed plant operations personnel of cor-
rosion risk in stack, thereby prompting remedial action. The monitoring system was the
subject of an EPRI "First Use" publication, which described how knowledge of the corrosion
activity allowed IPL to avoid relining the stacks and duct [15]. The resulting investment
saving was $3.2 million and savings in operating and maintenance costs of $0.5 million
would be achieved every five years.
Compressed Ai r Energy Storage
Continuous electrochemical monitoring was used in connection with an EPRI-sponsored
program in which materials were being considered for use in a recuperator to be fitted in a
FIG. 5--Schematic diagram of the Petersburg Unit 3 exhaust train showing location of corrosion-
monitoring points.
compressed energy storage system (CAES) at Al abama Electric Cooperative, Inc. A CAES
plant uses off-peak power to compress air into an underground reservoir. During peak de-
mand, the air is heated and released into an expansion turbine to produce electricity. Use of
a recuperator to preheat the compressed air with turbine exhaust heat can reduce operating
costs by 27%. However, the intermittent operation can put the recuperator at risk from
dewpoint corrosion. The program, which commenced in 1986, was managed by Encot ech
Inc. of Schenectady, New York, and the initial stages of work were conducted in a pilot-
scale recuperator at the Creare R&D Company in Hanover, New Hampshire.
Carbon steel was the onl y cost-effective material for the installation, but the normal tem-
perature excursions during operation allowed sulfuric acid condensation and corrosion. It
was decided, therefore, that instrumentation used on the pilot rig for three years would be
reconfigured to provide continuous surveillance on the full-scale recuperator. The Maclntire
CAES installation at Al abama Electric Cooperative, Inc. and its corrosion surveillance in-
strumentation were commi ssi oned in 1991 [16,17].
High-Temperature Monitoring
Field trials of an online high-temperature monitoring system commenced at Rougel ey
Power Station in England in 1986 [18]. The first such installation in the United States was
on behalf of Westinghouse in 1990 at a Waste-to-Energy plant in Panama City, Florida [19].
In 1992, EPRI financed a long-term, high-temperature corrosion trial on a 660- MW boiler
at the Drax Power Station operated by National Power in Yorkshire, England.
The Drax project was an investigator of the comparative corrosion performance of super-
heater and rebeater tube materials. An air-cooled coupon exposure lance was adapted to
incorporate electrochemical sensors for t wo candidate materials, and a twin-channel moni-
toring system was used to interrogate the samples. The results were evaluated along with
data obtained from the mass-loss coupon tests [20,21]. An interesting difference in corrosion
behavior was exhibited by the t wo candidate materials after a high-temperature excursion.
The corrosion rate of Type 316 stainless steel increased immediately after the excursion,
whereas on the Type 310 material, the rate decreased (Fig. 6). This information was not
evident from the conventional methods of cumulative metal loss assessment. Electrochemical
data also revealed that the predominant corrosion mechanism was sulfidation/oxidafion dam-
age and not the molten salt attack predicted. Inspection of the corrosion product films at the
completion of the trial confirmed this result.
The most recent EPRI monitoring feasibility study was conduct ed in collaboration with
PowerGen at the Ratcliffe Technol ogy Centre and Cot t am Power Station. Work in other
fields had indicated that it was possible to detect the electrochemical transients associated
with the onset and propagation of stress corrosion cracking (SCC). Slow crack growth is a
significant concern in certain steam turbine designs. The ability to detect the onset of crack-
ing in real time potentially offers considerable i mprovement in service life prediction and
safety.
The EPRI / Power Gen program had two primary goals: to characterize the onset and prop-
agation of SCC and to transmit the signals across a brushless contact interface as woul d be
necessary i f the data were to be obtained from a power turbine rotor while in service.
The first part of the program was conduct ed at the Ratcliffe Technol ogy Centre laboratories
of PowerGen. Characteristic SCC transients were obtained from a compact tension specimen
made from a rotor steel and exposed to caustic soda solution and then similar transients were
monitored in condensing steam. The electrochemical noise transients were then transmitted
across a brushless contact transducer without degradation of the signal. Finally, the instru-
mentation was moved to Cottam Power Station, and high-speed SCC transients were mon-
itored on a 550- MW power generation turbine without loss of signal integrity [22].
The Future
Each of the EPRI projects described above was successful. At each stage, greater confi-
dence has been developed in the technology, and the power industry is able to take advantage
of the cost savings available [23]. Practical experience is assisting the development of noise
theory [24,25], which has assisted in the understanding of empirical data obtained during
the early EPRI trials.
The feature that distinguishes electrochemical noise instrumentation from earlier corrosion
monitoring t echnol ogy is its capability to provide an online real-time indication of conditions
at a corrodi ng surface. Traditional corrosion monitoring methods do not offer "cont rol , " but
instead offer "accountability. " The resulting damage limitation strategy is consequently ex-
pensive. Real-time feedback allows control of corrosion to be redefined in terms of detection,
prediction, and prevention. For process control purposes, it is more useful t o detect the
threshold onset of corrosion than to quantify the rate and morphol ogy of attack. Plant inci-
dents can then be correlated with the occurrence of corrosion. The approach allows imprecise
data to be processed to produce an effective and robust corrosion control strategy, enabling
0. 4
0. 35
0.3-
, ~ o. 2s-
15
-~ o. 2-
: t
> .
= 0.15-
o
u 0.1
0.05
0
23/ I I
Alloy .316
, 2 2 o , 0 , ; ' 0 3 2 2 ) ' 0 , , , ; o , 5 , ) ' o ,
Oate
I I I I
I I I
T ~ t r o k e ' e ~ I ITch | l mpl r ol v r l ( ~ u r ~ Tl e-eem~rl ~ 2
t s/ os
0. 018
0. 016-
O.014-
E
E
' - - ' 0. 012-
o
~ 0.01
o
2 0. 008
!
~ 0.006-
~ 0. 0O4-
0. 002-
0
25/11
Alloy 310
12/01 0 ~ o 5 2 2 ~ 0 , , , ~ 0 6 5 , ; o 7
Oote
I I I 1
I I I
Tm~perdvre Scan I ~ Tenw4~kare Cxcurm Temeerakare S~n 2
FIG. 6--Cumulative metal loss profiles of Alloys 316 and 310.
t s/ os
SYRETI" AND COX ON ELECTROCHEMICAL NOISE INSTRUMENTATION 183
prompt and effective remedial measures to be initiated before measurable damage has been
sustained.
Open Systems
It is appropriate to consider the developing architecture of noise-based corrosion surveil-
lance instrumentation. The main components of a plant control and information display
system are shown in Fig. 7 [26]. The system consists of:
9 An information-gathering and plant control front-end that is distributed and connected
together using local area network (LAN) technology. The operator interfaces consist of
video display unit (VDU) screens with an interactive pointing device (mouse, tracker
ball, and touch screen), connected to the input/output ( I / 0) subsystems via LAN tech-
FIG. 7--Process plant data-gathering and information technology installation.
nology. This system forms the primary instrumentation layer and could be a proprietary
distributed control system (DCS).
9 The DCS system. This system can be supported by engineering configuration worksta-
tions, and, on may plants, a process data-archiving comput er is also provided. Such
facilities provide l ong-t erm storage of all measured plant variables.
9 Networked personal computers. These provide plant-based engineers and managers with
productivity tools, such as word processors, spreadsheets, databases, and electronic mail.
9 Remot e systems. These are used by head office personnel to interrogate plant systems,
company-wi de efficiency engineers, or senior company management who require access
to the day-t o-day status of operating systems to determine optimal company strategies.
New systems must be smoothly integrated with the existing infrastructure. "Open syst em"
control and instrumentation (C&I) architecture promotes system integration, and easy use
speeds introduction of new t echnol ogy solutions. System consistency is of particular impor-
tance, and compliance with the emerging system standards in these areas helps to avoid
premature obsolescence of the monitoring system.
For anticipated benefits to be realized, a corrosion management system must impact op-
erating and maintenance practice. I f this is not done, instrumentation and associated main-
tenance and spares support increase the operating cost of the plant. This process is understood
in the vibration-monitoring field. Here, the installation of a monitoring system is normally
preceded by a structured evaluation and audit program that defines potential cost savings
and compares t hem with the actual costs of the proposed condition-monitoring installation.
This procedure is not well established in the corrosion field. Corrosion control has become
the province of control instrumentation groups and operations engineers. Modem electro-
chemical corrosion surveillance methods interfaced effectively to standard C&I systems are
able to achieve continuing real-time savings.
Conclusions
During the past decade, demonstrations of electrochemical noise technology were under-
taken, in which EPRI played a significant role, on behalf of the U.S. power generation
industry. During these investigations, the initial uncertainties were explored, evaluated, and
clarified. Each case history discussed in this paper gave considerable insight into corrosion
problems previously considered to be complicated or not amenable to control. Modem elec-
trochemical surveillance systems are robust and can be used to provide a retrospective cu-
mulative corrosion rate estimate, but the benefits of real-time feedback of corrosion status
are considerably more valuable. Earlier hardware and software that were not based on stan-
dard instrumentation architecture are being replaced by equipment that incorporates "open
syst em" modular principles, which will assist successful technology uptake.
Acknowledgments
The authors wish to thank colleagues in CML, EPRI, and the numerous client organiza-
tions for support, advice, and encouragement during the projects mentioned in this paper.
References
[1] Moore, W., Willet, M. J . , Mok, W. Y., and Cox, W. M., "An Approach to Reducing Stack Losses
in Coal Fired Power Boilers," paper presented at the EPRI Symposium on Improved Technology
for Fossil Plants, Washington, March 1993.
SYRE'I-[ AND COX ON ELECTROCHEMICAL NOISE INSTRUMENTATION 185
[2] Cox, W. M., M.Sc. dissertation, University of Manchester Institute of Science and Technology,
Manchester, UK, 1979.
[4] Hladky, K., Callow, L. M., and Dawson, J. L., British Corrosion Journal, Vol. 15, 1980, p. 20.
[5] Dawson, J. L. and John, D. G., Journal of the Electrochemical Society, Vol. 110, 1980, p. 37.
[6] Hladky, K., UK Patent GB0084404; USA Patent 4575678; Canadian Patent 1210066.
[7] Eden, D. A., Dawson, J. L., and John, D. G., UK Patent 5139627: European Patent 0302073.
[8] EPRI Report CS-5605, Multitechnique Corrosion Monitoring in Flue Gas Desulfurization Systems:
Phase I, Jan. 1988.
[9] Cox, W. M., Phull, B. S., Wrobel, B. A., and Syrett, B. C., "On-line Monitoring of Desulfurization
Scrubber Corrosion with Electrochemical Techniques," Materials Performance, Vol. 25, No. 11,
Nov. 1986.
[10] EPRI Report CS-5734, Multisystem Corrosion Monitoring in FGD Systems, Phase 2, April 1988.
[11] "'Multisystem Corrosion Monitoring in a Cyclic Reheat Test Facility: Phase 1," Report CS-5776,
Electric Power Research Institute, April 1988.
[12] "Multisystem Corrosion Monitoring in a Condensing Flue Gas Heat Exchanger: Phase 2," Report
GS-7540, Electric Power Research Institute, Oct. 1991.
[13] Mok, W. Y., Moore, D. C. A., Cox, W. M., and Syrett, B. C., "On-line Electrochemical Corrosion
Assessment of Materials for FGD Outlet Ducts," Proceedings of the NACE Air Pollution Seminar,
Orlando, FL, 1992.
[14] "On-Line Corrosion Monitoring at the High Sulfur Test Center," Report TR-102538, Electric Power
Research Institute, June 1993.
[15] EPRI "First Use" publication, Electric Power Research Institute, Nov. 1990.
[16] "Corrosion Testing of Materials in a Simulated CAES Plant Exhaust Atmosphere," Final Report
for EPRI Project RP2488-04, Jan. 1993.
[17] Cook, E. T., Lucas, H., Mok, W. Y., Elmore, D., and Mehta, B., "The Development of an On-Line
Electrochemical Corrosion Monitoring System," Paper 93-JPC-GT-4, Joint Power Conference, Kan-
sas City, KS, Oct. 1993.
[18] Farrell, D. M., Mok, W. Y., and Pinder, L. W., "On-line Monitoring of Furnace Wall Corrosion in
a 125 MW P.F. Boiler," paper presented at the 2rid International Symposium of High Temperature
Corrosion of Advanced Materials and Coatings, Les Embiez, France, May 1989.
[19] Whitlow, G. A., Mok, W. Y., Gallagher, P., Cox, W. M., Elliott, P., and Lee, S. Y., "On-Line
Materials Surveillance for Improved Reliability in Power Generation Systems," NACE Corrosion/
91, Cincinnati, OH, March 1991.
[20] "Hi gh Temperature Fireside Corrosion Monitoring in the Superheater Section of a Pulverized-Coal-
Fired Boiler," Report TR-101799, Electric Power Research Institute, Dec. 1992.
[21] Mok, W. Y., Cox, W. M., Stokes, P. S. N., Chamberlain, J. R., and Bakker, W. T., "On-Line
Corrosion Surveillance in the Superheater Section of a Coal-Fired Power Boiler," EPRI Symposium
on Improved Technology for Fossil Plants, Washington, DC, March 1993.
[22] "Feasibility of On-Line Monitoring of Stress Corrosion Cracking in Rotating Components," Report
TR-102537, Electric Power Research Institute, June 1993.
[23] Syrett, B. C., "Corrosion Control in Electric Power Plants," Materials Performance, Vol. 31, No.
8, Aug. 1992, pp. 52-61.
[24] Bierwagen, G., "Theoretical Derivation of Resistance Noise," Journal of the Electrochemical So-
ciety, 1994, submitted for publication.
[25] Eden, D. A., "A Probabilistic Model of Electrochemical Noise Generation," presentation to ASTM
Committee GI , Atlanta, GA, June 1993.
[26] Collier, D. and Cox, W. M., "Modem Plant Corrosion Surveillance Systems," Institute of Electrical
Engineers, London, March 1994.
A. M. Br ennenstuhl , 1 Bl ai r Si m, ~ and Renata Cl audi 2
A Progress Report on the Use of
Electrochemical Noise to Investigate the
Effects of Zebra Mussel Attachment on the
Corrosion Resistance of AISI Type 304
Stainless Steel and Carbon Steel in
Lake Water
RE F E RE NCE : Brennenstuhl, A. M., Sim, B., and Claudi, R., " A Pr o g r e s s Re p o r t o n t he
Us e o f El e c t r o c h e mi c a l No i s e t o I nv e s t i g a t e t he Ef f e c t s o f Ze br a Mu s s e l At t a c h me n t o n
t he Co r r o s i o n Re s i s t a n c e o f AI S I Ty pe 3 0 4 St a i nl e s s St e e l a n d Ca r b o n St e e l i n La k e
Wat er , " Electrochemical Noise Measurement for Corrosion Applications, ASTM STP 1277,
Jeffery R. }(earns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson,
ABS TRACT: The electrochemical noise technique was used to determine the effect of zebra
mussel settlement on the corrosion performance of AISI Type 304 stainless steel and carbon
steel (ASTM A53 Grade B). These materials represent alloys commonl y used for handl i ng
untreated Great Lakes water at Ontario Hydro' s power generating plants. Thi s work was mo-
tivated by a concern that zebra mussel settlement will lead to accelerated attack of these
materials as a result of the establishment of stable crevice conditions and the growth of cor-
rosion influencing anaerobic sulfate-reducing bacteria (SRB). Corrosion monitoring was carried
out in a field test facility that uses the same untreated Lake Erie water as Ontario Hydro' s
Nanticoke Thermal Generating Station. The test program extended from May through Decem-
ber 1993. During this period, a number of electrochemical parameters were monitored simul-
taneously, including coupling current, electrochemical potential noise (EPN), electrochemical
current noise (ECN), degree of localization (DOLL and resistance noise (R,). Differences were
observed in the performance of the control samples and the samples to which mussels were
attached. The results for the AISI Type 304 stainless steel suggested that over the period
monitored, mussel at t achment reduced corrosion activity. Similarly, signals from carbon steel,
samples exposed to mussels, although initially displaying relatively hi gh corrosion rates, ex-
hibited less corrosion damage than did control samples over the longer term. The reason for
this difference in performance is not known but is considered to have resulted from a change
in the surface envi ronment as a result of mussel attachment, which appeared to di mi ni sh
corrosion. One possible explanation may be the generation of inhibitive species by the mussels.
KE Y WOR D S : coupling current, potential noise, current noise, degree of localization, resis-
tance noise, freshwater, zebra mussels, sulfate-reducing bacteria, corrosion monitoring
Research scientist, Materials Technology Unit, and technologist, Sustainable Development, respec-
tively, Ontario Hydro Technologies, 800 Kipling Ave., Toronto, Ontario, M8Z 5S4 Canada.
2 Senior scientist, Environmental Department, Ontario Hydro, 700 University Ave., Toronto, Ontario,
M5G l X6 Canada.
186
WW'vV.aStIll.OFg
BRENNENSTUHL ET AL. ON EFFECTS OF MUSSELS 187
The accidental introduction of zebra mussels into the Great Lakes has led to problems in
conveying water to process systems that use this important resource. Settlement of zebra
mussels on the inside surface of pipes that extract and discharge water from the lakes has
resulted in equipment outages as a result of reduced flow. In addition to the severe fouling,
there are also concerns that the crevice conditions created beneath the mussels could also
lead to accelerated corrosion of metallic substrates. Zebra mussel attachment may result in
the formation of differential aeration conditions. It was feared that mussels could cause the
establishment and growth of anaerobic sulfate-reducing bacteria (SRB) beneath the attach-
ment site. To ensure the continued reliable operation of process equipment and formulate
effective remedial measures, should these have been found necessary, it would be helpful if
the effect of zebra mussel settlement on the corrosion performance of metallic materials
exposed to untreated lake water was better understood.
Corrosion tests were conducted at Ontario Hydro' s (OH' s) Nanticoke Thermal Power Gen-
erating Station. This power station is located on the shores of Lake Erie and has experienced
problems associated with heavy zebra mussel fouling. Electrochemical instrumentation was
used to investigate the effects of zebra mussel settlement on materials commonly exposed
to untreated lake water. Carbon steel (ASTM A53 Grade B) and AISI Type 304 stainless
steel samples were monitored.
This paper presents the experimental methods used and the results obtained to date during
the field exposure. Consideration is also given to the possible causes of electrochemical
activity observed during the program.
Test Facility and Test Conditions
The exposure trials were conducted in a specially built facility located at the Nanticoke
Power Generating Station on the shores of Lake Erie. Figure 1 is a schematic of the test
setup. The test samples were held in aquaria. One aquarium contained zebra mussels. The
FIG. 1--Diagram of the Nanticoke zebra mussel corrosion test side stream facility.
TABLE l ~Appr oxi mat e analysis o f lake wat er (Lake Erie)
chemistry parameters at Nanticoke Thermal Power Generating
Station.
pH 8.1
CI, mg/ L 20.5
SO4, mg/ L 25.0
Alkalinity, mg CaCO3/L 99.0
Total iron, mg/ L 0.08
Specific conductivity, mS / cm 293.1
bot t om of this was carpet ed wi t h adul t mussels. A second aquari um, the " cont r ol " aquari um,
was mai nt ai ned essent i al l y mussel free, al t hough mussel vel i gers di d ent er the cont rol aquar-
i um duri ng the exposure per i od and became est abl i shed on the surface of the coupons.
However, the ar ea of coverage was very low ( <5%) and the mussel s were very smal l , less
than 2 mm in length. Unt reat ed wat er t aken from the station i nt ake was passed over the
sampl es at a nomi nal rate of 0. 6 L/ mi n. Duri ng the l at t er part of the exposure (at 3700 h),
the flow wat er t hrough the aquari a was st opped for 14 days to det ermi ne t he effect of no
flow condi t i ons on t he el ect rochemi cal response. Because the t ops of bot h aquari a were open,
the wat er had an i nt erface wi t h ai r and thus a suppl y of oxygen. However, the devel opment
of a bi ofi l m over the ent i re sampl e surface shortly aft er the flow was st opped woul d have
severel y l i mi t ed the access of oxygen to the met al surface. The composi t i on of the wat er is
gi ven in Tabl e 1. Wat er t emperat ure was moni t or ed cont i nuousl y and ranged from 8 to 26~
(the t emperat ure of the wat er duri ng the trial per i od is shown in Fi g. 2). Wat er sampl es also
were t aken rout i nel y for pH det ermi nat i on; no si gni fi cant changes were observed.
The test sampl es were i nspect ed on a weekl y basi s to i dent i fy when mussel s at t ached to
the surface and to i nvest i gat e how the mussel densi t y changed wi t h time. Compl et e coverage
30
2 5
s0
' j r
E
1o
5 J
o 1
l i i
2 3 4
Th o u s a n d s
Time/Hours
FIG. 2--Temperat ure variation o f the wat er f l owi ng into the test aquaria during the corrosion-mon-
itoring period.
of the surface of a sample with mussels was considered undesirable because this could have
resulted in the development of completely uniform anaerobic conditions and thus an envi-
ronment that is not conducive to significant corrosion [1]. It was suspected that the worst-
case condition would involve the presence of isolated anaerobic areas beneath crustatia and
adjacent mussel-free regions in which oxygen reduction could occur. During these trials,
zebra mussel coverage did not exceed approximately 25% coverage on the stainless steel,
and 50% coverage on the carbon steel.
Sample Design
Figure 3 illustrates the sample configuration used during the experiment. The electrode
assembly was comprised of three tube-coupons, each of which had a surface area of 27 cmL
Electrical isolation between each coupon was achieved with polymethyl methacrylate
(PMMA) insulators. Epoxy resin was used to join the coupons to the insulators. Electrical
leads were spot-welded to each coupon. The welds and the outer surface of the coupons
were then coated with a high-build epoxy paint.
Electrochemical Monitoring
Monitoring was performed using CML Ltd. electrochemical instrumentation. The instru-
ment collected, stored, and performed the following summary statistics:
I. The differential potential between two of each test electrode group.
2. Electrochemical potential noise (EPN)
3. The value of the overall coupling current between the third electrode of each group
and one common electrode.
4. The fluctuation in the coupling current or electrochemical current noise (ECN).
FIG. 3--Three-electrode tube sample used during this study. Samples were fabricated from AISI Type
304 stainless steel and ASTM A53 Grade B carbon steel.
5. Degree of localization (DoL) derived by dividing the current noise value by the root
mean square (RMS) of the coupl i ng current [2]. This parameter is used to classify
broadly the corrosion process occurring on the sample surface. Values between 0.1 and
1.0 were considered to be an indication of a Poisson-type process, that is, an unstable
system such as pitting, crevice corrosion, or stress corrosion cracking. Values less than
0.1 were assumed to be associated with uniform corrosion.
6. The value of the resistance noise (R,), derived from the ratio of the potential noise and
considered to be analogous to polarization resistance (Rp) in charge transfer resistance
(R, ) obtained by linear polarization resistance measurements and from electrochemical
impedance spectroscopy [2-4].
The instrumentation was multiplexed to interrogate twelve samples semicontinuously (six
control samples and six mussel samples). Each interrogation period consisted of collecting
1024 data points with a separation interval of 4 s. The time domain data were stored on the
hard drive of the logging computer. This cycle continued for the duration of the tests, which
started in May 1993 and continued until December 1993.
Results
A1SI Type 304 Stainless Steel
The results presented here were typical of the observations made for the "cont r ol " and
"mussel " sample covered test electrodes monitored during this study. Good reproducibility
was observed, and the trends described were consistent among samples of similar type.
A DoL plot for a typical control sample is given in Fig. 4. The data indicate relatively
high and erratic fluctuations during the first 500 to 700 h of exposure. Some values ap-
proached the maxi mum of 1. These values subsided to values on the order of 0.1 before
gradually increasing to around 0.3 after 2600 h of exposure, when a sudden large drop in
intensity occurred. This low-amplitude condition persisted for approximately 1200 h, sub-
sequent to which sharp short-duration increases became apparent, a condition that continued
for about 400 h. DoL results from the corresponding mussel sample are also given in Fig.
4. Initially high signal values, typically greater than those observed for the "cont r ol " samples,
were observed, a condition that continued for the first 200 to 400 h. This initial period of
high activity was followed by a period characterized by intermittent, relatively short, tran-
sients with no consistent pattern. After approximately 3500 h of exposure, an increase in the
frequency of the noise fluctuations became evident, and this lasted for 200 to 300 h. This
coincided with the increase in electrochemical activity observed for the control samples. This
increased activity corresponded to a 14-day period during which water was not flowing
through the aquaria.
A typical RMS coupling current plot for one of the "cont r ol " and "mussel " samples is
shown in Fig. 5. Initially, coupling current values for the control samples were relatively low
for all samples. A significant change in RMS coupling current occurred approximately 1000
h into the test, at which time a relatively sharp increase in the coupling current was observed.
For a period of approximately 1500 h after this increase was initially evident, the coupl i ng
current remained fairly steady at around 0.25 I~A. After approximately 2600 h of exposure,
the amplitude and frequency of the outputs increased dramatically, and coupling currents of
up to 5 I~A were reached. This condition persisted for the remainder of the test, despite a
large reduction in the water temperature. Occasional transients were detected, and one of the
largest decreases occurred during the period of no flow, during which the coupl i ng current
0.5 r
0. 4
0201 i '
o _ _ I _ _
0 1 2 3 4 5
Thousands
Time/Hrs
_ _ Control + Zebra
FIG. 4--DoL plot for AISI Type 304 stainless steel showing the outputs for "control" and "mussel"
samples.
values decreased on average to approximately 1 I~A for 300 to 400 h. However, the general
trend was toward increasing coupl i ng current with l onger exposure time. These results con-
trasted with those f r om the "mussel " samples, for which the coupling current values started
higher relative t o the "cont rol s, " peaked at around 2000 h into the test, and then gradually
fell. The peak current for the "mussel " samples was approximately 2 ixA. The no flow
condition at the end of the test did not appear to affect significantly coupling current values.
ECN data for the "cont r ol " sample were similar to the DoL data except that the ECN
values appeared to display the changes in activity more clearly (that is, the sensitivity seemed
to be greater for ECN dat a) dur i ng the last quarter of the exposure period. There was no
sign of the high-amplitude events seen at the start of the tests (Fig. 6a), but high-amplitude,
short-duration transients were evident, during the later stages of the exposure during the
period of no water flow through the aquaria. Figure 6a also shows the EPN data for the
same "cont r ol " sample. There was reasonable correlation between the EPN and ECN results.
A typical ECN trace for the "mussel " samples is shown in Fig. 6b. The plots were similar
to the DoL data for this sample, and good correlation between the ECN and EPN outputs
was evident.
None of the data from both the "cont r ol " and the "mussel " samples appears to display
any dependence on temperature during the exposure period. The increase in electrochemical
noise activity associated with the 14-day no-flow condition appeared greater with the "con-
trol" samples. This increase coincided with a decrease in the coupling current of the control
samples.
0.02
0.015
0.01
0.005
0
0.02
1 2 3
Thousands
Time/Hrs
__ EPN _r ECN
a)
2.5
2
1.5
1
0.5
0
5
0.015
Z 0.01
0.01)5
2.5
2
1
0.5
o o
0 l 2 3 4 5
Thousands
Time/Hrs
__ EPN + ECN
b)
FIG. 5--Typical ECN and EPN data f or (a) control AISI Type 304 sample, and (b) a "mussel" AISI
304 sample. Note the good correspondence between these two parameters.
3
.~ .~ 2
1
.
i
1 2
Thousands
Time/Hrs
3 4
Control + Zebra
FIG. 6--RMS coupling current plot for representative AISI Type 304 "control" and "mussel" samples.
Carbon Steel (ASTM A53 Grade B)
Bot h R, and DoL are presented here because it was believed a compari son of these data
might characterize better the corrosion behavior of the carbon steel samples, although the
latter parameter is normally associated with the evolution of localized corrosion.
Resistance noise outputs for the "cont r ol " samples are shown in Fig. 7. Significant data
scatter was evident for both the "cont r ol " and "mussel " samples. However, the general
tendency was toward an increase in R, (that is, a decrease in corrosion rate) with time for
both sets of samples. It was not possible to distinguish whether the mussel attachment made
any difference in the corrosion rate during the first 1000 h of exposure. However, as exposure
time was increased, activity decreased to a greater extent with the mussel samples.
A typical DoL output for the "cont r ol " and "mussel " samples is presented in Fig. 8. DoL
data for the "cont r ol " samples were generally of a very low amplitude throughout the ex-
periment, with occasional large transients which decayed quickly. These results were not
unexpected because general corrosion was prevalent. The mussel results appeared to differ
slightly from those for the "cont r ol " samples in that relatively hi gh short-duration, high-
value signals were initially observed, some being as high as DoL = 0.8. These high DoL
values were evident during the first 1000 h of the exposure, but subsequently values less
than 0.05 became normal. A very slight increase in activity was detected during the 14-day
no-flow period.
Typical EPN and ECN plots obtained during the study are shown in Fig. 9. A good
correlation between EPN and ECN was evident for the "cont r ol " samples. Bot h the EPN
and ECN signals were relatively low except at the middle and end of the exposure. EPN
outputs up to 1.8 mV and ECN values of up to 2.0 ixA were evident, but average values on
20
20
15
10
t
I
1 2 3
Thousands
Time/Hrs
m Sample #1 + Sample #2 __ Sample #3
0 4
a~
r ~
r~
15
10
g~
0 1 2 3 4
Thousands
Time/Hrs
Sample #1 + Sample #2 __ Sample #3
b)
FIG. 7- - R. data f or the carbon steel (a) "'control" and (b) "mussel " samples.
0.2
0.15
o 0.1
0.05
0
0 1 2 3 4
Thousands
Time/Hrs
_ _ Control + Zebra
FIG. 8--DoL data for the carbon steel samples showing "control" and "mussel" samples.
the order of 0.15 mV and 0.1 ~A were recorded for EPN and ECN, respect i vel y. Hi gher
values at the end of the exposure coi nci ded wi t h the 14-day no-flow condi t i on, as was t he
case for the st ai nl ess steel sampl es. Noi se dat a from " mus s el " sampl es appear ed to have a
di fferent pattern from t he "cont r ol s. " " Mus s el " sampl es exhi bi t ed si gni fi cant l y hi gher EPN
and ECN than di d t he " cont r ol " sampl es duri ng the first 3000 h of the exposure. The t rend
di d not persi st , and the noi se levels gr adual l y r educed wi t h l onger exposure t i me until it was
l ower than that of cont rol sampl es and st ayed for the r emai nder of the test. No si gni fi cant
i ncrease in act i vi t y was obser ved at the end of the experi ment , in cont rast to behavi or ex-
hi bi t ed by "cont r ol " sampl es.
RMS coupl i ng current pl ot s for t hese carbon steel " cont r ol " and " mus s e l " sampl es are
shown in Fi g. 10 The RMS coupl i ng currents for the " cont r ol " sampl es di spl ayed an erratic
behavior, with no cl ear trends with t i me, and out put ranged from 18 p~A to less than 1 I~A,
wi t h t he mean bei ng around 7 ixA. A slight i ncrease in coupl i ng current was evi dent duri ng
the per i od when the flow to the aquari a was st opped. Resul t s for the " mus s el " sampl es,
unl i ke t hose for the " cont r ol " sampl es, exhi bi t ed a pr onounced t rend in that the coupl i ng
currents started at rel at i vel y low values, t ypi cal l y 10 to 15 ixA, and aft er 700 to 1000 h of
exposure i ncreased sharpl y to a maxi mum of 30 I~A. A fluctuating hi gh- coupl i ng current
prevai l ed until about 1800 h of exposure, and then gr adual l y decr eased to values much l ower
than t hose obser ved for the cont rol sampl es.
The di fference in corrosi on act i vi t y det er mi ned by t he presence or absence of zebra mus-
sels on the surface was mor e pr onounced for carbon steel sampl es than was the case for
st ai nl ess steel, but agai n little evi dence of t emperat ure dependence was seen in ei t her case.
0. 5
1.5
0. 4
.~ 0. 3
z
t~
m ~ 0 . 2
0.1
0. 5
0 3
Th o u s a n d s
Ti me/ Fi r s
_ _ EPN + ECN
a)
o
0. 5
0
5
1.5
0 . 4
a~ 0. 3
t ~ 4 0 . 2
0. 1
0 1 2 3 4 5
T h o u s a n d s
T i me / Hr s
E P N + E C N
b)
1
0. 5
FI G. 9 - - ECN and EPN data f or carbon steel samples showing ( a) "control" signals, and ( b) zebra
mussel signals. Good correspondence between these parameters is evident.
0.035
0.03
< 0. 025
-~ 0. 02
~ ~ 0.015
~A
0.01
0.005
0
o 1 2 3 4
Thousands
Time/Hrs
_ _ Control + Zebra
FIG. IO--RMS coupling current plots for "control" and "'mussel" carbon steel samples.
Di scussi on
Electrochemical noise measurement was used to assist in the investigation into the effects
of zebra mussel attachment on AI SI Type 304 stainless steel and carbon steel ( ASTM A53
Grade B). Bot h materials were exposed to untreated lake water at Ontario Hydr o' s Nanticoke
power generation plant. Carbon steel normally sustains general corrosion, and, as such, its
service life in lake water should be predictable provided the chemistry of the environment
to which the steel is exposed is known. The stainless steel examined during this investigation
is the least corrosion-resistant of the stainless steels used at power stations and has a history
of failing by localized corrosion in untreated natural water. AISI Type 304 is susceptible to
microbiologically influenced corrosion (MIC) when exposed to Lake Erie water [5]. Micro-
environments beneath deposits may support SRB, which can induce severe damage on both
the carbon steel and stainless steel. There was concern, therefore, that the corrosion per-
formance of these alloys might be affected adversely by changes in the environment at metal
surfaces as a result of the attachment of zebra mussels. Crevice formation, and the estab-
lishment of differential aeration cells, might further accelerate corrosion by the establishment
and growth of SRB beneath the mussels. This study investigated the contribution of zebra
mussels to the corrosion behavior of these alloys. Not e that the trial is still in progress, and
that samples have not yet been removed for metallurgical examination.
AISI Type 304 Stainless Steel
The results for the AI SI Type 304L stainless steel show differences between samples that
had mussels attached to the surface and those that were mussel-free. Initially, very little
act i vi t y was observed on the cont rol sampl es. Thi s was in sharp cont rast to the mussel
sampl es, whi ch exhi bi t ed al most i mmedi at e activity. The di fference in per f or mance is ra-
t i onal i zed in t erms of the devel opment of crevi ce condi t i ons at the surface beneat h the
mussels, whi ch at t ached to the surface of t he sampl es in less than a week. The est abl i shment
of di fferences in the el ect rochemi cal pot ent i al bet ween t he crevi ce sites and the free met al
surface results in the format i on of di scret e anodi c and cat hodi c regi ons. Not e that the t erm
crevice does not refer to the cl assi cal geomet ri cal condi t i on. Zebr a mussel s at t ach fai rl y
l oosel y to the surface and di spl ay some mobi l i t y. Therefore, the condi t i on is more aki n to
underdeposi t corrosi on. The coupl i ng current for the "cont r ol " sampl es di d not show any
mar ked sust ai ned i ncrease duri ng this period. It can be i nferred that any di ssol ut i on was
qui ckl y fol l owed by repassi vat i on. The per i od of i ni t i al hi gh act i vi t y on the " mus s e l " sampl e
was short -l i ved, and it was suspect ed that the noi se det ect ed at the start of the experi ment
was possi bl y as a result of the di ssol ut i on and repassi vat i on at sites of weakness in the
passi ve fi l m at crevi ce location. These sites may have been caused duri ng the t ube fabri cat i on
and sampl e preparat i on. The act i vi t y di mi ni shes once t he l ocat i ons in whi ch t he film is
defect i ve have been repai red and pr ovi ded that the di ssol ut i on process has not reduced t he
pH in the crevi ce regi on to a level in whi ch pi t i ni t i at i on in " s ound" oxi de occurs. It was
concl uded that act i vi t y evi dent at the start of the exper i ment cor r esponded to t he r epai r of
such defects. Previ ous wor k [6] on the same test faci l i t y to i nvest i gat e the effects of chl o-
rination added credence to this hypot hesi s because chl ori nat i on tests on "as - r ecei ved" AI SI
Type 304 and on i dent i cal sampl es that were et ched before testing exhi bi t ed very di fferent
behavior. The et ched sampl es di spl ayed very little el ect rochemi cal noi se at the start of the
experi ment , whereas the "as - r ecei ved" sampl es exhi bi t ed many met ast abl e pi t t i ng events.
In t he case of the cont rol sampl es, very little noi se was det ect ed dur i ng the first 1000 h.
Previ ous studies i ndi cat ed that it may t ake as l ong as six months to est abl i sh deposi t s that
woul d pr omot e pi t i ni t i at i on [7]. Bet ween 1000 and appr oxi mat el y 2500 h of exposur e an
i ncrease in el ect rochemi cal act i vi t y was di scerni bl e, and the coupl i ng current, ECN, and
EPN were al l hi gher than t hose col l ect ed duri ng the earl y stages of the exposure. These
changes suggest a l arger number of di ssol ut i on repassi vat i on events on the met al surface. A
substantial i ncrease in the coupl i ng current was al so evi dent aft er 2500 h of exposure. Thi s
corresponded to hi gher EPN and ECN outputs and suggest ed that a rel at i ve i ncrease in the
rate of degradat i on was in progress. DoL dat a i ndi cat e that what was t aki ng pl ace duri ng
this per i od was not consi st ent with dat a from the " cont r ol " sampl es at the start of the test.
The DoL outputs were of a l ower ampl i t ude whi ch is i ndi cat i ve of less l ocal i zed attack.
Previ ous moni t ori ng wor k on AI SI Type 304 sampl es in Lake Eri e wat er i ndi cat ed that
ECN and EPN i ncreased with exposure t i me until the l ake wat er t emperat ure decreased
subst ant i al l y [6]. It was al so report ed that SRB l i kel y accel erat e at t ack [5]. An overal l in-
crease in the corrosi on rate of t he " cont r ol " sampl es wi t h t i me was t herefore expect ed, and
this was observed. Thi s di d not appear to be the case for sampl es exposed to mussel s. Af t er
the initial per i od of high noi se intensity, little further act i vi t y was observed, whi ch suggest s
that in the short t erm zebra mussel at t achment di d not have a del et eri ous effect on corrosi on
per f or mance and seemed to reduce corrosi on activity. The reason is unclear, al t hough it
woul d seem from the evi dence obt ai ned to dat e that the presence of zebra mussel s may
condi t i on the envi ronment in such a way that corrosi on is reduced. A possi bl e answer may
be the product i on of i nhi bi t i ve mat eri al s by the mussels. Pol yani oni c pept i des have been
report ed to i nhi bi t corrosi on. Hydr ophi l i c and hydr ophobi c prot ei n fractions are commonl y
found in the cal ci um carbonat e skel et al structures of mari ne organi sms. These can be rich
in pol yani oni c prot ei ns [8]. Cl ues to the cause for this r educed corrosi on may come from
the surface anal ysi s of the sampl es when the t est i ng is compl et ed.
The effect of zero waterflow was particularly evident from the control samples. ECN and
coupling current appeared to have decreased, and DoL and EPN increased. The decreases
can be explained by reduced oxygen available for the cathode reaction. A DoL high suggests
high localized activity, which is not consistent with the other outputs. This result highlights
the problems with this monitoring parameter. DoL is frequently at its highest during periods
when the noise resistance increases, that is, with very low rates of attack the noise data are
almost certain to indicate a relatively high degree of localization even if the rate of attack
is low. This problem with inconsistent DoL results is one reason why several noise pa-
rameters were considered during this study. The samples exposed to mussels exhibited almost
no discernible change in electrochemical behavior during the flow stoppage.
Carbon Steel (ASTM A53 Grade B)
The resistance noise data obtained from carbon steel samples were not consistent with the
differences in EPN, ECN, and coupling current data from the control- and mussel-covered
samples. A decrease in the corrosion rate with time was inferred from the R, outputs for
both test conditions. Results from the mussel-exposed samples suggested that the rate of
corrosion decreased at a greater rate with the mussel samples. The high starting electro-
chemical noise for the mussel samples was certainly not evident in the R, plots. The large
scatter in the R, data masked this detail and highlighted the importance of considering EPN
and ECN data outputs in addition to resistance noise values. DoL data, considered to be
only of use for evaluating localized corrosion, yielded information that may be of signifi-
cance. The results suggested that localized activity of mussel samples decreased slightly
during the first 1000 h of exposure. These data indicated that flow stoppage at the end of
the exposure period had less effect than was the case with stainless steel.
On the basis of electrochemical noise data obtained to date during this program, it would
be concluded that zebra mussel attachment may affect corrosion performance of the carbon
steel. Their presence on stainless steel may reduce corrosion. This is suspected to be the
case at least while the mussels are alive, although the behavior may be different with dead
or decaying mussels. The low EPN, ECN, and coupling current, after extended exposure and
relative to the control samples, may be indicative of either the formation of a protective film
or the conditioning of the chemistry of the "lake water" in the immediate vicinity of the
mussels or both, rendering it less corrosive. Again, a possible explanation may be the release
of inhibitive material from the mussels. Surface analysis may confirm if there is a difference
in the composition of the corrosion products.
Summary
Electrochemical noise instrumentation can be used to investigate the differences in cor-
rosion of ASTM 53A Grade B carbon steel and AISI Type 304 stainless steel samples
exposed to zebra mussels in lake water. The electrochemical outputs obtained from these
tests were compared with results from samples that were essentially mussel-free.
Data for the stainless steel revealed differences between the mussel-free and the mussel
environments. The mussel-free stainless steel samples exhibited the expected performance
for this material in untreated lakewater, that is, gradually increasing activity with time. A
different behavior was found with the samples exposed to mussels. After high initial activity,
infrequent short-duration events were detected with no real pattern to the signals. Overall,
the results suggested that zebra mussel attachment does not have a deleterious effect on the
corrosion performance in the short term, and this presence may even reduce corrosion. How-
ever, the effect of dead or decaying mussels or both on corrosion performance of the materials
is unknown.
Data for carbon steel revealed erratic outputs for the control samples. No clear trends were
observed. This contrasted with the data obtained from the mussel samples. Relatively high
initial activity was noticed. This peaked after 1800 h of exposure and then gradually de-
creased to very low values. The presence of zebra mussels appeared to inhibit corrosion, at
least during the period of the trials. The difference between the two test conditions was not
obvious from the R, parameter as a result of a very high degree of scatter. RMS coupling
current, EPN, and ECN outputs revealed greater differences between the "control" and
"mussel" samples than was the case with R, assessment. Hence, electrochemical noise data
were observed to identify differences in the behavior of samples that were free of zebra
mussels and those that had mussels attached, but it was concluded that single-output pa-
rameters such as the DoL or R, were insufficient to make a clear discrimination.
Ac k nowl e dgme nt s
The authors would like to acknowledge the helpful discussions and technical support from
Dr. E. G. Leitch and Dr. E Spencer.
Re f e r e nc e s
[1] Newman, R. C., Webster, B. J., and Kelly, R. G., ISIJ Int., Vol. 31, 1990, pp. 201.
[2] Rothwell, A. N. and Eden, D. A., Paper 223, Corrosion' 92, NACE, Nashville, 1992.
[3] Lumsden, J. B., Kendig, M., and Jeanjaquet, S., Paper 224, Corrosion' 92, NACE, Nashville, 1992.
[4] Mansfeld, E and Xiao, H., Journal of the Electrochemical Society, Vol. 140, No. 8, 1993.
[5] Brennenstuhl, A. M. and Gendron, T. S., "The Use of Field Tests and Electrochemical Noise to
Define Conditions for Accelerated MIC Testing," paper presented at the Symposium on Microbio-
logically Influenced Corrosion (MIC) Testing, Miami, FL, Nov. 1992.
[6] Brennenstuhl, A. M., in Proceedings of the 12 'h International Corrosion Congress, Vol. 6, p. 4102.
[7] Brennenstuhl, A. M., Doherty, P. E., Dunstall, T., and Evans, D., in Proceedings of the Fourth
International Symposium on Environmental Degradation of Materials in Nuclear Power Sys-
t ems - Wat er Reactors, 1989.
[8] Mueller, E., Sikes, C. S., and Little, B. J., Corrosion, Vol. 49, No. 10, 1993.
J ohn I . Mickalonis,' Ri chard J . J acko, 2 Graham P Qui rk, 3 and
Davi d A. Eden 3
The Use of Electrochemical Noise
Measurements with Nuclear Waste Tanks
RE F E RE NCE : Mickalonis, J. I., Jacko, R. J., Quirk, G. R, and Eden, D. A., " T h e Us e o f
El e c t r o c h e mi c a l No i s e Me a s u r e me n t s wi t h Nu c l e a r Wa s t e Tanks, " Electrochemical Noise
Measurement for Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R. Scully,
Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., Ameri can Society for Testing
and Materials, 1996, pp. 201-213.
ABSTRACT: Processing of nuclear materials for ei t her military or civilian purposes generates
waste products. The nuclear wastes are generally stored in plain carbon or stainless steel
underground tanks. Corrosive wastes are inhibited to minimize the corrosion of these tanks
and mai nt ai n tank structural integrity under normal and off-normal conditions. Storage tanks
have fairly static conditions, although processing of the waste in these tanks to more stable
forms will produce dynami c conditions, which may lead to localized corrosion. Corrosion
monitoring under either condition, therefore, would ensure t hat inhibitive conditions are
maintained.
A preliminary investigation was conducted to evaluate electrochemical noise measurement s
for corrosion monitoring of waste tanks. The initial results indicated that current and potential
noise correlate to the solution corrosivity. Further development is necessary to differentiate
among the various forms of corrosion.
Electrochemical noise measurements were made in the laboratory wi t h plain carbon steel
electrodes under simulated conditions for storage and processing of nuclear waste. Coupons
were also exposed in the laboratory test vessels. The pri mary aggressive species of the waste
was the nitrate anion, whi ch induces pitting. The simulated waste was initially i nhi bi t ed wi t h
sodium nitrite and sodium hydroxide. The nitrate concentration was increased over the test
period to increase the corrosivity of the solution. The temperature was held constant at 40~
The current and potential noise showed an increasing trend with nitrate concentrations. Under
i nhi bi t ed storage conditions, the noise data were fairly stable. Inspection of the electrodes
revealed little general corrosion with mi ni mal pitting. The coupons, however, had a significant
amount of pitting. This difference was attributed to the microstructure of the electrodes and
coupons.
KEYWORDS: electrochemical noise measurements, pitting, carbon steel, microstructure, nu-
clear waste tanks, nitrate, inhibitors
Nu c l e a r wa s t e r es ul t s f r o m t he ni t r i c aci d di s s ol ut i on of f uel a nd t ar get e l e me nt s dur i ng
t he p r o d u c t i o n of n u c l e a r ma t e r i a l s f or na t i ona l d e f e n s e a nd s pa c e pr ogr a ms . At t he Sa v a n n a h
Ri ve r Si t e ( SRS) , mo s t o f t hi s r a di oa c t i ve wa s t e i s s t or ed i n u n d e r g r o u n d t a nks ma d e o f
va r i ous gr a de s of c a r b o n st eel . Th e t a nks r a nge i n c a pa c i t y f r o m 0. 75 t o 1.3 mi l l i on gal
( 2. 84 t o 4. 9 mi l l i on L). Th e was t e, whi c h i s ne ut r a l i z e d be f or e p l a c e me n t i n t he t anks , i s
s t or ed i n t hr e e f or ms : a s l udge c o n t a i n i n g me t a l oxi des , me t a l c a r bona t e s , a nd mo s t o f t he
' Senior engineer, Westinghouse Savannah River Company, RO. Box 616, Aiken, SC 29802.
2 Westinghouse Electric Company STC, 1310 Beul ah Rd., Pittsburgh, PA 15235.
3 CAPCIS March Ltd., Bainbridge House, Granhy Row, Manchest er M1 2PW, Uni t ed Kingdom.
201
www.astm.org
radi oact i ve component s; a sal t cake pr i mar i l y cont ai ni ng sodi um nitrate; and a supernat ant
l i qui d cont ai ni ng sodi um nitrate, hydroxi de, and nitrite al ong wi t h the wat er - sol ubl e radi o-
active cesi um and strontium. Al l wast e forms cont ai n mi nor amount s of ot her chemi cal
const i t uent s such as sulfates and chl ori des.
Ni t rat e was found to be the most aggressi ve ion to the carbon steel t ank [1]. The pr i mar y
corrosi on mechani sms of concern for t he t anks are nitrate stress corrosi on cracki ng and
pitting. The wast e is i nhi bi t ed wi t h sodi um hydr oxi de and nitrite to prevent t hese forms of
corrosi on. General corrosi on of the carbon steel is bel i eved to be i nsi gni fi cant because of
the hi gh pH of the wast e [2]. At SRS, this corrosi on is moni t ored t hrough a pr ogr am con-
sisting of vi deo observat i on of t he t ank i nt eri ors and the surroundi ng annul us spaces, chem-
i cal anal yses of the wast e by grab sampl es, sporadi c use of short -t erm coupon tests, and
l i mi t ed ul t rasoni c t hi ckness measurement s of the t ank wal l s [2]. Trials are al so under way
wi t h a corrosi on coupon ri g for schedul ed, l ong-t erm corrosi on rate measurement s.
The nucl ear wast e wi l l be processed t o st abi l i ze the radi oact i ve component s for l ong-t erm
storage. The hi gh-l evel radi oact i ve component s wi l l be vitrified i nt o a bor osi l i cat e glass.
Low- l evel liquid wast e wi l l cont i nue to be mi xed wi t h grout to form a concret e. Several
tanks, whi ch were desi gned as st orage tanks, wi l l be used to prepare the hi gh-l evel radi o-
active wast e for vitrification. The envi ronment wi t hi n t hese tanks wi l l change f r om static to
dynami c condi t i ons. The dynami c condi t i ons coul d pr oduce operat i ng condi t i ons, such as
concent rat i on fluctuations, t hat coul d pr omot e l ocal i zed corrosi on. Therefore, a cont i nual ,
on-l i ne met hod of moni t or i ng corrosi on duri ng wast e processi ng is necessary t o det ect and
mi ni mi ze any del et eri ous l ocal i zed corrosi on.
An assort ment of cor r osi on- moni t or i ng t echni ques are avai l abl e commer ci al l y or under
devel opment [3]. For wast e t ank appl i cat i ons, a t echni que must be abl e to det ect various
forms of l ocal i zed corrosi on di rect l y on a cont i nual basis. These requi rement s l i mi t ed t he
number of candi dat e t echni ques. El ect r ochemi cal noi se measurement s (ENM) met t he re-
qui rement s. Al t hough avai l abl e commer ci al l y, this t echnol ogy needs further devel opment for
appl i cat i on to the wast e t ank envi ronment .
As part of a cor r osi on- moni t or i ng devel opment pr ogr am at SRS, a pr el i mi nar y l aborat ory
st udy was conduct ed to eval uat e ENM. The resul t s from this st udy show that ENM offers
pr omi se in det ect i ng pi t i ni t i at i on in a si mul at ed wast e solution. Dat a anal ysi s and i nt erpre-
tation t hrough the cal cul at i on of a pi t t i ng funct i on were requi red to det er mi ne the changes
in pi t t i ng suscept i bi l i t y. Duri ng the study, sodi um nitrate was var i ed t hrough a range of
concent rat i ons to i ncrease the corrosi vi t y of the si mul at ed wast e sol ut i on and to i nduce
pitting. The experi ment al results al so showed that t he mi crost ruct ure of carbon steel had a
si gni fi cant effect on t he pi t t i ng suscept i bi l i t y of a sampl e. Furt her devel opment al wor k is
necessary to det ermi ne i f ENM can accurat el y moni t or pi t propagat i on.
Ex p e r i me n t a l Pr o c e d u r e
The pur pose of the l aborat ory st udy was to det er mi ne i f ENM coul d det ect pi t t i ng in a
si mul at ed wast e sol ut i on when the ni t rat e concent rat i on was above t he l i mi t for i nhi bi t i on.
The experi ment al setup, dat a anal ysi s, and mi crost ruct ural anal ysi s are descri bed.
Experimental Setup
The t hree-mont h test was conduct ed wi t h t wo probe assembl i es. One probe assembl y was
pl aced in a covered vessel in whi ch the wast e composi t i on was hel d const ant and wi l l be
referred to as the cont rol t hroughout this paper. The second probe assembl y was pl aced in
a separat e cover ed vessel in whi ch the ni t rat e concent rat i on was i ncreased. Ni t r ogen was
MI CKALONI S ET AL. ON ENM WI TH NUCLEAR WASTE TANKS
TABLE 1--Composition of simulated waste solution.
Constituents Concentration, M
Aluminum nitrate 2.05E-2
Iron nitrate 5.50E-3
Sodium hydroxide 9.37E-2
Sodium nitrate 5.18E-3
Sodium nitrite 2.57E-2
Sodium oxalate 8.66E-3
Sodium sulfate 5.94E-3
Sodium carbonate 5.80E-2
Sodium bicarbonate 1.20E-2
Sodium hypophosphate 3.90E-4
Calcium carbonate 6.60E-4
Sodium chloride 1.03E-3
Sodium fluoride 7.30E-4
Sodium chromate 1.40E-4
Chromium chloride 6.00E-5
Sodium molybdate 1.85E-5
Sodium metasilicate 1.60E-4
Uranyl nitrate 3.30E-4
Cobalt nitrate 1.50E-6
Copper nitrate 2.00E-5
Manganese dioxide 1.14E-3
Nickel nitrate 5.20E-4
Mercury nitrate 1.10E-4
Zinc nitrate 4.00E-5
Lead nitrate 2.00E-5
Phenol 4.30E-6
203
slowly bubbled in each vessel to simulate the waste tank operation of maintaining a nitrogen
flow over the waste.
The initial solution, which was used in each vessel, had the simulated waste composition
shown in Table 1. The composition represents an average chemistry expected during SRS
waste processing and is based on the present waste inventory. For this study, the initial nitrate
concentration was set at the highest level for the specified inhibitor concentrations (that is,
the sodium hydroxide and nitrite concentrations) [1]. The nitrate concentration was adjusted
by adding variable quantities (8.8 to 300 mL) of a 5M sodium nitrate solution. The nitrate
additions and estimated resulting nitrate concentrations are given in Table 2.
The pH of the simulated waste was monitored during the test. The pH of the control
solution slowly decreased over the course of the test from 10 to 9.5. This pH drop may have
TABLE 2--Nitrate additions and estimated
nitrate concentrations.
0 0.022
1 "8~8 0.037
2 26.4 0.0797
3 66.0 0.184
4 75.0 0.298
5 300.0 0.704
Final Nitrate
Addition Quantity, mL Concentration, M
resul t ed from t he pi ckup of carbon di oxi de when the sol ut i on was exposed to the ai r weekl y.
The pH of the ni t rat e-adj ust ed sol ut i on decr eased f r om 10 to 9.0, at t ri but ed bot h to carbon
di oxi de pi ckup and t he addi t i ons of the 5M sodi um nitrate solution.
Each ENM probe assembl y consi st ed of t hree nomi nal l y i dent i cal cyl i ndr i cal el ect rodes;
t wo el ect rodes were coupl ed to moni t or the current noise, and the third moni t or ed the po-
tential noise. The el ect rodes were made of ASTM A537, Cl ass 1, carbon steel (A537) wi t h
the di mensi ons of 3.1 cm in length and 0.5 cm in diameter. This grade of steel is t he mat eri al
of const ruct i on for t he wast e t anks that are to be used as processi ng tanks. The nomi nal
composi t i on for A537 is 0. 24% carbon, 0.7 to 1.6% manganese, 0. 04% sulfur, 0. 035% phos-
phorus, and 0.15 to 0. 5% silicon. The el ect rodes were prepared wi t h a 600-gri t surface finish
by the manufacturer. The pot ent i al and current noi ses were measured on a CAPCI S Mar ch
Lt d. Deni s V4. 40 system. The noi se si gnal s were measured for 40 mi n every 3.5 h wi t hout
appl yi ng a pot ent i al . Duri ng each measur ement peri od, the soft ware cal cul at ed t he fol l owi ng
st at i st i cal val ues for t he current and pot ent i al noises: mean, st andard devi at i on, and r oot
mean square (rms).
Fl at corrosi on coupons were al so exposed in each vessel. The coupons had a cent ral hol e
for at t achment to the support. The coupons were al so made of A537 carbon steel wi t h the
di mensi ons of 5.1 by 2.6 cm. Several coupons were r emoved from t he test aft er approxi -
mat el y one and a hal f months. The removal was j ust bef or e i ncreasi ng the nitrate concen-
t rat i on to 0.298M.
D a t a A n a l y s i s
Several corrosi on paramet ers were cal cul at ed from t he ENM data: noi se resi st ance, whi ch
is a measure of t he general corrosi on rate; the l ocal i zat i on index, whi ch i ndi cat es the pre-
domi nant corrosi on mechani sm; and a pi t t i ng function, whi ch is an i ndi cat i on of t he si gni f-
i cance of l ocal i zed corrosi on.
The noi se resi st ance, R. , is defi ned as
R, = (rv/(r / (1)
where cry is t he st andard devi at i on of the pot ent i al noi se and ~ is the st andard devi at i on of
t he current noi se [4].
The l ocal i zat i on i ndex, L, is defi ned as
L = t r l / l ~ m ~ (2)
where l ~s is the rms val ue of the current noise. The l ocal i zat i on i ndex fal l s in a range of
0. 0 to 1.0. Values on the order of 0.001 i ndi cat e that uni form general corrosi on is the
pr edomi nant mechani sm, whereas values appr oachi ng 1.0 i ndi cat e the pr edomi nance of a
l ocal i zed mechani sm [5].
Dur i ng t he i ni t i al anal ysi s of the data, the l ocal i zat i on i ndex was found not to di fferent i at e
bet ween passi ve behavi or and l ocal i zed corrosi on in this envi ronment . However, further anal -
ysi s of the ENM dat a t hrough the appl i cat i on of a pi t t i ng funct i on was abl e to di fferent i at e
t hese behavi ors. The pi t t i ng funct i on was empi r i cal l y deri ved as descr i bed below. For br oader
appl i cat i on, the pi t t i ng funct i on must be refi ned and veri fi ed experi ment al l y.
The pi t t i ng funct i on quantifies l ocal i zed behavi or by combi ni ng the l ocal i zat i on i ndex wi t h
the average magni t ude of the current t ransi ent [6]. Therefore, passi vat i on and l ocal i zed cor-
MICKALONIS ET AL. ON ENM WITH NUCLEAR WASTE TANKS 2 0 5
rosi on can be di fferent i at ed because passi ve behavi or with smal l er current t ransi ent s wi l l
have smal l er pi t t i ng funct i ons than occur duri ng pi t t i ng.
The pi t t i ng function, P, is defi ned as
P = L {[di(1) + "" + di ( n) ]/ n}
where
L = the l ocal i zat i on i ndex gi ven by Eq 2,
di(n) = the current t ransi ent magni t ude or current i ncrease over a 1-s interval, and
n = the number of intervals.
(3)
I f the current t ransi ent cont i nues over mor e than 1 s, de(n) is the summat i on of al l the current
changes in the transient. For exampl e, i f the current i ncreased by t he quant i t i es of 1, 2, and
2 ~A over t hree successi ve seconds and the pot ent i al condi t i on ( descr i bed bel ow) was sat-
isfied in al l cases, di(n) = 5 I~A. The dat a were anal yzed in sect i ons of 4- mi n durat i on, s o
the pi t t i ng function was cal cul at ed for 1024 seconds or intervals, (that is, n -< 1024). Si m-
ilarly, tr I and I~n~, whi ch are used to cal cul at e L, are al so cal cul at ed for each section.
As ment i oned above, a pot ent i al condi t i on exists for accept i ng a current t ransi ent i nt o t he
summat i on of the mean current t ransi ent magni t ude t o sat i sfy pi t t i ng behavior. In the case
of i dent i cal el ect rodes, the current t ransi ent must have an opposi t e si gn to that of t he pot ent i al
transient. I f the current t ransi ent i ncreases, the pot ent i al t ransi ent decreases. The absol ut e
val ue of the current dat a is t aken bef or e det er mi ni ng the sl opes of t he t ransi ent s because
pi t t i ng may i ni t i at e on ei t her el ect rode. The pot ent i al on the t hi rd el ect rode, t herefore, must
be negative. Onl y dat a that sat i sfy t he pot ent i al t ransi ent condi t i on are accept ed.
The sl ope condi t i ons i mposed for t he summat i on of the mean current t ransi ent s came f r om
a consi derat i on of the Tafel sl opes duri ng pi t t i ng or l ocal i zed anodi c di ssol ut i on. Fi gur e 1
i l l ust rat es this behavior. As pi t t i ng occurs, the anodi c Tafel l i ne shifts down al ong the ca-
t hodi c Tafel curve as a resul t of an i ncrease in anodi c di ssol ut i on. As shown in Fi g. 1, this
shift resul t s in the pot ent i al havi ng a negat i ve change (that is, a shi ft t o mor e el ect ronegat i ve
val ues) and t he current havi ng a posi t i ve change.
Microstructural Anal ysi s
Af t er t hey were r emoved from the sol ut i ons, t he coupons and el ect rodes were r i nsed wi t h
wat er and bl own dry. The sampl es were vi sual l y exami ned bot h bef or e and aft er cl eani ng
wi t h l i ght - opt i cal ( LOM) and scanni ng el ect ron mi cr oscopes (SEM). Surface chemi st ri es
were eval uat ed usi ng an energy di spersi ve X- r ay syst em (EDS) on t he SEM. Measurement s
of pi t si ze were al so made on t he flat coupons wi t h a confocal l aser mi croscope. Af t er an
i ni t i al exami nat i on of t he sampl es, t he cor r osi on product s were cl eaned f r om t he surface
usi ng a Cl ar ke' s sol ut i on per t he ASTM Pract i ce for Prepari ng, Cl eani ng, and Eval uat i ng
Cor r osi on Test Speci mens ( GI ) .
Re s u l t s
The pr i mar y findings of this st udy were that t he ENM dat a, t hrough t he anal ysi s of a
pi t t i ng function, i ndi cat ed that t he cor r osi on act i vi t y of the t wo vessel s was different. The
ENM corrosi on paramet ers of noi se resi st ance and l ocal i zat i on i ndex showed no si gni fi cant
di fference bet ween the t wo vessel s because of the general passi vi t y of the syst em. Mi cr os-
r"
0
13_
- ve
r
(1)
* 6
I:L
E o.-
z~E
-Me
m/m+
Erev
r e ' ~ " ~ An o d i c
L ~ Active dissolution
9 Mi xed 7 1 1 t he p,t
Potential" ~
II Cathodic
" * Cu r r e n t De n s i t y , L o g i
At
+ve
An o d i c
~ Coupl ed Potential
ooo,c o 2 , ~
within the pit
AT Cu r r e n t , L o g I
+ve
FI G. 1--Schematic anodic and cathodic Tafel c ur v e s dur i ng pi t t i ng.
tructural anal ysi s o f the e l e c t r ode s f r om each v e s s e l s ho we d a di f f erence i n the degree o f
corros i on. The s t eel mi crost ruct ure wa s al s o f ound t o af f ect corros i on.
Noi se Resi stance
The no i s e resi st ance i s anal ogous t o the c o mmo n l y accept ed charge transfer res i s t ance
used f or es t i mat i ng general corros i on rates. In the St ern- Geary rel at i onshi p, the corros i on
current i s equal t o the St ern- Geary const ant di vi ded by the charge transfer resi st ance. Si m-
ilarly, the no i s e res i s t ance i s i nvers el y proporti onal t o the corros i on current. The corros i on
current i s convert ed t o a corros i on rate us i ng Faraday' s law. A noi s e res i s t ance o f 100 k f l
c m 2 corres ponds t o a general corros i on rate o f 0. 0035 mm ye ar - l i f a Stearn-Geary const ant
o f 30 mV i s us ed ( t ypi cal val ues range f r om 2 0 t o 5 0 mV) . Thi s corros i on rate i s i nsi gni f i cant ,
whe r e as a no i s e res i s t ance o f 100 f~ c m z corres ponds t o a cons i derabl e corros i on rate o f 3. 5
mm y e a r - k
The no i s e res i s t ances we r e rel at i vel y hi gh f or bot h v e s s e l s in t hi s st udy and di d not s ho w
any si gni f i cant di f f erence f r om the addi t i on o f nitrate. The no i s e res i s t ance val ues for each
MICKALONIS ET AL. ON ENM WITH NUCLEAR WASTE TANKS 2 0 7
vessel are pl ot t ed versus t he t i me in test in Fi g. 2. In the figure, changes in t he measuri ng
resi st or of t he zero resi st ance ammet er ( ZRA) are i ndi cat ed. These changes affect ed t he val ue
of the noi se resi st ance.
The average noi se resi st ance was of the or der of 100 kl~ cm 2, whi ch i ndi cat es that t here
was i nsi gni fi cant general corrosi on. Thi s resul t was expect ed because st eel gener al l y is pas-
sive in al kal i ne solutions. These val ues are in agr eement with pol ari zat i on resi st ance values
det er mi ned with DC t echni ques on a r od el ect r ode in si mi l ar sol ut i ons [7].
Localization Index
The l ocal i zat i on i ndex showed some response to the nitrate addi t i ons; however, the i ndex
values pr ovi ded l i mi t ed, i f any, i nformat i on because of the l ow rates of attack. The response
of the i ndex over the t est per i od is shown in Fi g. 3 for each vessel. The l ow corrosi on was
at t ri but ed to the passi ve behavi or of t he steel. The i ndex reached t he hi ghest val ues when
the noi se resi st ance i ncreased, i ndi cat i ng that at l ow rates of at t ack the noi se dat a showed a
hi gh degr ee of l ocal i zat i on even i f the l ocal i zed at t ack was mi ni mal . Therefore, in this
al kal i ne syst em, the l ocal i zat i on i ndex i ndi cat ed t hat passi ve film mai nt enance and l ocal i zed
corrosi on are si mi l ar processes, in that t hey are bot h random. Because current magni t udes
are not i ncl uded in t he i ndex, l ocal i zed cor r osi on and passi ve behavi or cannot be di fferen-
tiated. The i ndex, however, can di fferent i at e bet ween ei t her of t hese processes and uni f or m
corrosi on.
Pitting Function
The pi t t i ng funct i on combi nes the cor r osi on current measur ement wi t h the l ocal i zat i on
i ndex to quant i fy t he severi t y of pitting. The nitrate addi t i ons i ncr eased the corrosi on current
of t he el ect rode. Thi s i ncrease was at t ri but ed to pi t i ni t i at i on. The mi crost ruct ural anal ysi s,
as di scussed below, support ed this i nt erpret at i on of t he ENM data. For t he cont rol vessel,
I~ms was on the order of 10 -8 A. l~ms for t he ni t rat e-adj ust ed sol ut i on i ncreased by an order
of magni t ude to l 0 7 A aft er t he final nitrate addi t i on.
Fi gur e 4 shows t he changes in the pi t t i ng funct i on over the course of the test. The pi t t i ng
funct i on for t he cont rol vessel was flat t hroughout t he experi ment . The initial nitrate addi t i ons
of 8 and 26 mL had little effect. The l arger addi t i ons resul t ed in current transients, whi ch
t ended t owar d stable, hi gher values. The t ransi ent s were al so more i mmedi at e wi t h t he l arger
nitrate addi t i ons. The pi t t i ng funct i on di d not cont i nue to i ncrease aft er the i ni t i al response,
whi ch i ndi cat ed that t he el ect rodes were not forced i nt o pi t propagat i on. Pi t pr opagat i on may
have occurred i f t he exper i ment durat i on was longer. The pi t t i ng function, however, dem-
onst rat ed that the ENM dat a were di fferent for the t wo vessels.
Microstructural Analysis
Pi t t i ng of t he st eel in t hese si mul at ed wast e sol ut i ons was i ni t i at ed on t he exami ned cou-
pons and el ect rodes. The degree of pi t t i ng, however, was di fferent for the coupons and
el ect rodes. Thi s di fference was at t ri but ed t o t hei r mi crost ruct ures.
Electrodes--The macr oscopi c exami nat i on of t he el ect rodes from bot h vessel s reveal ed
superfi ci al r eddi sh brown cor r osi on product s l ocat ed bet ween t he surface gri ndi ng marks.
These product s were bel i eved to have resul t ed from ai r oxi dat i on aft er r emoval from the
vessel. The el ect rodes f r om t he ni t rat e-adj ust ed vessel al so had some areas of heavi er cor-
rosi on product s or great er degradat i on.
10000
= o o E 1 0 0 o
r r ' ~
wE
10
Control Solution
[ ]
i i ,
0 10 20 30
40 50 60 70 80 90
Ti me in Test (days)
100
Nitrate-Adjusted Solution
10000
r 1000
lO
0 10 20 30 40 50 60 70 80 90 100
Ti me in Test ( days)
FIG. 2 - - No i s e resi st ance val ues f o r car bon st eel in a s i mul at ed was t e sol ut i on.
At hi gher magni fi cat i on ( x500) in the SEM, the el ect rodes were found to have pi t t ed, as
shown in Fi g. 5 for an el ect r ode from the ni t rat e-adj ust ed test. The severi t y of pi t t i ng ap-
pear ed great er on the el ect rodes from the ni t rat e-adj ust ed vessel. The severi t y was not quan-
tified as a resul t of the l i mi t ed number and smal l si zes of t he pi t s. The pi t s were pr i mar i l y
hemi spher i cal and measur ed 10 ~Lm across. The pi t bot t oms were seen, whi ch i ndi cat ed that
the pi t s had not grown ext ensi vel y into the coupons. These resul t s were expect ed based on
the pi t t i ng funct i on anal ysi s of the ENM data. Al so, on one el ect rode, whi ch was cross-
sect i oned and vi ewed, pi t s coul d not be found, al t hough the cr oss- sect i on cut s may have
been in areas wi t hout pits. Most of the obser ved pi t s were associ at ed wi t h i ncl usi ons, al-
MICKALONIS ET AL. ON ENM WITH NUCLEAR WASTE TANKS 209
X
I1)
t . -
r
o
N
0
0
. . J
1
0.8
0.6
0.4
0.2
0
0 10 20
Cont r ol Sol ut i on
30
i i i i i i i
40 50 60 70 80
i
90 100
Ni t r at e- Adj ust ed Sol ut i on
1
x 0.8
~ 0.6
~ 0.4
~ 0.2
0 .
0 10 20 30 40 50 60 70 80 90
FIG. 3--Localization index values for carbon steel in a simulated waste solution.
100
t hough some i ni t i at ed near surface scratches. The i ncl usi ons, as anal yzed by EDS, were
composed pr i mar i l y of manganese and sulfur or of al umi num and silicon.
These mi crost ruct ural observat i ons, t herefore, support the i nt erpret at i on of the ENM data.
Pi t growt h on the coupons was si gni fi cant to that of t he el ect rodes where pi t s had initiated.
Pi t t i ng was al so mor e severe at hi gher ni t rat e concent rat i ons. ENM may al so be useful for
ot her mat eri al s, such as aust eni t i c st ai nl ess steels, whi ch al so have a pr opensi t y for pi t
i ni t i at i on at i ncl usi ons.
Coupons- - The coupons t hat were r emoved bef or e the 75- mL addi t i on ( 0. 298M nitrate
concent rat i on) were found to have numerous pi t s, as shown in Fi g. 6. Some l i ght staining
was al so not ed beneat h the washers that were used to fasten the coupons. The severi t y of
1E-06
Co n t r o l S o l u t i o n
O
O
t "
- i
t l
e "
CX.
1E-07
1E-08
1E-09
1E-10
1E-11
[ ] [ ]
I I I I I I I I I I I I I I
0 10 20 30 40 50 60 70 80 90
Ti me in Test (days)
100
t -
o
. _
O
t - -
I t
t ~
._c
. ~
1E-06
1E-07
1E-08
1E-09
1E-10
Ni t r a t e - A d j u s t e d S o l u t i o n
0 10 20
i ' i i i
30 40
1E-11 ' ' ' ' ' '
50 60 70 80
Ti me i n Test (days)
FIG. 4--Pitting function values f or carbon steel in a simulated waste solution.
i i
90 100
pi t t i ng on the coupons was si mi l ar for t he t wo solutions. In this case, the mi crost ruct ure of
the coupon was a mor e si gni fi cant vari abl e for i ni t i at i ng pi t t i ng than the sol ut i on corrosi vi t y.
Recal l that the cont rol sol ut i on was at the l i mi t for i nhi bi t i on. As can be seen in Fi g. 6, the
pi t s were in l i near arrays. Thi s f or mat i on resul t ed from t he steel mi crost ruct ure. The pi t s
were associ at ed with i ncl usi ons like the electrodes. These inclusions were along the ferri t e/
pearl i t e boundari es. These boundar i es were st rai ght because of the mat eri al processi ng, whi ch
resul t ed in a l ami nar mi crost ruct ure of ferri t e (l i ght grains) and pearl i t e (dark grai ns) as
shown in Fi g. 7.
MICKALONIS ET AL. ON ENM WITH NUCLEAR WASTE TANKS 211
FIG. 5- - SEM micrograph of pits on a carbon steel electrode (
The pit morphology for the coupons was similar to that for the electrodes--hemispherical
and approximately l0 p,m across, The severity of pitting was much greater on the coupons.
This difference in pitting susceptibility is attributed to the steel chemistry. More inclusions
were found on the surface of an untested coupon than of an electrode. Figure 8 shows an
SEM micrograph of a coupon surface. The small dark spots were identified as inclusions. A
probable explanation for this difference is that the steel used to make the electrodes had
lower impurities than that used for the coupons.
The difference in the severity of corrosion between the electrodes and the coupons high-
lights an important consideration for corrosion-monitoring techniques that use samples (that
FIG. 6--Photograph of pits on a carbon steel coupon.
FIG. 7--Microstructure of carbon steel coupons (Nital Etchant).
is, either electrodes or coupons). The microstructure of the sample must be representative of
the material of construction for the structure or equipment that is to be monitored. If not,
erroneous data may be obtained.
Conclusions
The results of this study show that:
1. Analysis of ENM data, through pitting function values, aided in distinguishing between
passivity and pitting.
FIG. 8--SEM micrograph of carbon steel coupon surface.
MIGKALONIS ET AL. ON ENM WITH NUCLEAR WASTE TANKS 213
2. The pi t t i ng funct i on i dent i fi ed the initiation of smal l pi t s (that is, 10 g,m or less).
3. The mi crost ruct ure of the steel si gni fi cant l y affect ed the corrosi on t hrough the presence
of i ncl usi ons and must be consi der ed when usi ng cor r osi on- moni t or i ng techniques.
The el ect rochemi cal noi se t echni que may meet the requi rement s for corrosi on moni t or i ng
of nucl ear wast e tanks. Furt her anal ysi s and devel opment , however, are necessary to confi rm
pi t pr opagat i on and to opt i mi ze the pi t t i ng funct i on anal ysi s. The t echni que may al so be
useful for the det ect i on of stress corrosi on cracki ng wi t h appropri at e sel ect i on cri t eri a and
anal yt i cal limits.
References
[1] Congdon, J. W., "Inhibition of Nuclear Waste Solutions Containing Multiple Aggressive Anions,"
Materials Performance, Vol. 27, No. 5, May 1988, pp. 34-38.
[2] Donovan, J. A., "Materials Aspects of SRP Waste Storage--Corrosion and Mechanical Failure,"
USDOE Report DP-1476, Savannah River Site, Aiken, SC, Nov. 1977.
[3] Moran, G. C. and Labine, P., Eds., Corrosion Monitoring in Industrial Plants Using Nondestructive
Testing and Electrochemical Methods, ASTM STP 908, American Society for Testing and Materials,
West Conshohocken, PA, 1984.
Rates and Mechanisms," Paper 223, Corrosion92, NACE International, Houston, TX, 1992.
[5] Webster, S., Nathanson, L., Green, A. G., and Johnson, B. V., "The Use of Electrochemical Noise
to Assess Inhibitor Film Stability," in UKCorrosion 92, 1992.
[6] Hearer, E. E., Lawson, K., and Eden, D. A., "Stress Corrosion Cracking In Refinery Systems," in
UKCorrosion'93, Institute of Corrosion, Surrey, United Kingdom, 1993.
[7] Mickalonis, J. I., "Corrosion of Steel in Simulated Waste Solutions," Paper 117, Corrosion94, NACE
International, Houston, TX, 1994.
He nni e J. De Br uy n, l Ke v i n Laws on, 2 a n d Ed wa r d E. He a v e r 2
On-Line Monitoring Using
Electrochemical Noise Measurement in
C0- C02- H20 Systems
REFERENCE: DeBruyn, H. J., Lawson, K., and Heaver, E. E., "On- Li ne Monitoring Using
Electrochemical Noise Measurement in CO-CO2-H20 Systems," Electrochemical Noise
Measurement for Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R. Scully,
Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., American Society for Testing
and Materials, 1996, pp. 214-229.
ABSTRACT: The stress corrosion cracking (SCC) susceptibility of carbon steel extends over
a narrow range of potentials in environments that contain a mixture of wet carbon monoxide-
carbon dioxide (CO-CO2) gas. Normal fluctuations in plant operation may cause movement in
and out of this range of potentials. Stress corrosion cracking in this case is discontinuous, and
an opportunity exists to prevent it by process control.
Electrochemical noise measurement, because of its capability for operation in thin film con-
densate conditions, is an attractive technique for monitoring corrosion in wet CO-CO2 systems.
Laboratory tests and plant trials were carded out to determine if electrochemical noise mea-
surement could be used to characterize periods of SCC.
KEYWORDS: carbon steel, stress corrosion cracking, process control, carbon monoxide-
carbon dioxide, on-line monitoring, oil industry
St ress cor r osi on cr acki ng ( SCC) is a pr obl em t hat affects a r ange of engi neer i ng mat er i al s
used i n a wi de vari et y of i ndust r i al appl i cat i ons. The pr obl em is t r adi t i onal l y appr oached by
sel ect i ng nons us cept i bl e mat er i al s or a stress r el i ef heat t reat ment . Bot h met hods of pr even-
t i on can ent ai l cons i der abl e expense, and t he l at t er ma y not al ways be effect i ve, par t i cul ar l y
i f t he heat t r eat ment is done i n t he field or aft er a l ocal i zed repair. Wh e n t he suscept i bi l i t y
to SCC for a steel ext ends over a nar r ow r ange of pot ent i al s, t here is a possi bi l i t y t hat nor mal
pl ant f l uct uat i ons wi l l cause move me nt i n and out of t hi s r ange, and cr acki ng wi l l be di s-
cont i nuous . Thi s pr ovi des an oppor t uni t y to pr event SCC by pr ocess cont r ol i f per i ods of
SCC act i vi t y can be i dent i f i ed and effect i ve count er meas ur es defi ned. Such a syst em is f ound
downs t r eam of r ef or mi ng uni t s i n whi ch pr essur i zed mi xt ur es of wet car bon monoxi de and
car bon di oxi de pr omot e stress cor r osi on cr acki ng of car bon steel. Thi s paper descr i bes t he
appl i cat i on of el ect r ochemi cal noi s e me a s ur e me nt ( ENM) to moni t or stress cor r osi on crack-
i ng i n such an envi r onment .
' Mossgas (Pty) Ltd., Duin Zicht Ave., Private Bag X14, Mossel Bay 6500, Republic of South Africa.
2 Real Time Corrosion Management Ltd., Rutherford House, Manchester Science Park, Manchester,
MI5 6SZ UK.
214
www.astm.org
DEBRUYN ET AL. ON ON-LINE MONITORING 215
Stress Corrosion Cracking in Wet Mixtures of Carbon Monoxide and
Carbon Dioxide
Transgranular SCC has been observed in as-welded carbon steel pipelines and equipment
exposed to wet mixtures of carbon monoxide (CO) and carbon dioxide (CO2) gas [1-4].
Cracking is most prevalent in the temperature range from 20 to 60~ and occurs in many
mixtures of CO/CO2 gas. Published test results [1-5] and service experience at Mossgas
and similar process plants are summarized in Fig. 1, which indicates a likelihood of cracking
in almost any wet mixture of CO and CO2. Potentiostatically controlled slow strain rate tests
carried out by Hannah [4] showed that in pressurized systems SCC is promoted by both
anodic and cathodic polarization, indicating that the system is capable of supporting both
SCC and hydrogen embfittlement. At the free corrosion potential, the mechanism is SCC
reportedly [3] as a result of film rupture. In CO/CO2 gas systems, an aqueous solution of
COz is the principal corroding agent, and surface adsorption of CO provides passivation
[1-3]. SCC occurs in a narrow band of potentials within which the steel exhibits active-
passive transition behavior. Dunlop and Olson [5] report cracking in the range from -475
to -575 mV (SCE). This is supported by results obtained by Harrison [3] who reports
cracking at a similar range of potentials with maximum crack growth at - 475 mV (SCE).
Berry and Payer [1] found SCC at potentials between - 510 and -625 mV (SCE).
The schematic in Fig. 2 reflects the corrosion behavior of carbon steel in aqueous solutions
of CO and CO2. The system behaves as a chemical potentiostat, depending upon CO2 con-
centration, CO adsorption, and the presence of oxygen [2,3]. There is a possibility that
normal fluctuations in the operation of an industrial plant will cause an excursion into and
out of the region of SCC susceptibility. Straightforward measurement of corrosion potential
would seem to offer a means of monitoring when an environment is capable of supporting
SCC in this system, however, the service media are principally gaseous, and cracking occurs
beneath a thin film of condensate. Meaningful measurement of potential is virtually impos-
FIG. 1--Summary of published test results and service experience showing range of SCC susceptibility
[1].
216 E L E C T R O C H E M I C A L NOI SE M E A S U R E M E N T
. ~ : ~ M a t e r i a l ::' :
: : 1 , n e e i~ :
B e h a v i o r
D e s c d p t i o n
E n v i r o n m e n t a l
C o n d i t i o n s
Act i ve
A p a s s i v e
film i s not
f o r me d
':::= a n d : ~: So~ce '
Tr ans )assive
A passi ve film i s f o r me d b u t i s ruptured by t he
appl i cat i on o f stress. Ma t e r i a l s e x p o s e d at ~}m
rupture s is sl ow t o repassivate a n d Iocalised metal
loss b y anodi c di ssol uti on resul ts in S C C
I ncreasi ng con' osi vi t y p r o mo t e d by:
Hi gher PCO 2
Hi gher PO 2
H i g h e r total acids
P a s s i v e
A pass! ve surf ace
i s f o r me d a n d full
passi vi t y i s
mai nt ai ned
Increasing passi vi t y p r o mo t e d b y :
Hi gher PCO
a n d
s o m e o r g a n i c c o m p o u n d s
FIG. 2--Schematic showing behavior of carbon steel in CO-CO 2 environments [ 1].
sible, and measurement of the corrosion potential in the bulk environment may not reflect
conditions at the crack tip. Electrochemical noise instrumentation, because of its capability
to moni t or under thin film conditions, is attractive for use in C0- CO2- H20 systems.
El ect rochemi cal Noi se Meas urement for SCC Appl i cat i ons
Electrochemical noise has been characterized from laboratory and plant observations. It
has been noted that the amplitude of low frequency potential or current electrochemical noise
is related to the rate of the corrosion process, and that the frequency range, as measured by
the shape of the power spectrum, is influenced by the nature of the process [6].
The ability of ENM to distinguish corrosion processes has led to an interest in its use to
detect SCC. Cottis and Lotto report that the noise technique can be used to moni t or SCC
processes in alpha-brass [7] and high-strength aluminum alloys [8]. In most cases, SCC gave
the highest EN amplitude and the highest standard deviation peaks. The source of the elec-
trochemical current noise (ECN) was believed to be repassivation transients resulting from
exposure of fresh metal following rupture of the passive film by cracking. Similar tests
carried out on high strength steel in conditions in which environmentally assisted cracking
was almost certainly because of hydrogen embrittlement resulted in characteristic noise only
when the specimen broke [9]. There is an opportunity to prevent SCC by process control i f
periods of SCC activity can be identified and effective countermeasures defined. Control
requires a signal that reflects the susceptibility of the material to SCC. Laborat ory tests and
plant trials were carded out to assess the use of electrochemical noise measurement in
CO-CO2-H~O systems.
Experimental Procedure and Results
Laborat ory Met hod
St ai nl ess st eel aut ocl aves were used to si mul at e t wo servi ce envi ronment s by pressuri zi ng
an aqueous condensat e to 2 MPa wi t h t he gas mi xt ures shown in Tabl e 1. The syst em was
i nvest i gat ed usi ng a prest ressed C-ri ng as one el ect r ode (Worki ng 1) coupl ed to a second
unst ressed count er-el ect rode (Worki ng 2) fabri cat ed f r om i dent i cal mat eri al . The aut ocl ave
body was used as the reference el ect rode. The C-ri ngs t ypi cal l y had an out si de di amet er of
appr oxi mat el y 48 mm and a wal l t hi ckness of 3 mm. They were f abr i cat ed f r om l ow-st rengt h
carbon st eel Type SA 106 Gr ade B, in accor dance wi t h t he requi rement s of t he ASTM
Pract i ces for Maki ng and Usi ng C- Ri ng Stress Cor r osi on Cr acki ng Test Speci men (G 38).
Several stress levels were exami ned: 50, 75, and 100% of yi el d stress. The el ect r ol yt e was
degassed by purgi ng wi t h oxygen- f r ee ni t rogen. The el ect r ode arrangement was then pl aced
in t he aut ocl ave whi ch was cl osed and subsequent l y repurged wi t h ni t rogen. A gas envi ron-
ment was used to br i ng t he aut ocl ave up to pressure, and the gas mi xt ure was cont i nuousl y
bubbl ed t hrough the el ect r ol yt e for the durat i on of the test. A pr eci si on l ow-noi se dat a
acqui si t i on syst em was used to col l ect and anal yze t he el ect r ochemi cal noi se data. The
i nst rument vol t age range was 0 to l 0 V, and t he current range was l 0 pA to 10 mA at a
resol ut i on of 2 mV and l 0 pA. The maxi mum r ecommended dat a acqui si t i on rat e was one
sampl e per second. A schemat i c of t he i nst rument at i on is shown in Fi g. 3.
At t he end of t he t est peri od, the C-ri ngs were opt i cal l y exami ned usi ng a st ereomi cro-
scope. Ar eas of i nt erest were marked, and aft er sect i oni ng, t he severi t y of SCC was assessed
usi ng met al l ography. The EN t races from each speci men were exami ned to det er mi ne i f t here
were charact eri st i cs that coul d be mat ched to the obser ved vi sual SCC.
Laboratory Results
Met al l ography
Met al l ogr aphy was used to est abl i sh the presence of SCC in the C-ri ngs. Speci mens ex-
posed to Gas Mi xt ur e 1 showed the hi ghest i nci dence of SCC. The maxi mum dept h of
penet rat i on and hi ghest frequency of cracks was obser ved in the speci mens st ressed to 100%
of yi el d stress. Cracks coul d be di st i ngui shed at about 60 ~ f r om t he center, whi ch corre-
sponded to appr oxi mat el y 45% of yi el d, as det er mi ned f r om t he t heoret i cal stress di st ri but i on.
The maxi mum crack dept h measured at t he most hi ghl y st ressed regi on at t he cent er of t he
speci mens was 0. 4 mm. The maxi mum crack dept h measur ed in t he C-ri ngs st ressed to 75
and 50% of yi el d was 0.17 and 0.05 ram, respectively. As before, no cracks were obser ved
at areas of t he speci mens in whi ch the t heoret i cal stress l evel fel l bel ow 45% of yi el d stress.
In Gas Mi xt ur e 2 onl y ver y shal l ow cracks, l ess than 0.015 mm, were observed. It was not
possi bl e to correl at e the i nt ensi t y of SCC to the magni t ude of the appl i ed stress.
TABLE l --Anal ysi s of the gas mixtures used during laboratory tests.
Carbon Monoxide, % Carbon Dioxide, % Hydrogen, % Methane, %
Gas Mixture 1 5 15 40 40
Gas Mixture 2 15 15 65 5
FIG. 3--Schematic of electrochemical noise measurement instrumentation.
El ect rochemi cal Noise Measurement
Figure 4 shows a typical set of electrochemical current and potential noise signals collected
from the samples of carbon steel stressed to 50, 75, and 100% of yield and exposed to Gas
Mixture 1 (5% CO). At high stress levels, positive-going potential transients and unidirec-
tional negative-going current transients were identified and appeared to be characteristic of
periods of stress corrosion cracking. The time traces showed an increase in transient ampli-
tude and frequency at increasing levels of stress. The electrode stressed to 100% of yield
showed potential transients approaching 0.5 mV, with several current transients in excess of
6 ~A. For the 50 and 75% specimens, the amplitude and frequency of the potential and
current transients was significantly less (Fig. 4). Figure 5 shows an example of SCC observed
during metallographic examination of a C-ring stressed to yield.
Samples monitored in Gas Mixture 2 containing a higher CO concentration exhibited less
transient activity, and the mean coupling current was substantially lower. This was indicative
of lower corrosion as a result of better inhibition by the CO. Positive-going potential tran-
sients and corresponding unidirectional negative-going current transients were present in the
electrochemical noise measurement traces of specimens stressed at the higher levels (Fig.
6).
Plant Method
Purpose-designed SCC sensors were fabricated for use with 50.8-mm (2-in.) high-pressure
access fittings (Fig. 7). The sensors comprised three elements which included stressed and
unstressed elements fabricated from carbon steel similar to that used for construction of the
pipeline being monitored. In this case, carbon steel Type SA 106 Grade B was used. The
reference electrode was fabricated from Type 316 stainless steel. The stressed electrode was
DEBRUYN ET AL. ON ON- LI NE MONI TORI NG 219
+8.47
A
+8.29
-4.30
g
-4.60
Time (seconds) 2048
50% yield-stress

+11.33
-5.00
g
-5.50
0 Time (seconds) 2048
75% yield-stress
+9.50
g

-6.40
g
-7.30
r .
0 lqme (seconds) 2048
100% yield-stress
FIG. 4- - Typi cal pot ent i al and current time traces obtained during laboratory tests using Gas Mixture
1 and working electrodes stressed to 50, 75, and 100% of yi el d stress.
I +18.882 [ A~
[ +18.615 L
0 Time (seconds) 2o48
50% yi el d-st ress
-378.45
g
-380.71
" i
0 "[]me (seconds) 2048
75% yi el d-st ress
I
- 3 " A 2 ' I
-369.70
-746.90
Time (seconds) 2o48
100% yi el d-st ress
FIG. 5- - SCC cracks found after microsectioning a specimen stressed to yield.
FIG. 6--Typi cal potential and current time traces obtained during laboratory tests using Gas Mixture
2 and working electrodes stressed to 50, 75, and 100% of yieM stress.
stressed to yield point, confirmed by strain gage measurements. The working electrodes were
electrically coupled so that the mean coupling current and electrochemical current noise
could be monitored. For the plant trials, the sensors were wired such that Working 2 was
the stressed electrode. This reversed the sign of the current transients. Electrochemical po-
tential noise between the couple and the reference electrode was measured simultaneously
against a stainless steel reference electrode included in the probe (Fig. 3). Three sensors
were placed at key locations in the plant, as shown by the simplified process diagram shown
in Fig. 8. Table 2 summarizes the operating conditions at each location. A high resolution
electrochemical noise system was used to interrogate sensors placed in the plant and log
data for a representative exposure period.
Plant Results
The salient features of electrochemical noise time traces obtained from Monitoring Probes
1 and 2 were similar. The data files exhibited positive-going potential transients and positive-
going current transients that were associated with active SCC conditions. The average mag-
nitude of current transients was 48 nA, but occasionally approached 200 nA, and the average
size of the potential transients was 1.0 mV. Periods of pitting were associated with a change
in the direction of the transients to the negative direction for both current and potential. An
absence of significant transients indicated periods when SCC or pitting was not occurring.
Typical examples of data traces are presented in Figs. 9 through 11. Unstable pitting is
characterized by sharp negative-going current transients as a result of film breakdown. The
signal returns to "baseline" once the passive film has reformed.
The corresponding potential transients showed an exponential-type recovery over a short
time period. Probe 3 was found to display consistently crevice-type behavior (Fig. 12) typ-
ified by a series of repetitive transients indicative of restricted diffusion. The time of recovery
to baseline levels was longer than for pitting corrosion.
Statistical analysis techniques normally used in conjunction with electrochemical noise
were not found to be particularly useful for identifying periods of high and low SCC activity.
Neither degree of localization, which is the ratio of the standard deviation (current) to rms
(current), nor MEM spectral analysis, was able to differentiate between SCC, pitting corro-
sion, and crevice corrosion.
The observation that positive-going transients are recorded during periods of SCC gave
an opportunity to use a simple algorithm to identify periods when the collected data signify
that SCC is occurring. The algorithm assesses SCC activity in terms of a function (F), which
is a measure of the frequency and magnitude of positive-going transients:
f(frequency, SCC/Intensity) = l/n EfT_ 7 Ai "Tt~ ~E . . . .
3t ' r
where
FIG. 8--Simplified process diagrams showing location of sensors.
TABLE 2---Summary of operating conditions at the probe locations.
Nominal Gas Composition
Temperature, Press, CO, CO2, CH4, H2, N2, PCO, PCO2,
~ kPa tool% mol% mol% mol% tool% kPa kPa
Probe ] 40 2660 1.7 12 36 36 Bal 45 319
Probe 2 40 1810 1.7 12 36 36 Bal 30 217
Probe 3 18 3600 1.7 12 36 36 Bal 61 432
n = number of t ransi ent s measured in the sampl er per i od (256 s),
Ai = peak hei ght of the t ransi ent s, ~A,
Gr i = st andard devi at i on of the current, and
i . , s = r oot mean square of the current.
The peak hei ght and number of t ransi ent s are onl y count ed when Oi/Ot and OE/Ot are bot h
positive.
Fi gur e 13 shows t ypi cal traces of SCC i nt ensi t y (F) in real t i me for Probes 1 and 2. Al so
i ncl uded in t he figure is the CO cont ent of t he process gas measured at the t i me of el ect ro-
chemi cal noi se moni t ori ng. Act i vi t y was hi ghest on Probe 2, and per i ods of i ncreased SCC
act i vi t y ( F) coul d be coor di nat ed wi t h i ncreases in the CO cont ent in the gas.
Di scussi on
Characterization of ECN During Periods of SCC
Met al l ogr aphy of C-ri ngs aft er exposure to the l aborat ory test envi ronment confi rmed the
presence of stress corrosi on cracks. The severity of SCC was est i mat ed from t he number
and dept h of cracks found in the speci mens. Those exposed to Gas Mi xt ur e 1 cont ai ned
more cracks t han speci mens exposed to Gas Mi xt ur e 2. Cr acks were al so mor e frequent and
deeper in the speci mens stressed to hi gher levels.
Scrut i ny of t he cor r espondi ng EN traces from the speci mens reveal ed an i ncrease in tran-
sient behavi or at hi gher levels of stress. At stress levels near to the yi el d stress of t he mat eri al ,
posi t i ve- goi ng pot ent i al and uni di rect i onal negat i ve- goi ng current t ransi ent s were i dent i fi ed
duri ng l aborat ory moni t ori ng. It was concl uded that t ransi ent behavi or of this t ype was
sympt omat i c of SCC.
The si gn of the current t ransi ent s was dependent upon whet her Wor ki ng 1 or Worki ng 2
made the st ressed el ect rode, but, in all cases, el ect rons flowed to the st ressed el ement .
Mechanism
The si gn of the current t ransi ent s recorded duri ng per i ods of SCC suggest ed that SCC
events were associ at ed wi t h an el ect r on- consumi ng react i on: cat hodi c di scharge on the
st ressed el ect rode. A cat hodi c- cont r ol l ed process is consi st ent wi t h a model for hydrogen
embr i t t l ement and is in agr eement with fract ographi c observat i ons in t hese syst ems (Fi g.
14). The ori gi n of the embr i t t l i ng hydr ogen is as fol l ows:
C02 + H20 =- FI2CO 3
DEBRUYN ET AL. ON ON-LI NE MONI TORI NG 225
a . , . , , , . , . .
-2.834
+I.320
8
- ~ A 4 0
e Ti me (seconds) 2048
Fig. 9: Probe 1. Pa s s i ve - no SCC
-17.91 -
g -
- 1 9 . 3 3 - -
- 1 3 0 . 0
-155.9
Fig. 10: Probe 1. SCC
, , I . . . . L, , . ,
0 Ti me (seconds) 102,
+16.15
"36.20
"1(/0.2
8
- 5 1 1 1 . 2
i i i
0 Ti me (seconds) 1024
Fig. 11: Probe 1.
Fig. 12: Probe 3.
Pitting Corrosion
+~a3s
A
: >
o
o.
+0.910
-7.990
=
- 2 2 . 4 2
.ti me (seconds) 1024
Crevicing
o
(J
g
0.00001
0.000001
1E-07
1E-08
1 E - 0 9
1E-10
1E-11
1E-12
01/10/92
O.0QO~l
0.000001
09/10/92
i
17110/92 25/10/92
Pr obe I
02/11/92
1F-07
1E-08
IE-09
I E-I 0
1E-11
IE-12 I
01 I10/92 09110/92
9
8
7
6
5
4
3
2
1
[
17110/92
Pr obe 2
25/10/92
0 n .
01/10/92 17/10/92 09110/92
Co mmo n t o
Pr obe s l & 2
OP-J11192
FI G. 13--Stress corrosion cracking activity and CO content monitored in the plant.
I
!
I
1
25/10/92 ~1t 92
FIG. 14--Fracture appearance of a carbon steel specimen stressed in a C0-C02-H20 environment.
H2CO 3 + e- ---, H'.a ~ + HCO 3
H2CO 3 ~ H + + HCO 3-
HCO3- =- H + + CO3 2-
Once a crack has been initiated by hydrogen embrittlement, the freshly exposed iron is
able to catalyze water reduction to hydroxyl ions and hydrogen atoms. The electrons con-
sumed in this process appear to be supplied by a discharge of the electrochemical double
layer at metal exposed to the bulk of the solution. This results in a spontaneous polarization
of the bulk metal surface to a more noble value measured as transients in the electrochemical
potential noise signal.
Electrochemical Noise Measurement to Identify Periods of SCC
During the period of on-line monitoring, intermittent episodes of stress corrosion cracking
were identifiable as were periods of pitting and crevice corrosion. To understand the reasons
for the variance, consider briefly the CO-C02-H20 system. Carbon monoxide and carbon
dioxide act as a chemical potentiostat with carbon monoxide the passivating agent and carbon
dioxide the principal corrodant. Additionally, SCC does not take place if water is absent.
Consequent l y, any process change that i nt erferes wi t h the absor bed CO passi vat i ng l ayer
influences the nature of the corrosi on observed.
SCC was obser ved to coi nci de wi t h i ncrement s in CO concent rat i on (Fig. 13), however,
little di fference was obser ved as a resul t of rai si ng the part i al pressure of CO f r om 30 t o 45
kPa. Lean gas mi xt ures l ow in carbon monoxi de favor pi t t i ng and crevi ci ng in exi st i ng
cracks, as evi denced by fluctuations bet ween per i ods of pi t t i ng and SCC on bot h probes
(Figs. 10 and 11).
Ot her process vari abl es that are capabl e of i nfl uenci ng the corrosi on behavi or are: carry-
over of wat er - sol ubl e aci d compounds (acet i c and pr opi oni c aci ds) that favors pi t t i ng and
hi gh t urbul ence and t emperat ure ( > 150~ t hat dest roy the CO passi vat i ng l ayer and pr omot e
corrosi on as a resul t of wet carbon di oxi de. The resul t i ng mesa corrosi on t akes its name
from the geogr aphi c feat ure it resembl es, consi st i ng of st eep-si ded pl at eaus. Operat i ng the
pl ant above the dew poi nt prevent s at t ack altogether.
Cr ack i ni t i at i on and pr opagat i on in t he CO-CO2-H20 syst em is si gni fi cant l y i nfl uenced by
process fluctuations t hat make the syst em amenabl e to i nvest i gat i on by on- l i ne moni t ori ng
t echni ques. El ect rochemi cal noi se has pr oved capabl e of di fferent i at i ng bet ween peri ods of
active SCC and others of no SCC act i vi t y in CO-CO2-H20 envi ronment s.
Conclusions
El ect rochemi cal current and pot ent i al noi se moni t ori ng of st ressed el ect rodes exposed to
a CO-CO2-H20 envi ronment gi ve charact eri st i cs noi se traces that can be det ect ed bot h in
the l aborat ory and on-l i ne.
The si gn of the current and pot ent i al t ransi ent s suggest ed that cracki ng in this syst em was
due to hydr ogen embr i t t l ement rather than anodi c di ssol ut i on.
The pl ant moni t ori ng was abl e to i dent i fy peri ods when the servi ce condi t i ons favored
SCC, pi t t i ng, and cr evi ce corrosi on.
Lean gas mi xt ures low in carbon monoxi de favor pitting. Hi gher concent rat i ons of CO
pr omot e SCC.
There is an opport uni t y to use el ect rochemi cal noi se dat a gat hered on-l i ne to opt i mi ze the
operat i on of t he pl ant to mi ni mi ze the ri sk of SCC.
In pract i ce, it was found that process changes to operat e the pl ant out si de t he i dent i fi ed
SCC scenari o were l i mi t ed. The i nvest i gat i on, however, has proven to Mossgas t hat peri ods
when the envi ronment wi l l support SCC can be identified. Thi s assi st ed the pl anni ng of
r egul ar i nspect i on wor k for t he earl y det ect i on of cracki ng in cri t i cal lines.
References
[1] Berry, W. E. and Payer, J. H., Proceedings of the 6th Symposium on Line Pipe Research, American
Gas Association, Texas, 1979, pp. 251-268.
[2] Kowaka, M. and Nagata, S., Corrosion, Vol. 32, No. 10, 1978, pp. 396-401.
[3] Brown, A., Harrison, J. T., and Wilkins, R., paper presented at the Conference on Stress Corrosion
Cracking and Hydrogen Embrittlement of Iron Base Alloys, 12-16 June 1973.
[4] Hannah, I. M., Ph.D. thesis, UMIST, Manchester, 1991.
[5] Dunlop, A. K. and Olson, E. E., "Inhibition of Stress Corrosion Cracking of Steel in Aqueous
CO/CO 2 Environments," in Proceedings of the Sixth International Congress on Metallic Corrosion,
1975, pp. 332-342.
[6] Zanki, A. L., Gill, J. S., and Dawson, J. L., "Electrochemical Noise Measurements on Mild Steel
in 0.5 M Sulfuric Acid," in Electrochemical Methods in Corrosion Research, M. Duprat, Ed.,
Materials Science Forum, Vol. 8, 1986, pp. 463-476.
[7] Lotto, C. A. and Cottis, R. A., "Electrochemical Noise Generation During Stress Corrosion Crack-
ing of Alpha-Brass," Corrosion, Vol. 43, No. 8, Aug. 1987, pp. 499-505.
DEBRUYN ET AL. ON ON-LI NE MONI TORI NG 229
[8] Lotto, C. A. and Cottis, R. A., "Electrochemical Noise Generation During Stress Corrosion Crack-
ing of High Strength Aluminum AA 7075-T6 Alloys," Corrosion, Vol. 45, No. 2, Feb. 1989,
p. 136.
[9] Lotto, C. A. and Cottis, R. A., "Electrochemical Noise Generation During SCC of a High Strength
Carbon Steel," Corrosion, Jan. 1990, pp. 12-19.
[10] Schmitt, G. and Rothman, B., "Corrosion of Unalloyed and Low Alloyed Steels in Carbonic Acid
Solutions," Werkstoffe and Korrosion, Vol. 29, 1978, p. 816.
[11] Schmitt, G., "Fundamental Aspects of CO2 Corrosion," Paper 53, Corrosion ' 83, NACE, 1983.
Mi c hae l A. Winters, l Pat ri ck S. N. St okes, 2 and He nr y F. Ni chol s ~
Simultaneous Corrosion and Fouling
Monitoring Under Heat Transfer in Cooling
Water Systems
REFERENCE: Winters, M. A., Stokes, E S. N., and Nichols, H. E, "Simultaneous Corro-
sion and Fouling Monitoring Under Heat Transfer in Cooling Water Systems," Electro-
chemical Noise Measurement f or Corrosion Applications, ASTM STP 1277, Jeffery R. Keams,
John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., American
Society for Testing and Materials, 1996, pp. 230-246.
ABSTRACT: Corrosion and fouling in cooling water systems can potentially reduce heat-
transfer capability, increase maintenance costs, reduce plant availability, and contaminate pro
cess lines. Conventional monitoring systems have measured corrosion and fouling separately.
Fouling monitors alone are not able to indicate real-time corrosion activity beneath surface
deposits. Traditionally, corrosion information has been derived from destructive evaluation of
heat exchanger tubes, weight loss coupons, and probes under nonheat flux conditions. To
overcome these shortcomings, a monitoring system has been developed that measures corrosion
and fouling simultaneously. By using electrochemical noise measurement technology, the sys-
tem is particularly sensitive to detecting localized corrosion beneath a fouled surface, a major
and frequent mode of corrosion failure in heat exchangers. Development of the system has
progressed from field trials with a prototype unit to a commercially available system. This
paper reports and discusses the most recent evaluation of the system at Amoco's Corporate
Research facility in Naperville, Illinois, focusing on the sensitivity of electrochemical noise
measurement in detecting localized corrosion (pitting and so forth) on a heat transfer surface
in a cooling water environment.
KEYWORDS: fouling, under-deposit corrosion, electrochemical noise measurement, heat
exchangers
Inadequate control of cooling water treatment programs results in high operating and
maintenance costs in many situations. Pitting corrosion, scaling, and microbial fouling cause
damage to the installation and result in efficiency losses. Heat transfer surfaces are especially
prone to fouling and associated corrosion damage. A major drawback of field monitors has
been the inability to indicate real-time corrosion activity beneath fouled deposits. In the past,
it has been necessary to destructively evaluate heat exchanger tubes or rely on the results of
coupons and probes exposed under nonrepresentative conditions, for example, without heat
flux conditions, or both. Higher operating temperatures promote scaling and microbial growth
(up to =50~ which subsequently impedes access of a corrosion inhibitor to the heat
transfer surfaces. This can result in high rates of localized corrosion (pitting attack), which
is not detected by conventional control instrumentation. A combined corrosion and fouling
monitoring instrument (CFM500 Unit) has been recently developed that incorporates state-
Water technology specialist, Amoco Corp., WEC, 3700 Bay Area Blvd., Houston, TX 77058.
2 Business development manager, CML, Manchester M15 6SZ, UK.
3 Corrosion specialist, Amoco Corp., P.O. Box 3011, Naperville, IL 60566.
2 3 0
Www.astIII.OFg
WINTERS ET AL. ON SIMULTANEOUS CORROSION 231
of-the-art electrochemical techniques for corrosion assessment under in-plant service con-
ditions. This paper reports and discusses recent results from a "shakedown" evaluation of
the system at the Amoco Corporate Research Center before commercial use at an Amoco
chemical plant. This paper summarizes the continuing evolution of the monitoring technology
being used to evaluate corrosion behavior on a heat transfer surface.
Instrumentation
The system is comprised of a miniature heat exchanger (incorporating an integrated cor-
rosion sensor arrangement), an electronic flow and heat control unit, and a data collection
device that is linked to an electronic storage device (Fig. 1). The heat exchanger uses a
segmented tube (typically carbon steel). Tube segments are externally coated with heat trans-
fer paste and mechanically clamped in an electrically heated block. A side stream of cooling
water is fed through the exchanger and a paddlewheel flow meter enables the flow to be
FIG. 1--Schematic representation of the corrosion and fouling monitoring system (CFM500 unit).
mai nt ai ned bet ween 0.15 and 4.6 ms -~, whi ch equat es to Reynol ds numbers bet ween
100 000 and 100 000. The flow is kept wi t hi n +_0.02 ms -I of t he set value. The ot her
vari abl e that may be set is ei t her heat t ransfer rate or wal l t emperat ure. Pl at i num resi st ance
t emper at ur e det ect ors (RTD) measure the t emperat ure of t he fluid and the t emperat ure of the
bl ock out si de the tube. The i nsi de wal l t emperat ure is cal cul at ed from t hese measurement s.
I f t he heat t ransfer rat e is set, then as t he surface of t he t ube fouls, t he wal l t emper at ur e wi l l
ri se to mai nt ai n the set heat rate. I f the wal l t emperat ure is set, the heat i ng rat e woul d
decrease to mai nt ai n the set wal l t emper at ur e as the resi st ance to heat t ransfer i ncreases.
Maki ng al l owances for convect i ve and conduct i ve resi st ance, changes in heat t ransfer resi s-
t ance (HTR) from that of the cl ean surface condi t i on are found anal yt i cal l y. Measur ed val ues
of vari abl es, scanned every minute, are fed t o a personal comput er for storage. Heat t ransfer
rat e can be set bet ween 50 and 1000 W. Thi s equates to a t ypi cal ski n t emperat ure bet ween
30 and 90~ The heat t ransfer rate is set t ypi cal l y at 200 W.
In conj unct i on wi t h the foul i ng tendency, t he corrosi on i nformat i on is obt ai ned (by means
of an i nt egrat ed sensor array) usi ng four el ect r ochemi cal t echni ques that make measurement s
si mul t aneousl y under heat flux: zero resi st ance ammet r y ( ZRA) , el ect r ochemi cal current
noi se (ECN), el ect r ochemi cal pot ent i al noi se (EPN), and l i near pol ar i zat i on resi st ance (LPR).
Zer o resi st ance ammet r y has been used convent i onal l y to det er mi ne the gal vani c current
bet ween t wo di ssi mi l ar el ect rodes, but may be al so used to det er mi ne the current bet ween
t wo nomi nal l y i dent i cal el ect rodes. It has been found t hat "i dent i cal " el ect rodes nor mal l y
have di fferent bal ances of anodi c and cat hodi c areas and hence t ake up sl i ght l y di fferent
pot ent i al s. When the el ect r odes are coupl ed vi a the ZRA, a measur abl e current wi l l flow.
The ZRA out put is t he root mean square ( RMS) of t he ZRA current. The DC val ue of the
current dur i ng act i ve cor r osi on is proport i onal t o t he corrosi on act i vi t y in progress on the
el ect rodes [1].
The EPN t echni que measures l ow-l evel r andom fluctuations of the corrosi on pot ent i al
bet ween t wo nomi nal l y i dent i cal el ect rodes. The fluctuations are usual l y of l ow ampl i t ude,
l ess than a mi l l i vol t , and of l ow frequency, in the range of 1 Hz and bel ow [2]. The EPN
measur ement out put is a l ow frequency bandpass filtered RMS value. The EPN measur ement
provi des dat a that can be correl at ed wi t h t he mode of corrosi on attack, because the r andom
fluctuations recorded are rel at ed to surface corrosi on event s/ act i vi t i es. The si gnat ures of
pi t t i ng corrosi on and crevi ce at t ack are especi al l y clear. For a fi xed el ect r ode area, it has
been shown t hat dat a obt ai ned at t he free cor r osi on pot ent i al can be rel at ed to t he degr ee of
l ocal i zed at t ack occurri ng at t he t i me of measur ement [3]. The el ect rochemi cal noi se t ech-
niques are sensi t i ve to the onset of uni form at t ack (general corrosi on) and can charact eri ze
pr opagat i on of pi t t i ng or cr evi ce corrosi on. The ECN measur ement t echni que is si mi l ar to
EPN measurement , except t hat fl uct uat i ons in t he coupl i ng current bet ween t he t wo si mi l ar
el ect rodes, t ypi cal l y less than 1 CA, are r ecor ded and anal yzed. The out put is a l ow-frequency
bandpass filtered RMS val ue (DC and hi gh-frequency AC component s removed). It corre-
sponds to the l ow-l evel frequency noi se (the di fferent i al of the ZRA signal), whi ch is part
of the ZRA signal, but has a much l ower ampl i t ude when general corrosi on is occurri ng.
ZRA t i mes records compl ement the i nformat i on obt ai ned by EPN and ECN measurement s.
Passi ve fi l m breakdown, for exampl e, is char act er i zed by sporadi c t ransi ent s in t he current
flow [3]. These current s are drawn from any avai l abl e cat hodi c site, i ncl udi ng t hose of the
second el ect rode, and the current t ransi ent s are obser ved vi a the ZRA.
It is possi bl e to rel at e el ect r ochemi cal current and pot ent i al noi se to l ocal i zed at t ack pr o-
pensi t y [4]. The l ocal at t ack fact or is det er mi ned from the rat i o of t he ECN measur ement
val ue and t he ZRA out put value. Thi s rat i o gi ves an i ndi cat i on of the st ochast i c nat ure of
t he processes occurri ng on t he el ect r ode surface. When this val ue is low, that is, 0.001, the
at t ack is l i kel y to be general in nature because this rat i o i ndi cat es a rel at i vel y gaussi an
distribution of the electrochemical events. Pit initiation events, whi ch are identifiable as low-
level transients in the EPN (<1 mV) and ECN (<0. 1 I~A) traces, indicate when the system
is becomi ng unstable. At this point, the local attack factor will begin to increase (as the ECN
measurement increases against a relatively stable ZRA value) depending on the amplitude
and frequency of the events. The stochastic nature of the installation process produces a
more Poisson-type behavior in which the limit is indicated by the levels of the ECN and
ZRA being very similar, that is, the local attack factor approaches a value of 1. This reflects
film instability, which invariably relates to chemistry or hydrodynami c changes or both in
the corrosion process. The value of the local attack factor will increase to perhaps 0.01 for
low-level activity. When pits begin to propagate (active pitting), several features will become
noticeable. The electrochemical potential noise (EPN) level will increase dramatically t o
values >1 mV. The electrochemical current noise (ECN) activity will increase t o >0. 1 I~A.
The ZRA will begin to show signs of transients, which correspond with the ECN activity.
The local attack factor will rise to values >0. 1 and may reach a maxi mum value of 1. Pit
death is associated with general cessation of local activity as indicated by a decrease in the
frequency of events and signal amplitudes. In the extreme case in which very active pit
propagation occurs, the overall amplitude of the signals will stay high, and the local attack
factor may drop slightly.
ECN and EPN are also used to obtain the resistance noise (R, ) value [2]. This value is
used to estimate corrosion rates from the Stern-Geary approximation [5,6]. Unlike the linear
polarization resistance (LPR) technique, the electrochemical noise techniques are nonpertur-
bative: No extemat voltage or current is applied. The potential and current measurements
that were made are due to naturally occurring, spontaneous fluctuations associated with the
corrosion processes taking place on the surface of the material.
Linear polarization resistance is a DC met hod used for measurement of uniform corrosion
[ASTM Practice for Conduct i ng Pot ent i odynami c Polarization Resistance Measurements
(G 59)]. The technique assesses the electrode potential versus current relationship close to
the corrosion potential. This is achieved by monitoring the external current flow between
two nominally identical electrodes held at a known potential difference. The difference is
kept small, typically 10 mV, and the change of potential relative to the change of current
gives the polarization resistance R p . The corrosion current is then given by the simple rela-
tionship (again from Stern-Geary):
ioo~r = B / R e
where B is a polarization constant dependent on the type of metal or alloy used for the
electrode probe and on the environment. The LPR met hod is used extensively for prediction
of general or uniform corrosion rates but has limited value in the presence of scales or
deposits, which can introduce an increased resistance as can low-conductivity electrolytes.
The technique is also insensitive to localized corrosion.
Applications
The CFM500 unit gives real-time corrosion information on fouled heat transfer surfaces.
The unit gives a continuous online indication of the corrosion rate, local attack factor (pitting
tendency), and the heat transfer resistance (HTR fouling tendency) on a single graphical
output. The data are also stored for more detailed retrospective evaluation. In the past, the
heat flux and flow parameters of fouling monitors [ 7 - 9 ] have been set to encourage contin-
uous fouling, that is, high heat flux and low flow. This mode of operation is known to be
sensitive t o small changes in water treatment chemistry, pH, and so forth, in terms of im-
mediate changes in the fouling tendency that may occur. Conditions of operation can also
be set t o mimic a critical heat exchanger, thus tracking fouling at a key location in the
cooling system. By using the CFM500, this will allow the corrosion reading to be used as
an alarm for both corrosion and fouling changes because the corrosion readings are sensitive
enough to be a good indication of minute changes in fouling behavior. I f operated under
nonrepresentative (heavy) fouling conditions, the CFM500 system is likely to indicate unduly
high rates of corrosion that are not representative of the heat exchanger unit. However, the
"posi t i ve fouling mode" operation may be acceptable i f the water treatment inhibits under-
deposit corrosion. Otherwise, the information can be misleading.
In the past, there has been a tendency to consider that foul ed/ scal ed heat transfer surfaces
are protected by the presence of the scale. This assumption has been shown to be misplaced
by the recent experiences/results from the field studies. Fouling has an immediate and sig-
nificant impact on the surface corrosion condition. Operation of the unit such that it mimics
critical heat exchanger conditions is therefore imperative to obtain a representative indication
of corrosion activity in that location.
Res ul t s
Introduction
Laboratory and field trials on the prot ot ype CFM500 unit have been carried out previously
and are reported elsewhere [10,11]. This paper reports on the most recent evaluation on the
fully commercialized unit at the Amoco Corporate Research facility in Naperville, Illinois.
The CFM500 unit was installed in a pilot plant cooling water system within the research
and development facility. Throughout this evaluation period, a number of operational para-
meters were changed to investigate the relationship between flow, wall temperature, and
localized and general corrosion attack. The effect of operational upsets, such as chlorine
overfeed or inhibitor underfeed on the corrosion and fouling behavior, was also investigated.
The CFM500 unit was installed in the hot return line of a recirculating cool i ng water
system fed with municipal makeup water. Typical recirculating cooling water quality was
pH 8.5 t o 9.0, alkalinity 300 to 350 ppm as cal ci um carbonate (CaCO3), calcium 280 to 320
ppm as CaCO3, and total dissolved solids (TDS) of 800 to 1200 ppm equating to a Langelier
Scale Index (LSI--CaCO 3 scaling tendency) between + 1.9 and +2. 4 at the estimated max-
i mum wall temperature of 43~ (110~ corresponding to a relatively "l i ght -dut y" service.
The cooling water was continuously treated with a zinc-molybdate-based program incorpo-
rating zinc mol ybdat e as primary carbon steel corrosion inhibitor and tolytriazole (TTA) as
a "copper al l oy" corrosion inhibitor coupled with hydroxyet hyl enedi phosphoni c acid
(HEDP) and a compl ex pol ymer for scale deposit control and particulate dispersancy. Chlo-
rine was also fed on a periodic basis to control microbiological activity.
Baseline Tests
The CFM500 unit was initially set up with a constant heat input of 300 W and a flow
rate of 0.76 ms- t to generate a skin temperature of ~43~ and reflect the typical extreme
hydrodynami c operating conditions in the cooling water system. A typical set of raw data
collected during this phase of testing is illustrated in Fig. 2. These data show (1) no fouling
tendency as the cooling water quality falls well within the chemical treatment scale control
limit of +2. 5 LSI, (2) a mean general corrosion rate of 1.5 mpy, and (3) a local attack factor
of 0.0002, suggesting more generalized corrosion over this period.
W I N T E R S E T A L . O N S I M U L T A N E O U S C O R R O S I O N 235
U n i t # I
C o r r o s i o n D a t a
+I .OOE+Q1
L P K
M a x : + ! . 4 9 E + 0 3
M i n : + ! . 4 0 E + 0 3
M e a n : + ! . 4 6 E + 0 3
S D e v : + 2 . 2 2 E + 0 1
C V a r :
U n i t s : O h m s
~ 1 . 0 0 E - O 2
, ' 1 . p O E t 0 9 t ,
I r I I i r ~ r i r J r I i i ~ i r
Z R A
M a x : + 0 . 4 5 E - 0 5
M i n : + 0 . 3 9 E - 0 5
M e a n : + 0 . 4 2 E - 0 5
S D e v : + 0 . 2 3 E - 0 6
C V a r : + 0 . 1 3 E - 0 7
U n i t s : A m p s
t-1.00E-Q2
. I . 9 0 E . - ~ , ~ l ~ i r T 1 , , = r , l , , l ,
E P N
M a x : + 0 . 5 2 E - 0 5
M i n : + 0 . 2 0 E - 0 5
M e a n : + 0 . 3 0 E - 0 5
S D e v : + 0 . 4 5 E - 0 6
C V a r : + 0 . 6 9 E - 0 7
U n i t s : V o l t s
*'1 .nOE-O6
+ I J O O E r 1 O , r i I I r i f i I r I r r I I t = t x ,
ECN
M a x : + 0 . 1 2 E - 0 8
M i n : + 0 . 6 8 E - 0 9
M e a n : + 0 . 8 3 E - 0 9
S D e v : + 0 . 6 6 E - ! 0
C V a r : + 0 . 5 3 E - I I
U n i t s : A m p s
I . . , 1 , 0 0 ~ , , , , - 0 5 , i ' 9 f r r ' : ! ' ~ [ , T I ; . , , T
0 0 : 0 0 T i m e O f D a y 2 4 : 0 0
FIG. 2--24-h time record of raw corrosion and summary data recorded during baseline tests.
E R N
M a x : + 5 . 5 9 E + 0 3
M i n : + 2 . 2 0 E + 0 3
M e a n : + 3 . 6 5 E + Q 3
S D e v : + 5 . 6 8 E + 0 2
C V a r : + 8 . 8 3 E + 0 1
U n i t s : O h m s
U n i t # i
C F M 5 0 0 S u m m a _ ~ y
1 0
0 r I I ] J l I t I f I I I I i ] I I I 1 T
; I . OOE.,.O0
+ 1 . D O E : - 0 3 ,
9 ( - 0 .&OE-02
; , r I r I I , I t ' I I , * r I i
00:00 Time Of Day ,?.&:O0
FIG. 2--Continued.
G e n e r a l R a t e
M a x : + l . 5 0 E + 0 0
M i n : ~ 1 . 4 2 E + 0 0
M e a n : + 1 . 4 5 E + 0 0
S D e v : + 0 . 2 2 E - 0 !
C V a r : + 0 . 3 5 E - 0 3
U n i t s : m p y
L o c a l A t t a c k F a c t o r
M a x : + 0 . 2 7 E - 0 3
M i n : + 0 . 1 5 E - 0 3
M e a n : + 0 . 2 0 E - 0 3
S D e v : + 0 . 1 9 E - 0 4
C V a r : + 0 . 1 8 E - 0 5
U n i t s :
H T R
M a x : + 0 . 3 0 E - 0 4
M i n : - 0 . 7 0 E - 0 4
M e a / l : - 0 . l i E - 0 4
S D e v : + 0 . i 2 E - 0 4
C V a r : - 0 . 1 4 E - 0 4
i t s : h r . f t 2 . ~
t
Biocide Overfeed
The unit has demonstrated the sensitivity of corrosion behavior to biocide overfeed in a
previous field trial [10]. A similar response to chlorine overfeed was observed during the
evaluation at Naperville and is illustrated in Fig. 3. This time record shows the increase in
local attack factor corresponding to a period of chlorine overfeed in the cooling water system.
The general rate of corrosion (derived from the LPR measurement) did not detect the in-
creased localized activity. Transients in the local attack factor trend corresponded to transients
in the ECN, whi ch is symptomatic of pitting behavior. Not e that the chlorine overfeed was
detected by an operator who was able to identify quickly the process excursion by the online
visual histogram ( VI SI COR TM software) display of the localized corrosion activity.
Several local corrosion transients related to chlorine overfeed occurred during the early
stages of testing. Once recognized, the operating remedy was to reduce chlorine feed and
blowdown, as indicated by the reduction in local attack factor in the last 2 h of the time
record (see Fig. 3). Ultimately, the incidence of upsets lessened as a result of tighter chlorine
feed control implemented t o minimize chemical wast age/ overfeed and potential corrosion.
U n i t # I
C F M 5 0 0 S u m m a r y
1 0
J
r
I I ~ I , , , I I ~ 7 I I I I
M ~ x : + ! . 4 3 E + 0 0
M i n : + 0 . 2 1 E - 0 i
M e a n : + 1 . 3 7 E + 0 0
S D e v : ~ 0 . 4 6 E - 0 !
C V a r : + 0 . 1 5 E - 0 2
U n i t s : m p y
" 1 . O O E + O 0
R e d u c t i o n
C h l o r i n e o v e r f l o w in c h l o r i n e
f e e d ",
9 ~ ~ . . . . . .~.~.,,.~,~,~,.~.,. ~ . . . . . .
* 1 . ~ 0 E r 0 3 , r i I J , , T T I f f r ~ ~ I , ~ ~ , ~
M a x : + 0 . 1 4 E - 0 1
M i n : + 0 . 9 7 E - 0 3
M e a n : + 0 . 5 5 E - 0 2
S D e v : + 0 . ! 5 E - 0 2
C V a r : + 0 . 4 3 E - 0 3
U n i t s :
~.4oE-o2 h ~ f R
- - M a x : + 0 . 2 0 E - 0 4
M i n : - 0 . 6 0 E - 0 4
- - M e a n : - 0 . 1 5 E - 0 4
S D e v : + 0 . 1 1 E - 0 4
C V a r : - 0 . 8 0 E - 0 5
Z n i t s : h r . f t = . ~
i
- 1 .,OOE:'O 3 , r , [ , , r l , I , I J [ , ! a , , r T J
0 0 : 0 0 T i m e O f D a y 2 4 : 0 0
FIG. 3- - 24- h time record of corrosion and f oul i ng summary data showing the increase in the local
attack f act or as a result o f chlorine overfeed and the remedial effect o f reducing chlorine feed.
St at i c Test
Before i sol at i ng t he unit wi t h ent r apped cool i ng water, zero flow, and zer o appl i ed heat
flux, the CFM500 was i nt ent i onal l y f oul ed/ s cal ed by i ncreasi ng the heat i nput ( ~400 W)
and reduci ng flow vel oci t y ( - 0 . 3 0 ms-1) to generat e a ski n t emperat ure of - 8 2 ~ ( - 180~
LSI ~ +3. 0) and cl ear l y to exceed the scal e cont rol capabi l i t y of the cool i ng wat er treatment.
Ul t i mat el y, the "s hut - i n" si mul at i on was desi gned to reflect a t ypi cal operat i ng si t uat i on in
whi ch a " f oul ed" unit is shut in for some t i me, such as duri ng a mai nt enance shutdown. To
si mul at e st agnant condi t i ons in a heat exchanger, t he heat flux and flow t hrough the unit was
shut off compl et el y for seven days. The cool i ng wat er in t he model heat exchanger was
i sol at ed, and corrosi on moni t or i ng in the st agnant condi t i ons cont i nued. Af t er appr oxi mat el y
t hree days of passi ve behavi or, t ransi ent s in the current and pot ent i al noi se (i ndi cat i ve of
l ocal i zed corrosi on) were r ecor ded (Fi g. 4). The operat i ng dat a showed a cl ear combi nat i on
of general and l ocal i zed corrosi on: a st ep reduct i on of general corrosi on as rel at ed to LPR
measur ement and a cor r espondi ng i ncrease in l ocal i zed cor r osi on t endency as r el at ed to EPN
and ECN measurement . Af t er the shut -i n test, t he modes of corrosi on were confi rmed to be
i ni t i at i on of l ocal i zed cor r osi on beneat h deposi t s based on t he observat i on of the presence
U n i t # I
+ 1 ~ 0 0 E + 0 1
E n O E * 0 5 , r I l I r
~
O O E - 0 2
O e ~ 0 9 , , , I r
r I I I I I I r ! r f I I
r e f I r i I I
" I . O O E - O 2

D
~ , ~ 9 ,--.,7-..r M-' : ' ~ l ~
t " p , i i i , l I i
+1.00E~I
L P R
M a x : + 1 . 7 8 E + 0 4
M i n : + I . 1 9 E + 0 3
M e a n : + 2 . 8 8 E + 0 3
S D e v : + 4 . 4 0 E + 0 3
C V a r : + 6 . 7 3 E + 0 3
U n i t s : O h m s
Z R A
M a x : + 0 . 3 5 E - 0 6
M i n : + 0 . 2 7 E - 0 6
M e a n : + 0 . 3 ! E - 0 6
S D e v : + 0 . 2 0 E - 0 7
C V a r : + 0 . 1 3 E - 0 8
U n i t s : A m p s
E P N
M a x : + 0 . 4 6 E - 0 5
M i n : + l . 0 0 E - 0 6
M e a n : + 0 . 2 0 E - 0 5
S D e v : + 0 . 6 2 E - 0 6
C V a r : + 0 . 2 0 E - 0 6
E C N
M a x : + 0 . 4 2 E - 0 8
M i n : + I . 0 0 E - 1 0
M e a n : + 0 . 2 0 E - 0 9
S D e v :
C V a r : + 0 . 2 5 E - 0 9
U n i t s : A m p s
M a x : + 2 . 0 8 E + 0 4
M i n : + 8 . 3 7 E + 0 2
M e a n : + 9 . 6 2 E + 0 3
S D e v : + 4 . 7 7 E + 0 3
C V a r : + 2 . 3 7 E + 0 3
U n i t s : O h m s
~ - 1 . , 0 0 E + 0 5 , v ~ I r r f ~ i i t i 1 . , , i ,
0 0 : 0 0 T i m e O f O a y 2 4 : 0 0
FIG. 4--24-h time record of raw corrosion data collected during the static test illustrating current
and potential noise transients associated with localized corrosion.
WINTERS ET AL. ON SIMULTANEOUS CORROSION 2 3 9
of active tubercles on the internal tube surface (activity was verified by boroscopic exami-
nation) and an inordinately high iron content of precipitated solids in the "ent rapped" cooling
water. It is t hought that the interaction of general and localized corrosion reflects suppression
of generalized corrosion by cathodic protection of locally corroding regions.
Acidification/Repassivation
After the shut-in test, the unit was run with a heat input of 400 W and a flow rate of 0.46
ms -~ to induce a positive fouling tendency. Increasing the fouling rate in the unit, which
resulted in an increased heat transfer resistance value, was intended to assess online repas-
sivation of under-deposit corrosion under nonopt i mum operating conditions as well as to
enhance fouling on the CFM500 unit in preparation for online acidification. Acidification of
the cool i ng water with hydrochloric acid was designed to simulate an on-stream descaling
treatment or an extreme acid pH excursion. Summary fouling and corrosion data before and
after acidizing are seen in Fig. 6. Before acidizing, the CFM500 unit flow rate was progres-
sively reduced to 0. 20 ms-~ to induce the heaviest fouling tendency and assess the impact
of running at very low flow rates. Immediately before acidification, the CFM500 unit was
internally inspected by a boroscopic unit to establish the baseline "f oul ed" condition. This
inspection found:
1. that the CFM500 unit was heavily scaled with a whi t e/ t an deposit, subsequently found
to be mainly cal ci um carbonate;
2. that the previously active tubercles formed during the shut-in test had been repassivated
in-service; and
3. that deposits had been mechanically dislodged by the boroscope, which woul d explain
the reduced level of HTR after internal inspection.
After inspection, the CFM500 unit was returned to service and the cool i ng water pH
depressed to < 1 with hydrochloric acid. Figure 6 illustrates the increased corrosion activity
on all the electrochemical techniques during the acidification. This corresponded to a max-
i mum general corrosion rate of 2.25 mm/ year . The HTR time record (see Fig. 5) also clearly
shows the effect of mechanical removal of deposit during inspection and the effect of acid-
ification. Mechanical cleaning of the unit reduced HTR to - 3 0 percentile of t he range
between the baseline HTR and full-scale HTR value. For the first 11 h of this time record
(Fig. 5), the HTR value was full scale. After the addition of acid, the HTR trace returned
to a baseline level once all the deposit had been removed.
After cessation of acidification, the CFM500 unit showed a repassivation trend, as illus-
trated by the downward trend in corrosion rate through the following day (Fig. 7). However,
an increased general rate of corrosion and local attack factor was seen the next day (Fig. 8).
Based on the unusually high level of general corrosion, the unit operator investigated and
found the main bl owdown valve was j ammed open, resulting in increased discharge to waste
and low inhibitor level in the cool i ng water. Remedyi ng this problem corrected the inhibitor
dosage and promot ed full repassivation of the CFM500 unit over the next 24 h.
Localized Corrosion Versus General Corrosion
On several occasions, transients in the electrochemical current and potential noise (with
associated transients in the local attack factor) correlated with instability in the LPR trace
(with associated increase in the polarization resistance and reduction in general corrosion
rate), as illustrated in Figs. 9 and 10. The initiation and growth of pits on the sensor surface
U n i ~ #1
I Q
- - A c i d i f i c a t i o n
0 , , r , J I I ; , , , ~ I
9 ' 1 . O Q E , ~ 3 Q
l i a I L t T r '
9 . - ~ . ~ . ~ .
- - 9 ' - ~ , i : ' , ~ : . ;
9 . - ~ . . . . - i . - " - ~ " ~ ; ~
1 ; P Q E F O 3 1 , ' l f , I , - . " ; " i k . . [ ,~ , t I "~ "
4 ~ . t ~ E - O 2
*~JO(]E = 0 3 r z :
00:00
[ r f r
L
I J 1 I r I I T : l I . T I I r i I i I
T i m e O f D a y 2 4 : 0 0
M ~ x : + 8 . 9 9 E + 0 1
M i n : + 0 . 2 1 E - 0 i
M e a n : + 4 . 0 7 E + 0 0
S D e v : + 9 . 6 8 E + 0 0
C V a r : + 2 . 3 0 E + 0 1
U n i t s : m p y
L o c a l A t t a c k F a c t c r
M a x : + 0 . 4 3 E + 0 0
M i n : + 0 . 1 3 E - 0 4
M e a n : + 0 . 3 8 E - 0 2
S D e v : + 0 . 1 7 E - 0 1
C V a r : + 0 . 7 3 E - 0 1
U n i t s :
H T R
M a x : + 0 . 1 0 E + 0 0
M i n : - 0 . 3 6 E - 0 1
M e a n : + 0 . 2 3 E - 0 2
S D e v : + 0 . 5 0 E - 0 2
C V a r : + 0 . ! I E - 0 !
h i t s : h r . f t 2 . ~
J
Z32
r i I r I i i I ! r 1 I I r
B l o c k T e m p
M a x : + 2 . 2 2 E + 0 2
M i n : + 5 . 8 3 E + 0 !
M e a n : + 1 . 6 6 E + 0 2
S D e v : + 4 . 0 9 E + 0 1
C V a r : + I . 0 1 E + 0 1
U n i t s : ~
z3Z W a l l T e m p
M a x : + 2 . 1 9 E + 0 2
M i n : + 5 . 8 3 E + 0 1
_ _ .:~ M e a n : + I . 6 3 E + 0 2
-; ~ S D e v : + 4 . 0 4 E + 0 !
\ '
! ; ~ ' ~ - - ~ " - ~ " ~ C V a r : + ! . 0 0 E + 0 1
!. . U n i t s : ~
1 2 , , , , , , L r L 9 I , L I i ~ i
FIG. 5- - 24- h time record of corrosion and foaling summary data showing the increased general rate
of corrosion during acidification, the reduction in HTR, and the effect of acidification on the wall
temperature.
WINTERS ET AL. ON SIMULTANEOUS CORROSI ON 2 4 1
U n i t # !
r 1 . O O E ' , " O 1
- - A c i d i f i c a t i o n
~ I . , Q O E * 0 5 ,
+ 1 . O O E - O 2
+ 1 . , O O E ; ' 0 9 t I I I I I 1 I I I
+ 1 . 0 0 E - Q 2 " ' . : . ; :
~ v
i ~ . '
t i t ~ I I ~ i 1 i
- - ~=.~ . ~.. - ~ 3 ~ : ~ s t h , ~
- ' I O E ; - 0 6 t I l I r l I r i I = ] t = I I I I 1 l [
. ~ O ( ] E - 0 6 - . - . . r
_ : - : : - . . . t . ~
L P R
M a x : + 5 . 4 4 E + 0 3
M i n : + 2 . 3 5 E + G I
M e a n : + 1 . 2 0 E + 0 3
S D e v : . 7 . 3 0 E + 0 2
C V a r : + 4 . 4 5 E + 0 2
Units : O h m s
Z R A
M a x : + 0 . 4 9 E - 0 3
M i n : + 0 . 3 8 E - 0 6
M e a / l : + 0 . 1 6 E - 0 4
$ D e v : + 0 . 3 0 E - 0 4
C V a r : + 0 . 5 5 E - 0 4
U n i t s : A m p s
E P N
M a x : + 0 . 7 0 E - 0 2
M i n : + 0 . 2 6 E - 0 5
M e a n : + 0 . 9 0 E - 0 4
S D e v : + 0 . 5 9 E - 0 3
C V a r : + 0 . 3 9 E - 0 2
ECN
M a x : + 0 , 9 6 E - 0 6
M i n : + 0 . 1 9 E - 0 9
M e a n : + 0 . 3 3 E - 0 7
S D e v : + 0 . 1 3 E - 0 6
C V a r : + 0 . 5 2 E - 0 6
U n i t s : A m p s
~ 1 . 0 0 E + O l ~ i ~ l : ~ ,
_ _ ~ M a x : + I . 5 1 E + 0 7
~ ~ ; . _ ~ j : ~ , ~ : ~ , : : , : , ~ , M i n : + 1 . 6 3 E + 0 1
.-:~,---~,:.-:~,,~.~< ~.~:..tT~'~:-:;~', M e a ~ : + I . 3 6 E + 0 4
" ~ 9 .... " "" S D e v : + 4 . 0 1 E + 0 5
" r . : . ~ - . : ~ ~ . . . . ~. :.. ~-~ :, : .:./.:..~- C V a r : + I . 1 9 E + 0 7
- - . ' h A t : " " ' ~! 9 U n i t s : O h m s
' , I . B O E ~ . 0 5 i ' ' 1 I ~ I , :
9 ' = r ] ~ , t
O 0 : O O T i m e O f D a y Z & : O 0
F I G . 6- - 24- h time record of raw corrosion data collected during acidification illustrating the in-
creased activity on al l the electrochemical techniques.
U n i ~ # 1
1 0
r I I [ I I I [ I
M a x : + ~ . 4 6 E + 0 0
M i n : + I . 2 0 E + 0 0
M e a n : + 2 . 7 2 E - 0 0
S D e v : + I . 0 9 E + 0 0
C V a r : + 0 . 4 4 E + O O
U n i t s : m p v
+I .OOE~O
I 1 I ~ I I ' I l I [ ' l " I ; ' I " [ I I - - " ' "
M a x : + 0 . 2 0 E - 0 1
M i n : + 0 . 2 3 E - 0 3
M e a n : + 0 . 5 7 E - 0 3
S D e v : + 0 . 8 6 E - 0 3
C V a r : + 0 . 1 3 E - 0 2
U n i t s :
+0 . 4 0 E- 0 2
- :
" l . n 0 E , ' 0 3 1 , r I t r , , , I r , L , I I , , , , ,
00:00 Time Of Day Z4:00
M a x
M i n
M e a n
S D e v
C V a r
~ n i t s :
H T R
: + 0 . 5 5 E - 0 1
: - 0 . 1 6 E - 0 2
: + 0 . 2 7 E - 0 3
: + 0 . 1 5 E - 0 2
: + 0 . 8 0 E - 0 2
h r . f t =. Q F / B T ~
FIG. 7- - 24- h time record of corrosion and fouling summary data showing the downward trend in the
general corrosion rate during repassivation.
appear to protect cathodi cal l y the surrounding surface area and, consequentl y, i ncrease the
measured pol ari zati on resistance suggest i ng s ome associ at i on bet ween l ocal i zed and gener-
al i zed attack. Thi s type o f behavi or was observed onl i ne as wel l as during the shut-in test.
Moreover, the occurrence o f this behavi or on both the noi se and LPR measurements suggest s
that similar corrosi on processes occurred over all the corrosi on sensors.
Di s c us s i on
The results obtai ned during this eval uati on cl earl y demonstrate the capabi l i ty o f the c om-
bi ned corrosi on and f oul i ng moni tori ng syst em to moni t or corrosi on and differentiate type
o f attack under deposi ts, whi l e expos i ng the shortcomi ngs o f convent i onal moni t ori ng ap-
proaches. The i nformati on obtai ned f rom the el ect rochemi cal met hods o f corrosi on appraisal
has s hown that a cont i nuous i ndi cati on o f corrosi on status beneath a scal e or f oul i ng deposi t
can be obtained. The unit and the techni ques used therein have proven sensi ti ve in changes
in cool i ng water process and chemistry. Changes in l ocal attack factor and the general rate
o f corrosi on have gi ven an i nsi ght i nto the passi vat i on/ repassi vat i on behavi or o f the heat
WI NTERS ET AL. ON SI MULTANEOUS CORROSI ON 243
U n i t # I
1 0
O I : , , I 1 I [ J I I , 1 I T I I r
M a x : + 2 . 7 5 E + 0 0
M i n : + ! . 3 2 E + 0 0
M e a n : + 2 . 1 7 E + 0 0
S D e v : + 0 . 2 7 E + 0 0
C V a r : + 0 . 3 4 E - 0 !
U n i t s : m p y
+ 1 . OOE+Orl
m
. . . . . . . . . ~. ~-~ ;~;: : ~ : ~ . : ~ : ~ 2 ~ :~ " " " ~ ; : : ! ~ ~ ' : ~ : - U ' ~
9 , " I . D O E : : . O ] I ~ , I ' " ~, " r , ~ ' , , ~ , : - u ; ~ - 4 ~ ' ; ; ' ; " ~ , ' i ~ a ' ' ~ ' ~ ' ~ ' : ' ' ' x ' = - 5 ; ; ' v ; ' - i " ; " I l I I " l ~
+ O . , ; O E - O 2
M a x : + 0 . 5 4 E - 0 2
M i n : + 0 . 3 9 E - 0 3
M e a n : + 0 . 1 6 E - 0 2
S D e v :
C V a r : + 0 . 5 3 E - 0 3
U n i t s :
H T R
M a x : + 0 . 6 7 E - 0 3
M i n : - 0 . 1 8 E - 0 3
M e a n : + 0 . 1 8 E - 0 3
S D e v
C V a r
: + 0 . 5 6 E - 0 4 1
- - : + 0 . 1 7 E - 0 4
I J - I J ] O E r 0 3 , , ~ 1 , , , [ r r ~ ~ r ~ I r r , ~ L T
0 0 : 0 0 T i ~ of Day 2 4 . : 0 0
FIG. 8--24-h time record of corrosion and fouling summary data showing an increased general
corrosion rate and increased local attack factor as a result of low inhibitor level.
transfer surface during normal operati on and after process upsets such as bi oci de overf eed,
acidification, and so forth.
Severe l ocal i zed attack was not detected during this eval uati on al though s ome transient
bursts o f pitting behavi or were observed in the el ect rochemi cal noi s e measurement data.
Not e that the l ocal attack factor does not indicate rate but, in associ ati on wi th the rate
esti mates from LPR, can be used to provi de an i ndi cati on o f worst case pit penetration rates.
It i s difficult to esti mate actual pit penetration rates because the geomet ry and number o f
the pits were not determined, and, because pits have a l i fe c yc l e (birth, growth, and death),
the active l i fe o f a si ngl e pit is difficult to determine.
From the vi ewpoi nt o f corrosi on control , it is much more important to be aware o f s ys t em
stability and whether there is general corrosi on, pit initiation, or pit propagation. At the pit
initiation stage, there is no real criticality, but it i s an early warni ng sign. More important
operati onal l y is to kno w when initiation occurs and to track subsequent change. The key
steps are: ( l ) initiation (alarm), (2) repassivation ( no action), and (3) propagat i on- - s us t ai ned
or intensified l ocal i zed activity (action). The individual pit penetration rate esti mates need
interpretation because they may be very hi gh but the l i feti me may be so short as to be
244 E L E C T R OC H E MI C A L N OI S E ME A S U R E ME N T
U n i t # i
_ ~ O O E ' ~ ' O 1
[ , , , * ~ I , , , , , I , , , ,
I + 1 . 0 0 E - 0 2
- 2
!*1.p0Er09. = , I . . , , , , , I , ,
I I r I
L ~ R
M a x : + 1 . 5 2 E + 0 4
M i n : + 2 . 5 6 E + 0 3
M e a n : + 4 . 6 B E + 0 3
S D e v : + 2 . 7 1 E + 0 3
C V a r : + ! . 5 6 E + 0 3
U n i t s : O h m s
Z R A
M a x : + 0 . 2 0 E - 0 5
M i n : + 0 . ! 2 E - 0 5
M e a n : + 0 . 1 6 E - 0 5
S D e v : + 0 . 2 0 E - 0 6
C V a r : + 0 . 2 6 E - 0 7
U n i t s : A m p s
~ ' 1 . 0 0 6 - 0 2
E P N
M a x : + 0 . 9 5 E - 0 5
M i n : + 0 . 1 1 E - 0 ~
M e a n : + 0 . 1 ~ E - 0 5
S D e v : + 0 . 6 5 E - 0 6
C V a r : + 0 . 2 6 E - 0 6
I ' 1 . 0 0 E - 0 6
e 1 - ~ O E r l O l I , t f , * z 9 " ' J ~ ' ,~ I ~ I t ~ 1 I
E C N
M a x : + 0 . 3 1 E - 0 7
M i n : + 0 . 1 9 E - 0 8
M e a n : + 0 . 3 6 E - 0 8
S D e v : + 0 . 1 7 E - 0 8
C V a r : + 0 . 8 1 E - 0 9
U n i t s : A m p s
~' I . ~ 1
9 . . . . . , , . . . : : 9 . . . . " - . ~ -
+ I . ~ ] O E . * C ] 5 , I t I I L ~ I 9 ' E ~ :
( ] O : O 0 T i m e O f O a y 2 4 . : 0 0
E R N
M a x : + 1 . 4 8 E + 0 3
M i n : + 1 . 5 2 E
M e a n : + 4 . 8 0 E + 0 2
S D e v : + 1 . 4 1 E + 0 2
C V a r : + 4 . 1 5 E + 0 1
U n i t s : O h m s
FIG. 9- - 24- h time record o f raw corrosion data illustrating the current and pot ent i al noise transients
and LPR instability caused by localized corrosion.
WI NT E RS ET A L ON SI MUL T ANEOUS C O R R O S I O N 245
U n i t # l
10
, 0 , , , T I I I I I r I I ~ ' ~ ' ~ I - - ~ ' !
+I.00E+O0
- - " . - _
9 : . . . . . . . - : . - . . . . . : . , , i ? " " : . 3 : . ,
" J ] g E r 0 3 1 I I [ I I r I t / I r l I " 1 ~ [ r r " i " ' ~ [ " I "
*O.~E-OZ
I-1.DOErO 3r , , I , , , l , I r , , , [ I i i
00:00 Time Of O a y Z&:O0
M a x : + 0 . 8 2 E
M i n : + 0 . 1 4 E + 0 0
M e a n : + 0 . 5 9 E
S D e v : + 0 . 2 5 E + 0 0
C V a r : + 0 . 1 i E + 0 0
U n i t s : m p y
M a x : + 0 . 1 8 E - 0 Z
M i n : + 0 . 1 2 E - 0 2
M e a n : + 0 . 2 3 E - 0 2
S D e v : + 0 . 1 0 E - G 2
C V a r : + 0 . 4 4 E - 0 3
U n i t s :
Ma x
M i n
M e a n
S D e v
C V a r
[ n i t s :
blTR
: + 0 . 1 9 E - 0 2
: + 0 . 1 6 E - 0 2
: + 0 . 1 7 E - 0 2
: + 0 . 3 5 E - 0 4
: + 0 . 7 5 E - 0 6
h r . f ~ Z . O F / B ~ " 7 ~
I
i
FIG. 10- - 24- h t i me record o f corrosion and f oul i ng summary data showing the reduction in the
general corrosion rate and transient increases in the local attack factor.
insignificant; on the other hand, the pit penetration rate may be very significant i f attack i s
sustained. It is therefore consi dered to be dangerous to attempt to linearize pit penetration
rates, rather to use i ndi cati ons o f pitting initiation as a means o f process control to hel p
operati ons in a safe, nonpitting regi me.
So, what was learned about this particular cool i ng water syst em? Overall, it was f ound
that the normal c ool i ng water servi ce was not particularly aggressi ve from the standpoint o f
f oul i ng and related corrosi on activity. Indeed, under normal operating ( hydrodynami c) con-
ditions, the cool i ng water s howed no f oul i ng tendency and was not corrosi ve to carbon steel:
this was attributed to l ow chl ori de content and hi gh al kal i ni t y/ pH coupl ed wi th a hi ghl y
ef f ect i ve anodi c/ cat hodi c corrosi on inhibitor. Thi s was reflected by an average general cor-
rosi on rate o f - 0 . 0 1 2 5 mm/ y e a r ( f rom LPR data) and mi ni mal l ocal i zed attack seen on the
CFM500 unit during the trial. Thes e results compared favorabl y wi th corrosi on coupon re-
sults and post exposure assessment o f the CFM500 sensors: average general corrosi on rate
o f 0. 0025 mm/ y e a r wi th s ome l ocal i zed attack correspondi ng to a corrosi on rate o f 0. 125
mm/ ye ar .
Not wi t hst andi ng the general l y unaggressi ve nature of the c ool i ng water, it was possi bl e
t o sti mul ate f oul i ng on the CFM500 unit by appl yi ng higher heat duty or l ower fl ow rates
than that ordi nari l y exper i enced in the cool i ng wat er syst em or both. In doi ng this, it was
possi bl e to demonst rat e the sensi t i vi t y of the CFM500 to hydr odynami c changes of heat flux
and flow rat e as wel l as to verify the operat i ng l i mi t s and scal e cont rol capaci t y of the
chemi cal treatment.
In t erms of l ocal i zed corrosi on tendency, the cool i ng wat er showed some defi ni t e insta-
bi l i t y as a resul t of chl ori ne overfeed or i nhi bi t or underfeed or both. Accent uat ed in the
presence of deposi t s, the l ocal i zed corrosi on act i vi t y faci l i t at ed opt i mi zat i on of bot h the
chl ori ne and i nhi bi t or t reat ment , and rei nforced t he need to mai nt ai n effect i ve scal e deposi t
control. Cri t i cal l y, this l ocal i zed corrosi on sensi t i vi t y offers a means of i dent i fyi ng an unsta-
bl e operat i ng situation before any si gni fi cant at t ack has mani fest ed. Of concern was t he fact
that LPR r emai ned unaffect ed by corrosi vi t y changes ot her than duri ng the aci di fi cat i on
t reat ment . Al so, the evi dent reduct i on of LPR measur ement coi nci dent wi t h l ocal i zed cor-
rosi on act i vi t y quest i ons the convent i onal i nt erpret at i on of LPR measur ement data.
Conclusions
1. Moni t or i ng corrosi on and foul i ng si mul t aneousl y in a cool i ng wat er syst em enhances
the capabi l i t y of measuri ng represent at i ve corrosi on that occurs beneat h scal e or foul i ng
deposi t s when compar ed wi t h convent i onal techniques.
2. The combi ned moni t or i ng approach has been used to st udy t he oper at i ng l i mi t s of
chl ori ne (as a bi oci de) and some corrosi on i nhi bi t ors used to cont rol cor r osi on and
foul i ng in a pi l ot pl ant cool i ng wat er system.
3. The CP-M500 unit has proven sensi t i ve to t he onset of l ocal i zed corrosi on and has
i dent i fi ed unst abl e operat i ng in the pi l ot pl ant cool i ng wat er syst ems.
4, The CFM500 unit has faci l i t at ed the opt i mi zat i on of bi oci de and i nhi bi t or t reat ment in
a pi l ot pl ant envi ronment and has been used effect i vel y to cont rol scal e deposi t i on in
this part i cul ar appl i cat i on.
5. Duri ng this study, suppressi on in general corrosi on rat e (as deri ved from LPR mea-
surement ) has oft en cor r esponded to i ncreased l ocal i zed act i vi t y as det ect ed by el ec-
t rochemi cal noi se measurement s. Thi s may reflect t he cat hodi c prot ect i on afforded by
l ocal l y corrodi ng regi ons and is si gni fi cant in t erms of whi ch t echni ques are used to
assess bot h general and l ocal i zed corrosi on damage.
References
[2] Dawson, J. L., Eden, D. A., and Hladky, K., "Electrochemical Noi se--Some New Developments
in Corrosion Monitoring," paper presented at UK Corrosion 83, Birmingham, UK, CCEJV/ICorrSt,
Nov. 1983.
[3] Dawson, J. L., Farrell, D. M., Aylott, P. J., and Hladky, K., Paper 31, in Corrosion 89, NACE, New
Orleans, LA, 1989.
[4] Hladky, K., UK Patent Application 8,200,196, Jan. 1982, US Patent 4,575,678, March 1986.
[5] Eden, D. A., Dawson, J. L., and John, D. G., UK Patent Application 8,611,518, May 1986.
[6] Stem, M. and Geary, A. J., Journal of the Electrochemical Society, Vol. 56, 1957, p. 104.
[7] DATS Fouling Monitoring System, Bridger Scientific, Inc., P.O. Box 1923, Sandwich, MA 02563.
[8] Zuniga, P. O., Klee, H., Miller, K., and Winters, M. A., Corrosion 90, NACE, Houston, TX, 1990.
[9] Zuniga, P. O., Miller, K., and Winters, M. A., "Cooling Water Fouling Monitor Senses Upsets,
Evaluates Changes." Chemical Processing, April 1990.
[10] Winters, M. A., Stokes, P. S. N., Zuniga, P. O., and Schlottenmier, D. J., Corrosion Science, Vol.
35, No. 5-8, 1993, pp. 1667-1675.
[11] Winters, M. A., Stokes, P. S. N., Zuniga, P. O., and Schlottenmier, D. J., Paper 392, Corrosion 93,
NACE, New Orleans, 1993.
Di gby D. Macdonal d, l Chun Liu, 2 and Mi chael P. Manahan, S i r : . 3
Electrochemical Noise Measurements
on Carbon and Stainless Steels in
High Subcritical and Supercritical
Aqueous Environments
REFERENCE: Macdonald, D. D., Liu, C., and Manahan, M. E, St., " El e c t r o c h e mi c a l No i s e
Me a s u r e me n t s o n Ca r b o n a n d St a i nl e s s St e e l s i n Hi g h Subc r i t i c a l a n d Supe r c r i t i c a l Aq u e -
o u s Env i r o nme nt s , " Electrochemical Noise Measurement for Corrosion Applications, ASTM
STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John
ABSTRACT: The electrochemical noise induced in a pair of corroding carbon steel probes in
simulated heat transport circuit fluids of a supercritical fossil-fueled power plant at temperatures
up to 550~ and at pressures as high as 276 bar (4000 psi) was measured as a function of
oxygen concentration, flow rate, temperature, and pressure. Additionally, electrochemical noise
measurement (ENM) was explored as a means of detecting and monitoring stress corrosion
cracking in sensitized Type 304 SS in high-temperature water (up to 288~ Experimental
results from these studies indicate that the electrochemical noise induced from corrosion of
steels in high-temperature aqueous systems can be measured in a reproducible manner. The
magnitude of the electrochemical noise responds sensibly to changes in the chemical and
physical properties of the fluid, and the pattern of the electrochemical noise contains infor-
mation on the nature of the corrosion processes that occur, including general corrosion, pitting
attack, and stress corrosion cracking.
KE Y WOR D S : electrochemical noise, supercritical aqueous system, corrosion, pitting attack,
stress corrosion cracking
The effect i ve cont r ol of cor r osi on and of mass t r anspor t and deposi t i on i n the heat t r anspor t
ci rcui t s of t her mal and nucl ear power pl ant s requi res t he cont i nuous moni t or i ng of key wat er
chemi st r y and syst em paramet ers, not abl y t he pH, concent r at i ons of oxygen and hydr ogen,
cor r osi on pot ent i al , conduct i vi t y, and cor r osi on activity. Nor mal l y, onl y a few of t hese pa-
r amet er s are moni t or ed, and meas ur ement s are gener al l y rest ri ct ed t o ambi ent t emper at ur e
and pressure. Consequent l y, onl y a part i al pi ct ur e of t he devel opment of damagi ng condi t i ons
i n an oper at i ng pl ant can be obt ai ned, becaus e t he r el evant par amet er s are not det er mi ned
under t he act ual oper at i ng condi t i ons. Thi s pr obl em has been r ecogni zed for ma ny years,
but t he l ack of sensor s for moni t or i ng key par amet er s at el evat ed t emper at ur es and pressures
has i mpeded t he i nt r oduct i on of i n si t u moni t or i ng syst ems.
1 Professor of materials science and engineering and director, Center for Advanced Materials, The
Pennsylvania State University, University Park, PA 16802.
2 Research associate, Center for Advanced Materials, The Pennsylvania State University, University
Park, PA 16802.
3 President, MPM Research and Consulting, PO Box 840, Lemont, PA 16851.
247
Www.astIII.OFg
All general and localized corrosion processes, such as general corrosion, pitting attack,
crevice corrosion, and stress corrosion cracking, result in fluctuations in the free corrosion
potential and in the anodic and cathodic partial currents. These fluctuations are observed as
electrochemical noise that is thought to contain significant information about both the activity
and mechani sm of attack. Electrochemical noise measurement (ENM) has been used exten-
sively for monitoring corrosion activity in a variety of systems [1-17], although the sources
of the electrochemical noise are still not clearly defined [2 ]. Some believe that the electro-
chemical noise is due principally to the formation of hydrogen bubbles [3], at least in the
case of general corrosion, or the absorption of hydrogen by the first layers of metal beneath
the surface of passive film [4 ]. In the case of localized corrosion, such as pitting attack,
crevice corrosion [5-9], and stress corrosion cracki ng [10-12], the noise frequently arises
from discrete events that can be related to the development of damage. In some instances,
it has been suggested that ENM can distinguish between different corrosion mechanisms
[14]. However, in most cases, the experiments are preliminary, and viable theories for the
origin of the noise have yet to be developed [3].
A program has been established in this laboratory to develop in situ monitors for moni-
toring various physical, chemical, and electrochemical parameters in the heat transport cir-
cuits of thermal power plants. The monitors include reference electrodes, pH sensors, probes
for measuring the concentrations of oxygen and hydrogen in water, probes for measuring
electrochemical noise, and a fracture unit to detect the onset of stress corrosion cracking
(SCC) and to moni t or its propagation rate, all of which operate at elevated temperatures and
pressures [18,19]. In this paper, we describe the development of an electrochemical noise
analyzer (ENA) for monitoring corrosion activity at temperatures above the critical point of
water. The ENA monitors fluctuations in the galvanic coupling current between identical
electrodes, which, in this case, were fabricated from carbon steel. In parallel, we have also
explored ENM as a means of detecting and monitoring stress corrosion cracking in sensitized
Type 304 stainless steel (SS) (UNS $30400) in water at temperatures up to 288~ using an
experimental setup that isolates the external surfaces of a precracked compact tension (CT)
specimen from the environment, but couples the specimen to cathodes located on the spec-
imen sides.
Experimental Apparatus
The ENA developed in this study is shown schematically in Fig. 1. The analyzer operates
on an analog basis for simplicity and to maintain a very low cost. The circuit consists of a
] H ea ter [
FIG. 1--Schematic of the electrochemical noise analyzer (ZRA = zero resistance ammeter, RM = root
mean square).
MACDONALD ET AL. ON CARBON AND STAINLESS STEELS 249
zero resistance ammeter (ZRA), the output of whi ch passes through a band-pass filter with
independently adjustable upper and lower roll-off frequencies. The lower roll-off frequency
can be set at 1 Hz, 10 Hz, 100 Hz, and 1 KHz, whereas the upper roll-off frequency can be
set at 10 Hz, 100 Hz, 1 KHz, and 10 KHz. Because there is virtually no electrochemical
noise at very high frequencies, we have selected 10 KHz as the high limit of upper-roll-off
frequency. Therefore, the bandwidth of the signals that pass this filter can be selected between
10 Hz and 10 KHz. Amplification of the signals can be regulated through a gain from 0.1
to 2000. In addition, the sensitivity of the analyzer can be regulated by adjusting the response
time over the range from 250 ms to 10 s. All of these regulation functions are accessible
from the front panel of the analyzer. After amplification by the ZRA (AMP-05) and filtering
by the band pass filter, the signal is processed by a root -mean square module (RMS, AD636)
and is then presented on a digital display and on a strip-chart recorder. The electronic circuits
are carefully shielded to exclude electronic noise from the environment and from sources
other than the probes. The probes consisted of two identical SAE- AI SI 1013 (UNS GI 0130)
carbon steel rods (+ = 1.3 mm), with 12 mm being exposed to the environment through a
high-pressure fitting in the autoclave. The probe assembly was located in a pressure vessel
that was part of a once-through, recirculating, high-temperature/high-pressure loop capable
of operating at temperatures to 550~ and at pressures to 310 bar ( - 4 5 0 0 psi or 31.0 MPa).
A schematic of the loop is presented in Fig. 2. The operating parameters of the loop are
such that the density of water in the supercritical region at 550~ could be varied from zero
to less than 0.1 g / c m 3 [20].
For stress corrosion cracking studies on sensitized Type 304 SS in high-temperature water,
a precracked compact tension (CT) specimen was loaded in a high-temperature, high-pressure
cell and was isolated (except for the crack) from the environment using baked-on polytet-
rafluoroethylene (PTFE). The specimen was coupled to side-mounted cathodes via a ZRA
(Fig. 3). Because the cathodic reaction occurs on the external surface (in this case, the
cathode) whereas the anodic reaction is restricted to the crack, a current is detected by the
ZRA. It is the electrochemical noise in this coupling current that is of prime interest in this
work [21, 22].
Resul t s and Di s cus s i on
Electrochemical noise measurements on corrodi ng carbon steel were carried out at high
subcritical (T < 374.12~ and at supercritical (T > 374.12~ aqueous environment under
N2
inlet
Valve
to drain
_
r~e~s~e l ~ ~ . ~ l --H-ZZ-I
reducing ~ ~ u 2 Pm~
cheek valve[I ...... II II - I
Test Cell
i
Heater
_ / Hi P fitting
[ I ~ Carbon steel probes
' ~ x (to ENA)
Modified
Cooling Conax
coil fitting
FIG. 2--Experimental loop (HPLC = high pressure liquid chromatography, HiP = High Pressure
Equipment Co.).
Cathode over
specimen side
surface
J,
To ZRA
T
Machi ned Notch
Beneath Cat hode
I
Side Back
FIG. 3--Schematic of CT specimen: (1) Specimen, (2) Clevis, (3) Cathode, and (4) PTFE washer.
conditions of temperature, pressure, and oxygen concentration that simulate those in the heat
transport circuits of supercritical power plants. However, because of the limited capacity of
the high pressure liquid chromat ography (HPLC) pump used to pressurize the system, it was
not possible to simulate the flow conditions fully. Nevertheless, our studies demonstrate that
ENM is a powerful means of monitoring corrosion activity, as will become evident from the
material presented below.
In the present design of the monitoring system, we used an RMS module for signal
conditioning. The purpose of this module was to convert any sinusoidal component in the
electrochemical noise into a DC output that could be easily displayed on a digital meter.
However, the output was found to be "noi sy, " thereby indicating that the electrochemical
noise generated on the carbon steel is stochastic in nature and is not simply sinusoidal (Fig.
4). Other possible sources that may be responsible for the measured noise have been dis-
cussed, and it was demonstrated that the measured noise is indeed from the corrodi ng probes
in high-temperature aqueous environment [20]. As shown below, the electrochemical noise
consists of principally of low-frequency component s (1 to l 0 Hz), as determined by the
bandpass filter.
An important finding of this study is that electrochemical noise is generated on carbon
steel corrodi ng in low density (p < 0.1 g / c m 3) supercritical water, and that the noise can be
used to moni t or corrosion activity. To our knowledge, the present work represents the first
0
e-
r
10'
J ~ a n n i ~ I 1 6 o " C I C o o t i n a
I
I
1 "
E
0 6 0 0 0 1 2 1 ~ 1 8 0 0 0
" l ' b n e i s )
FIG. 4- - Evol ut i on of electrochemical current noise induced by corrosion o f A/ S / 1 0 1 3 carbon steel
during an experimental heat i ng-cool i ng cycle (oxygen pressure = 40 psi (0.28 MPa), in-vessel
pressure = 1200 psi (8.28 MPa), gain = 1000, l ower roll-off f requency = 1 Hz, upper roll-off
f requency = 10 Hz).
attempt to perform ENM in supercritical aqueous systems and, hence, to demonstrate the
potential application of this technique in supercritical power plant technology.
Analysis of the electrochemical current noise from the compact tension test indicates that
the electrochemical current noise consists of domi nant low-frequency components of - l to
2 Hz, depending on the load. This finding is consistent with crack growth being due to
discrete events (jumps), perhaps resulting from an embrittlement phenomenon at the crack
tip. Details of this work are given below.
The Ef f e c t o f Temper at ur e
The general response of the electrochemical noise as a function of temperature in sub-
critical water (liquid phase) is shown in Fig. 4. The amplitude of the electrochemical noise
is observed to increase with increasing temperature. This is an expected response, because
elevation in temperature increases the activity of the corrosion process. The observed elec-
trochemical noise is found to be reversible with respect to temperature, in that lowering
temperature decreases the amplitude of the noise in a predictable and reversible manner.
In the supercritical region, however, the amplitude of the electrochemical noise versus
temperature is found to be complicated (Fig. 5). It is observed that the amplitude of the
electrochemical noise initially increases with increasing temperature to a temperature of
- 434~ but then decreases as the temperature increases to 550~ The origin of the maxi-
mum in the electrochemical noise is most likely due to the compet i ng effects of temperature
and water density on the corrosion processes. Thus, we speculate that, for T < 434~ the
change in the noise amplitude is due principally to the effect of increasing temperature on
the kinetics of the corrosion process, but at higher temperatures, decreasing water density
exerts a dominant effect. Not e that in this figure and subsequent figures the error bars rep-
resent the range of fluctuation in the noise signal as observed over a 1-min period for the
indicated gain and for the stated rol l -off frequencies.
The Ef f e c t o f Pr e s s ur e
Pressure is found to have strong impact on the amplitude of the electrochemical noise
from corroding carbon steel measured in supercritical water (Fig. 6). Our experiments have
2 . 0 1. 00
. . . . . . . . . I . . . . . . . . . I . . . . . . . . . I . . . . . . . . . I . . . . . . . . .
I [Oe] = 0 . 0 0 6 ppm
g"
E / P = 3 5 5 0 p s i
T [ Flow r a t e 172.5 ml / mi n
v 1.5 ~ 0. 75
gmt . ude
,-. 1 . 0 0 . 5 0 o
t.O
r t'*3
0 II
2 ,',
~ '
" 0. 5 - 0. 25 "N
. , . o e - *
0 . 0 . . . . . . . . i . . . . . . . . . ; . . . . . . . . . I . . . . . . . . . r . . . . . . . . . O.00
3 . 5 0 4( 30 4 5 0 5 0 0 5 5 0 6 0 0
T e mp e r a t u r e (~
FIG. 5--Dependence of electrochemical current noise amplitude for AISI 1013 carbon steel in su-
percritical water as a function of temperature (data compiled from three heating-cooling cycles), and
water density (water density data from Ref 15 ).
shown that t he ampl i t ude of the el ect r ochemi cal noi se i ncreases sharpl y wi t h i ncreasi ng
pressure of t he supercri t i cal fluid to 241 bar (3500 psi or 24.1 MPa), cor r espondi ng to a
densi t y i ncrease from 0.062 to 0.091 g / c m 3. The i ncrease in the noi se ampl i t ude wi t h in-
creasi ng densi t y is pr esumabl y due to ei t her an i ncrease in conduct i vi t y of the fluid bet ween
t he carbon steel probes or to an i ncrease in the effect i ve concent rat i on of oxygen at the
met al surface, or bot h (see Fi g. 6).
The Effect of Stirring and Flow Rate
The sol ut i on in t he aut ocl ave coul d be agi t at ed t hrough a st i rrer act i vat ed by magnet i c
drive. Exper i ment s carri ed out at subcri t i cal t emperat ures demonst r at e that st i rri ng has a
strong qual i t at i ve influence on the ampl i t ude of the el ect rochemi cal noi se (Fi g. 7). Thus,
activation of the stirrer, in this part i cul ar case, results in a great er than fivefold i ncrease in
the noi se ampl i t ude, pr esumabl y a result of enhanced mass transport. By varyi ng the pump
speed, it was al so possi bl e to regul at e the flow rate. The i nfl uence of mass flow rat e t hrough
the test cel l i nner channel di amet er 3.18 mm on the el ect rochemi cal noi se has been st udi ed
over the range of 0 to 20 mL/ mi n, and the ampl i t ude of the noi se was found to i ncrease
modest l y as t he flow rate was i ncreased over the accessi bl e range (Fi g. 8). Part of the
observed i ncrease in the noi se ampl i t ude may be at t ri but ed to a modi fi cat i on of the hydro-
dynami cs of t he syst em, but it is al so l i kel y that t he hi gh flow rat es count eract the con-
sumpt i on of oxygen by corrosi on of the l oop wal l s (especi al l y in the hot zone), so that a
great er effect i ve oxygen concent rat i on is present in the vi ci ni t y of the pr obes at hi gher
flow rates. The dat a shown in Fi gs. 7 and 8 cl earl y demonst r at e the i mport ance of
MACDONALD ET AL ON CARBON AND STAINLESS STEELS 253
1.5
De n s i t y ( g / c m 3)
0. 061 0 . 0 7 4 0 . 0 9 1
. . . . . . . . . I . . . . . . . . . 1 . . . . . . . . . 1 . . . . . . . . .
~" [ 0o] = 0 . 0 0 6 p p m
E
- - - T = 4 8 1 o c
Fl ow r a t . e 12. 5 r n l / mi n
-~ 1. 0
1 1 ,
.1~ / /
( , 1
0 . 5
. =
0
0 9
e ~
__.n . . . . . . . . . ' . . . . . . . . . r . . . . . . . . . I . . . . . . . . .
2000 2500 5000 3500 4000
P r e s s u r e o f t h e s y s t e m ( p s i )
FIG. 6--Electrochemical current noise amplitude for AISI 1013 carbon steel in supercritical water
as a function of pressure (water density data from Ref 15).
hydr odynami c/ mas s t ransport effects in det er mi ni ng the ampl i t ude of the el ect r ochemi cal
current noi se i nduced by the corrosi on of carbon steel in the subcri t i cal and supercri t i cal
water.
The Effect of Oxygen Concentration
The effect of oxygen concent rat i on was st udi ed under bot h supercri t i cal and subcri t i cal
condi t i ons. The sol ut i on was pr epar ed to be sat urat ed wi t h pure oxygen (wi t h an oxygen
concent rat i on in t he sol ut i on [02] = - 3 2 ppm). The reservoi r was then sparged wi t h ni t rogen
to deaerat e t he wat er (see Fi g. 2). The pressure in t he sol ut i on reservoi r was mai nt ai ned
sl i ght l y hi gher than one at mosphere to prevent ai r f r om ent eri ng i nt o t he l ow- pr essur e sect i on
of the syst em. By varyi ng the ni t rogen bubbl i ng rate, the oxygen cont ent in t he sol ut i on
coul d be decr eased at a desi r ed rate. A t ypi cal deoxygenat i on curve is shown in Fi g. 9. The
oxygen concent rat i on was measured at ambi ent t emperat ure usi ng a commer ci al oxygen
probe ( I ngol d Model 170) at the out l et of an aut ocl ave aft er cool i ng the process stream.
Because a sl ow deaerat i on rate was chosen, and because of t he smal l i nner channel di amet er
and vol ume of the t est cel l (4) = 3.18 mm, effect i ve heat ed l engt h L = 101.6 mm), t he t i me
for the sol ut i on to flow from t he aut ocl ave to the oxygen probe was an or der of magni t ude
>
E
0
._.9,
0
10 i
No st m' m|
" r l mr
F I G. 7--E f f ect of sti rri ng on the el ectrochemi cal current noi se i nduced by corrosi on of A1Sl 1013
carbon steel in water at 244~ (oxygen pressure = 40 psi (0.28 MPa), i n-vessel pressure = 1200 psi
(8.28 MPa), gai n = 1000, l ower rol l -off frequency = 1 Hz, upper rol l -off frequency = 10 Hz).
s ma l l e r t han t he t i me r e qui r e d f or a n o t i c e a b l e c h a n g e i n t he o x y g e n c o n c e n t r a t i o n ( s e e Fi g.
9 f or a t y p i c a l de a e r a t i ng p r o c e s s ) . Th u s , w e c o n c l u d e t hat t he o x y g e n c o n c e n t r a t i o n me a -
s ur e d b y t he o x y g e n pr o be r e pr e s e nt s t he o x y g e n c o n t e n t i n t he s o l u t i o n wi t h i n t he t e s t c e l l ,
t o a r e a s o n a b l e a p p r o x i ma t i o n .
2. 0 . . . . , . . . . . . . . . . . . . . . . . . , . . . .
E
0
t.-
o
E
@
c-
O
0
-d
e ~
1.5
].0
T = 4 7 0 " C
P = 3 5 0 0 p s i
[ 0 2 ] = 0 . 4 p p m
t J - l J i
0. 5 , , . , I . . . . . . , , , , I , , , , , , , , , f ' ' ' '
4 5 G
Fl ow r a c e ( m l / m i n )
FIG. 8--Electrochemical current noise from AI SI 1013 carbon steel in supercritical water as a f unc-
tion of flow rate (lower roll-off frequency = 1 Hz, upper roll-off frequency = 10 Hz).
MACDONALD ET AL, ON CARBON AND STAINLESS STEELS 255
E
e~
3
O
O
= 2
t _
r "
o
t -
O 1
o
x
0
0
T=410~ ml / mi n
I P = 3 5 0 0 pm
LFlow r a t e 8. 4
.~ A O
U 2UU 4 0 0 ~UU 8(.)(.-) 100U
Ti me (rai n),
FI G. 9- - Typi cal deoxygenation curve as determined by sparging the reservoir tank with nitrogen
([02 ] measured at the outlet of the autoclave at ambient temperature).
o
e -
" ~ . 0 1
. 00,
. 0 0 0 1 9 - ~ . . . . . , . . . . . . . . J . . . . . . . ~ . . . . . . . ", . . . . . .
. 0 0 1 , 0 1 . 1 1 1 0 1 0 0
Oxygen concentr=ion (ppm)
FIG. l O- - Evol ut i on o f electrochemical current noise induced by corrosion of AI Sl 1013 carbon steel
as a f unct i on o f oxygen concentration in the solution (T = 250~ in-vessel pressure = 1400 psi (9.66
MPa), gain = I, lower roll-off f requency = I Hz, upper roll-off f requency = 10 Hz).
In subcritical systems, the magnitude of the electrochemical noise is found to decrease
monotonically with decreasing oxygen concentration in the solution (Fig. 10). Although the
data are of only moderate precision, particularly at high oxygen concentrations, the noise
amplitude is found to be represented by
RMS = 0.01 [02] 0.5 (1)
where RMS is the root-mean square of the noise amplitude, in units of millivolts and [02]
is the oxygen concentration in ppm. The square root dependence of RMS on [02] appears
to indicate that the amplitude of the noise is not controlled by the diffusion of oxygen to
the surface, because, in that case, a linear dependence might be expected. However, the
stirring and flow-rate experiments discussed above clearly demonstrate a mass transport-
controlled component in the observed electrochemical noise. At the present time and until
the mechanism of noise generation is better understood, the observed relationship between
the electrochemical noise amplitude and the oxygen concentration should be considered
purely empirical in nature.
In supercritical systems (Fig. 11), the amplitude of the noise was again found to decrease
monotonically with decreasing oxygen concentration for [02] > 0.1 ppm, with approximately
the same exponent (0.5) as observed at lower temperatures. However, for [02] < 0.1 ppm,
the amplitude was found to be independent of [O2], although the magnitude of the fluctua-
tions in the noise (as expressed by the error bars) renders this observation only semiquan-
titative in nature. We note that in this experiment the density of the water is less than 0.1
g/cm 3, compared with -0. 75 g/cm 3 for the subcritical system shown in Fig. 10. Thus, the
data shown in Fig. 11 may well indicate that the amplitude of the noise at low oxygen level
o
' ' . . . . . . . . '
[hieh b a n d pass I K H z I
/ T = 4 1 0 * C / T
I P = a s o o I T , I ,
i i i . . . . . I
0.01
FIG. 11--Electrochemical current noise amplitude f or AISI 1013 carbon steel in supercritical water
as a function of oxygen concentration.
0 . 0 1 , . . . . . . a . . . . . . . . r . . . . . . . . i . . . . . .
0 . 0 0 1 0 . 1 I 1 0 1 0 0
[02] in the solution (ppm)
is controlled by the density of the fluid (and presumably, by the resistance of the fluid
between the probes), and that the effect of oxygen become apparent only for [02] > 0.1
ppm. This interpretation is consistent with a model that supposes that an electrical analog
for the probes used in this study consists of a series of resistance (Rs), representing the
resistance between the probes that is inversely related to the density of the fluid, and two
(identical) interfacial independences that describe the corrosion processes that occur at the
surface of the two probes. For [O2] < 0.1 ppm, the impedance of the cell is dominated by
R s 9
The Fr equency Composi t i on o f the El ect r ochemi cal Noi se
It has been demonstrated in previous studies [18, 19] that at high oxygen concentrations
and at subcritical temperatures the electrochemical noise generated by the corrosion of carbon
steel is composed mainly of low-frequency components (1 to 10 Hz). A similar distribution
in frequency of the components of the electrochemical noise from corroding carbon steel is
observed at supercritical temperatures, as shown in Fig. 12. The spectra show that the noise
is composed principally of low-frequency components (1 to 10 Hz). Although no literature
data are available for the corrosion of carbon steel in supercritical water, data from the
literature for systems at ambient temperature show that the electrochemical noise consists
principally of low-frequency components [2,14,17].
Observat i on o f Pi t t i ng Corrosi on
During the experiments carried out in this work, certain patterns in the electrochemical
noise could be associated with specific experimental conditions. Figure 13 shows two dif-
g
2
o
-g
0. 15
0. 10
0.05
,=.
I T=4IO~ P=3500 psi
[02]= 7 ppb
Flow r at e 8.4 ml / mi n
0.00
1-10 I0- lO0 IO0-1K IK-IO K
Fr equency r ange (Hz)
FIG. 12--The distribution in frequency of the electrochemical noise from AISI 1013 carbon steel in
supercritical water (lower roll-off frequency = 1 ttz, upper roll-off frequency = 10 KHz, gain = 1 ).
D
E
2
50
4O
30
2O
lO
_,/
0
P-- 1 ~0 )si
:!
i
1
I
a. ,.# ,~.
1 2
P=2750 psi
5 1 2 3 4 5
Tune (min)
50
40
30
20
I0
0
FIG. 13--The electrochemical current noise from AISI 1013 carbon steel as a function of time in
supercritical water (T = 405~ [02] = ppb, flow rate = 4.6 mL/min, gain = 20, lower roll-off
frequency = 1 Hz, upper roll off frequency = 10 KHz, Pressure = 2150 and 2750 psi (14.84 and 18.98
MPa ), as indicated).
ferent patterns in the magnitude of the electrochemical noise that were observed under two
different set of conditions. Shown on the right-hand side of Fig. 13 is a continuous, steady
level of the electrochemical noise, whereas on the left-hand side, the noise pattern consists
of a series of spikes. The only difference between the two cases is the pressure in the test
cell. In searching for a relationship between the noise pattern and the mechanism of corro-
sion, the surface morphology of the steel specimens before and after exposing to the high-
temperature water was examined. (Scanning electron microscopy (SEM) micrographs shown
in Figs. 14 and 15 clearly demonstrate the occurrence of pitting corrosion during these
FIG. 14--Surface morphology of the AISI 1013 carbon steel specimen before the experiment.
9 Copyright 1994 by NACE International. All Rights Reserved by NACE; reprinted with permission.
FIG. 15--Surface morphology of the AISI 1013 carbon steel specimen after the experiment. 9 Copy-
right 1994 by NACE International. All Rights Reserved by NACE; reprinted with permission.
experiments. Although the electrochemical noise pattern shown on the left-hand side in Fig.
13 cannot be directly linked to the occurrence of pitting corrosion because SEM examination
was performed at ambient temperature after disassembling the system, the experiments
clearly associate the occurrence of discrete events in the noise pattern with localized cor-
rosion, as has been found for ambient temperature systems [8].
As noted in the Experimental Apparatus section, in these studies we monitored the cou-
pling current that flows from the crack to the external cathodes where it is consumed by
oxygen reduction. Thus, the observed current and the noise contained therein are expected
to reflect the properties of the source (the crack) as well as the properties of the sink (the
external cathodes). We have previously shown [18,19] that corrosion-resistant alloys, such
as stainless steel (and presumably nickel and nickel alloys), exhibit low-amplitude noise in
oxygenated pure water that is random in character. Therefore, any structure in the coupling
current noise is presumed to arise from processes occurring within the crack. A typical
coupling current versus time trace on loading and subsequently unloading the specimen is
shown in Fig. 16. Thus, on increasing the load to a stress intensity (K0 of 27.5 MPa.m '/2,
the ZRA current initially increases to a plateau at - 50 I~A, corresponding to the growth of
the crack through the highly damaged plastic zone ahead of the crack (as a result of fatigue
precracking). Subsequently, the ZRA current increases to - 150 to 200 I~A as the crack
propagates through the virgin steel. On unloading, the current immediately decreases to the
previously observed unloaded value of - - 50 I~A (this is not zero because the nickel cath-
odes were lightly platinized, so that a galvanic couple exists in the system; Fig. 17).
The data acquisition rate used for recording the trace shown in Fig. 16 was low (0.07 Hz)
so that the noise observed on the trace does not accurately reflect the actual noise structure.
On increasing the acquisition rate to 100 Hz (in this case, for a specimen with Type 304 SS
cathodes), a remarkable pattern is discerned (see Fig. 17). Thus, the noise consists of a
dominant components of ~2 Hz with periodic bursts of higher frequency noise at about
Water Temperature = 252 Degrees C
Pressure = 82.7 bar
7 0 0 2 5 0
6 0 0 K~ = 27.5 ~a ~m 2 0 0
( , . )
<E
5 0 0 1 5 0 : 1 .
C
4oo lOO
300 5 0
2 0 0 ~ 0
100 ~ - 5 0
0 ~ o t u t n p - 1 0 0
0 . 0 0 0 . 5 0 1 . 0 0 1 . 5 0 2 . 0 0 2 . 5 0 3 . 0 0 3 . 5 0 4 . 0 0
Time (hours)
FIG. 16- - Load and ZRA coupling current versus time f or the initial l oadi ng/ unl oadi ng of a pre-
cracked specimen (platinized nickel cathode, test conducted at a temperature o f 252~ pressure 1200
psi [82. 7 MPa ]).
every 5 s. Because of t he ext r aor di nar y nature of this noi se pattern, we went to consi der abl e
l engt hs to ensure that the noi se was real. Thus, the noi se was no l onger obser ved when the
speci men was unl oaded to K l < 11 MPA-m 1/2, whi ch apparent l y rul es out i nduct i on from
ext ernal sources. Al so, the noi se (at K~ > 11 MPA. m 1~) persi st ed when vari ous el ect ri cal
equi pment was swi t ched off, i ncl udi ng the servohydraul i c l oad frame (not e t hat t he noi se in
the l oad is due to the acqui si t i on syst em and does not si gni fy fluctuations in t he act ual load).
Fi nal l y, t he frequency of t he noi se in t he coupl i ng current (i ncl udi ng bot h the backgr ound
noi se and t he frequency of the bursts) was found to i ncrease wi t h i ncr easi ng/ ( 1 [22], whi ch
cl ear l y shows that the noi se ori gi nat es from the crack.
The effect of l oadi ng to successi vel y hi gher stress i nt ensi t i es is shown in Fi g. 18. Loadi ng
to K[ = 11 MPa. m ~/2 di d not cause a response in t he ZRA current, but l oadi ng to 22 MPa-m 1/z
did, t hereby i ndi cat i ng that the val ue of the cri t i cal stress i nt ensi t y for stress corrosi on crack-
i ng (K~scc) is bet ween 10 and 22 MPa. m 1/2. Furt hermore, stress i nt ensi t i es above 33 MPa. m 1~2
di d not cause a si gni fi cant i ncrease in t he ZRA current, whi ch is consi st ent wi t h the current
ari si ng from crack growt h in the St age II regi on for this al l oy/ envi r onment combi nat i on
[23]. These observat i ons further support our cont ent i on that t he ZRA coupl i ng current (in-
cl udi ng the noi se) arises di rect l y from crack advance, and hence, that the structure of the
noi se pr ovi des val uabl e i nformat i on on the mi cr oscopi c processes that l ead t o cr ack pr opa-
gation. Fi nal l y, the magni t ude of the coupl i ng current is much great er than that expect ed
t heoret i cal l y, i f it is assumed that al l of the current ori gi nat es from the crack tip. However,
as we show el sewhere [22], the current can be account ed for i f it is assumed t hat crack
advance occurs by mi cr oscopi c brittle fracture events, wi t h the current ori gi nat i ng from the
crack t i p and the near-t i p crack flanks. In this model , the mean current is apparent l y domi -
nat ed by the current from the cr ack flanks, whereas the current noi se reflects, pri nci pal l y,
processes that occur at the crack front,
As not ed above, a model that is consi st ent wi t h the noi se dat a for crack pr opagat i on is
one that proposes that cr ack advance occurs by di scret e events, the frequency of whi ch
( V ~ i ) ; u ~ u n o v ~ z
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depends on the stress intensity. By assuming that each spike in the noise corresponds to a
single semicircular event of dimension, g, we can write the crack growth rate as
da _ 2g 2
dt L f (2)
where
a = the crack length,
L = the specimen width, and
f = the event frequency (1 - 2 Hz).
From the measured crack growth rate and the specimen dimension [22], it was found that
the average dimension is of the order of 3 ~m, which is considerably smaller than the grain
size of the steel (30 to 50 ixm) [21, 22].
We can test the internal consistency of this model for crack advance by calculating the
current density at the interfaces of the discrete events from the amplitude of the noise and
the dimensions of the events. Thus, taking the previous estimate of g = 3 I~m, and assuming
that the event is semicircular, we calculate the total area exposed per event as 2.8 1 0 - 7
cm ~. Now, the amplitude of the noise (see Fig. 17), on average, is about 15 IxA, which yields
an instantaneous current density at the moment of fracture of - 5 3 ~LA/cm 2. This value is
consistent with the results from fast-straining experiments on austenic stainless steel [24],
allowing for the fact that these alloys do not accurately simulate the sensitized grain bound-
aries of the materials used in this study and recogni zi ng the approximate nature of the
calculation.
To our knowledge, the experiment described above is unique, and it provides a powerful
illustration of how ENM may be used to monitor the rate of crack growth and explore the
mechani sm by which growth occurs. The method is particularly convenient for use in high-
temperature (supercritical and subcritical) systems, because of its great precision and sensi-
tivity (afforded by our ability to measure very small currents) and its simplicity. Al t hough
experimental challenges do exist (for example, in coating the specimen with plasma-sprayed
ZrO2 rather than with PTFE), the technique has already been proven at 288~ and we see
little impediment to extending the temperature to T > T c.
Summary and Conclusions
An electrochemical noise analyzer has been developed that is capable of detecting and
measuring the electrochemical noise induced in the coupling current between two identical
metal or alloy probes when exposed to conditions that simulate the heat transport circuits of
supercritical fossil-fuelled power plants. This study shows that the electrochemical noise
induced on carbon steel in high subcritical and supercritical water depends on temperature,
pressure, flow rate, and oxygen concentration in an understandable manner. These experi-
ments demonstrate thai: the electrochemical noise analysis is a sensitive technique for mon-
itoring corrosion activity in high subcritical and supercritical aqueous systems.
The compact tension testing experiment on sensitized Type 304 SS in high-temperature
water demonstrates that noise in the coupling current between the crack and the external
cathodes reveals important information on the mechani sm of crack propagation. The exper-
imental results are co~asistent with crack growth being due t o a discrete event cleavage
mechanism, in which tile events are possibly induced by embrittlement of the grain boundary
matrix.
Acknowledgment
The aut hors gr at ef ul l y acknowl edge t he suppor t of t hi s wor k by UNI ON FENOSA, Ma-
dri d, Spai n, and by t he Ni agar a Mohawk Power Cor por at i on, Syr acuse, New York.
References
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Coatings by Electrochemical Noise Methods," in Proceedings of the 12th International Corrosion
Congress, Vol. 1, NACE, Houston, 1994, p. 182.
[2 ] Gabrielli, C., Huet, F., and Keddam, M., "Introduction of Metallic Corrosion by Electrochemical
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[3] Gabrielli, C., Huet, E, Keddam, M., and Macias, M., "Electrochemical Noise Generated by a
Corroding Electrode, Effect of Metallurgy and Inhibitors," in Surface, Inhibition, and Passivation,
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Pennington, NJ, 1986, p. 507.
[4] Benzaid, E., Huet, F., Gabrielli, C., Jerome, M., Wenger, E, and Galland, J., "Investigation of
Electrochemical Noise in the Study of Hydrogen Embrittlement of a 42CD4 Carbon Steel Elec-
trode," in Progress in the Understanding and Prevention of Corrosion (Proceedings, lOth European
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[5] Hladky, K. and Dawson, J. L., Corrosion Science, Vol. 21, No. 4, 1981, p. 317.
[6] Dawson, J. L., Farell, D. M., Aylott, P. J., and Hladky, K., "Corrosion Monitoring Using Electro-
chemical Noise Measurements," Paper 31, NACE Corrosion~89, April 1989, New Orleans, LA,
NACE, Houston, TX.
[7] Kending, M. and Anderson, D., Corrosion, Vol. 48, No. 3, 1992, p. 178.
[8] Bertocci, U., Mullen, J. L., and Ye, Y. X., "Electrochemical Noise Measurements for the Study of
Localized Corrosion and Passivity Breakdown," in Passivity of Metal and Semiconductors, M.
Froment, Ed., Elsevier Science Publishers B. V., New York, 1983, p. 229.
[9] Flis, J., Dawson, J. L., Gill, J., and Wood, G. C., Corrosion Science, Vol. 32, No. 8, 1991, p. 877.
[10] Eden, D. A. and Rothwell, A. N., "Electrochemical Noise Data: Analysis, Interpretation and Pres-
entation," Paper 292, Corrosion 92, the NACE Annual Conference and Corrosion Show, May 1992,
Nashville, TN, NACE, Houston, TX.
[11 ] Eden, D. A., Rothwell, A. N., and Dawson, J. L., "Electrochemical Noise for Detection of Sus-
ceptibility to Stress Corrosion Cracking," Corrosion 91, The NACE Annual Conference and Cor-
rosion Show, Paper 444, March 1992, Cincinnati, OH, NACE, Houston, TX.
[12] Stewart, J., Wells, D. B., Scott, P. M., and Williams, D. E., Corrosion Science, Vol. 33, 1991,
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[13] Monticelli, C., Brunoro, G., Frignani, A., and Trabanelli, G., Journal of the Electrochemical Society,
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[14] Mansfeld, E and Xiao, H., "Electrochemical Noise Analysis of Iron Exposed to NaCI Solutions
of Different Corrosivity," in Proceedings, 12th International Corrosion Congress, Vol. 3A, NACE,
Houston, TX, p. 1388.
[15] Bain, R. W., Steam Tables, Her Majesty' s Stationary Office, Edinburgh, UK, 1964.
[16] Roberge, P. R., "Analysis of Spontaneous Electrochemical Noise with Stochastic Pattern Detector
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[17] Dowling, N. J. E., Thual-Duret, C., Auclair, G., Audouard, J. P., and Combrade, P., "Assessment
of the Pitting Susceptibility of AISI 303 and 304 Stainless Steels as a Function of Sulphur Content
Using Electrochemical Noise," in Progress in the Understanding and Prevention of Corrosion
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The Institute of Materials, London, 1993, p. 1328.
[18] Macdonald, D. D., Pang, J., Liu, C., Medina, E., Villa, J., and Bueno, J., "Development of Sensors
for In-Situ Monitoring of Corrosion and Water Chemistry Parameters For Electric Power Utility
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[19] Macdonald, D. D., Pang, J., Liu, C., Kriksunov, L. B., Medina, E., Villa, J., and Bueno, J., "Mon-
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[20] Liu, C., Macdonald, D. D., Medina, E., Villa, J., and Bueno, J., Corrosion, Vol. 50, No. 9, 1994,
p. 687.
[21] Manahah, M P., Sr., Newman, K. E., Macdonald, D. D., and Peterson, A. J., Jr., "Experimental
Validation of the Basis for the Coupled Environment Fracture Model," paper presented at EPRI
Workshop on Secondary Side-Initiated IGA/ SCC, Minneapolis, MN, Oct. 1993.
[22] Manahah, M. P., Sr., Peterson, A. J., Jr., and Macdonald, D. D., Corrosion Science, Vol. 37, No.
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[23] Gerberich, W. W. and Chen, S., "Environment-Induced Cracking of Metals Fundamental Processes:
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Ives, Eds., NACE, Houston, TX, 1990, p. 167.
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A. M. Brennenstuhl, t G. Palumbo, l F. S. Gonzalez, l and G. P. Qui re
The Use of Electrochemical Noise to
Investigate the Corrosion Resistance
of UNS Alloy N04400 Nuclear Heat
Exchanger Tubes
REFERENCE: Brennenstuhi, A. M., Palumbo, G., Gonzalez, E S., and Quirk, G. E, " Th e
Use of El ect r ochemi cal Noise t o I nvest i gat e t he Cor r os i on Resi st ance of UNS Alloy N04400
Nucl ear Heat Exchanger Tubes, " Electrochemical Noise Measurement f or Corrosion Appli-
cations, ASTM STP 1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L
Reichert, and John L. Dawson, Eds., Ameri can Society for Testing and Materials, 1996, pp.
266-287.
ABSTRACT: Underdeposit corrosion of freshwater-cooled shutdown heat exchangers (SHX)
and steam generators (SG) resulted in unscheduled unit shutdowns very early in the life of the
Ontario Hydro Pickering B Nuclear Generat i ng Station, whereas the same SHX and SG i n the
identical A station had not experienced any problems in over 19 years of operation. UNS alloy
N04400 tubes were used for SHX and SG at bot h stations. Because detailed metallurgical
analysis of tubes removed from the A and B stations suggested that alloy differences may be
a maj or factor to the early failures at the B station, an investigation to characterize the corrosion
resistance of the two alloys was carried out. From standard accelerated corrosion t est methods
it was inferred that the A and B alloys had similar corrosion resistance, suggesting t hat subtle
but important material differences may have been masked by the aggressiveness of the test
methods. Therefore, the electrochemical noise measurement (ENM) technique in conjunction
with less aggressive test environments was used to characterize better the corrosion resistance
of the A and B alloys. Variations in the corrosion resistance of the material removed from
Pickering A and B heat exchangers (HX) were evident. During an initial exposure to deionized
(DI) water at a pH of 5, the B alloy generally displayed greater passivity t han the A material.
However, the B alloy exhibited far less corrosion resistance t han the A material when the pH
of the water was reduced to 1 by the introduction of a nitric aci d/ acet i c acid mixture. The
predomi nant mode of degradation in the B material was intergranular attack with some local-
ized corrosion in grain interiors. The A alloy, on the other hand, exhibited general corrosion.
The study also showed that the corrosion resistance of the A alloy was markedly reduced
by heat treatment. A solution heat treatment at 900~ for 1 h followed by a cold-water quench
or furnace cool from this temperature led to a corrosion performance similar to the nonheat -
treated B alloy. The same heat treatment di d not significantly alter the corrosion performance
of the B alloy. Changes in the mode of attack of the A and the B alloys were also observed
when samples had been thermally treated. Bot h exhibited crystallographic attack, whi ch was
very localized in some areas. Transmission electron microscopy and secondary ion mass spec-
trometry revealed changes in the microstructure, whi ch may account for the differences in t he
mode of attack. The predomi nant precipitate chemistry in the A alloy was Cr23C6, whereas in
the B material it was titanium carbide. The B alloy also displayed boron segregation at t he
grain boundaries. Thi s seemed to influence the extent of intergranular attack i n this alloy.
Research scientists, Ontario Hydro Technologies, 800 Kipling Ave., Toronto, Ontario, Canada, M8Z
5S4.
2 CML Ltd., Manchester, Uni t ed Kingdom.
2 6 6
Www.astIII.OFg
BRENNENSTUHL ET AL. ON NUCLEAR HEAT EXCHANGER TUBES 2 6 7
KEYWORDS: UNS N04400, alloy heat exchangers, steam generators, resistance noise, pitting
function, degree of localization, electrochemical potential noise, microstructure, intergranular
corrosion, pitting corrosion, nuclear power
The exceptionally good performance of UNS N04400 alloy heat exchanger (HX) tubes at
the Picketing A Nuclear Generating Station (PNGS A station) resulted in the use of this
alloy in the Picketing B Nuclear Generating Station (PNGS B station). This alloy is used
for shutdown heat exchangers (SHX) and steam generators (SG), which have essentially the
same design and same water sources at both stations. No problems as a result of corrosion
had occurred at the A station during its ten years of operation before the commi ssi oni ng of
the first unit at the B station. However, after onl y six months of service, the first B unit
developed leaks in the SHX tubes, whi ch led to an unscheduled shutdown. Failure analysis
of the leaking tubes suggested that perforation was the result of underdeposit corrosion. Pits
had developed on the outside surface of the tubes. Leaks also developed in the SG at the B
station; these occurred after approximately six years of operation. Again, the leaks were
confined to locations where deposits had developed on the outer diameter (OD) surface. To
establish why the N04400 alloy performed so poorly at the B station, tubes were removed
from both stations for a comparative study.
Detailed metallurgical analysis of the A and B tube samples revealed some differences,
specifically bulk chemistry, inclusion size, and distribution, Analysis of deposits found on
the surface of the A and B SHX tubes indicated that they were similar and typical of what
was expected on SHX tubes exposed to untreated Lake Ontario water. This result seemed
to indicate that metallurgical variations might be an important factor influencing the corrosion
performance of the SHX. The deposits found on the A and B SG tubes were of a compl ex
nature and exhibited both compositional and physical differences. The consequence of this
was that it was impossible to separate alloy and deposit contributions to the degradation
process without carrying out difficult SG simulations involving the two alloys and represen-
tative SG deposits. Therefore, the initial approach used to understand the difference in per-
formance focused on characterizing the corrosion resistance of the two alloys in a simple
test environment.
A corrosion assessment using anodic polarization and open circuit accelerated laboratory
tests failed t o highlight any large variations between the t wo alloys [1]. Because it is possible
that these tests were t oo severe to emphasize subtle but important differences in corrosion
resistance of the A and B alloys, electrochemical noise measurement (ENM) was used to
study corrosion response of the A and B alloys. ENM was selected because its high sensi-
tivity would facilitate the use of a less aggressive test medium, thus potentially providing
more detailed information on the corrosion processes. This technique also has the attraction
of being electrochemically noninvasive and could provide information on the mechanisms
of corrosion [2-4].
This paper outlines the testing carried out on UNS N04400 alloy tubes obtained from the
two stations and describes the results. The effect of heat treatment, specifically quench rate,
was also investigated because the corrosion resistance of this alloy depends on its thermal
treatment history. The thermal history is known to be different for the A and the B alloys
[5].
Bulk Chemical Analysis
Table 1 gives the results of the bulk chemical analysis of the A and B material used in
this investigation. The composition of the t wo materials both conformed to the nominal for
268 ELECTROCHEMICAL NOISE MEASUREMEN'f
TABLE 1--Chemical composition of the A and B UNS Alloy
N04400 investigated during this evaluation.
Element PNGS A PNGS B
Ni 65.30 64.5
Cu 31.3 33.5
Fe 1.93 1.16
Mn 1.01 1.0
Si 0.23 0.15
Mg 0.104 0.079
C 0.097 0.083
Ti 0.006 0.040
B 0.0013 0.0021
Cr 0.066 0.007
S 0.011 0.011
Ca 0.0019 0.001
UNS N04400 alloy; however, some differences between the two batches were evident. This
was particularly the case with iron and copper.
Heat Treat ment s
Two treatments were used. Both included a solution treatment at 900~ for 1 h. One set
of samples was quenched in cold water from this temperature; the other series was allowed
to cool in the furnace. The heat treatments were conducted in an argon atmosphere to elim-
inate oxide scale formation.
The effect of heat treatment was investigated because the A and B HX were subjected to
different thermal conditions during the HX fabrication. No accurate records of the thermal
treatments were available.
Mat eri al s Charact eri zat i on
The microstructure of the as-received (AR) and heat-treated samples were characterized
using transmission electron microscopic/scanning transmission electron microscopic (TEM/
STEM), scanning electron microscopic/energy dispersive spectroscopic (SEM/EDS), and
secondary ion mass spectrometry (SIMS) techniques. Thin foils were extracted from tube
samples and examined with a Philips CMI2 TEM/ STEM with a LaB 6 electron source,
operating at 120 keV. The location density and composition of precipitates found were care-
fully recorded. Information on the distribution of boron in the two alloys was obtained using
a Cameca IMS 3f ion microscope using a positive oxygen primary beam current of 1000
nA and an acceleration voltage of 12.5 kV. The beam was rastered over an area of 250 ~m 2,
and transfer optics of 150 and 400 ~Lm 2 were used. The boron distribution was studied
because a previous examination of the A and B materials revealed large differences in the
distribution of this element in the two alloys [1]. Grain boundary misorientation, inclusion
composition data, and the mode of corrosion were obtained using SEM/EDS. A JEOL 840
SEM, operated at 20 kV, was used for this study. The grain boundary microstructure data
were extracted from electron channeling patterns; misorientations are expressed in terms of
the proportion of special boundaries [6,7].
BRENNENSTUHL ET AL. ON NUCLEAR HEAT EXCHANGER TUBES 269
Corros i on Testi ng
The corrosion resistance of the A and B material was assessed using a CML Ltd. digital
electrochemical noise integrated system (DENIS) instrument and a three-electrode arrange-
ment. Two "i dent i cal " N04400 alloy electrodes and a saturated silver chloride electrode
(Ag/ AgC1 4M) were used in each cell. The coupling current between the pair of N04400
electrodes was monitored, and the corrosion potential between one of them and the standard
reference electrode was obtained simultaneously. The ENM equipment was programmed to
acquire signals from the electrodes every 4 s. Each file included 1024 data points. Onl y two
cells were monitored at any one time, one cell containing the A material and the other the
B alloy. The monitoring was carried out in series, that is, 1024 data points were obtained
from the A cell before the instrument switched to the B cell. The DENIS system collected,
stored, and performed summary statistics on the raw time domai n data. The summary sta-
tistics included corrosion potential, electrochemical current noise (ECN), coupl i ng current,
electrochemical potential noise (EPN), degree of localization (DoL), and resistance noise
(R,,).
ENM Meas urement s
The ECN and EPN have their usual significance. DoL is the result of the ECN divided
by the rms coupling current and broadly classifies the corrosion process occurring on the
sample surface. DoL shows the variation of localized attack during an experiment but does
not reflect the severity of pitting because the absolute current level from the electrochemical
current noise is not factored in. In fact, the DoL is at its highest during periods when the
noise resistance increases, that is, with very low rates of attack the ENM data are almost
certain to indicate a reasonably high degree of localization even i f localization of attack is
actually low. Therefore, pitting function, a new parameter recently derived by CML Ltd. to
overcome this problem, was used in addition to DoL during this study. The pitting function
is an indication of the significance of localized corrosion and is derived from the DoL, but
is weighted by the average magnitude of the current transients. The calculation of the pitting
function is as follows:
[Ai(1) + . . . + Ai(n)] cri
Pitting Function = " - -
n / ~s
where Ai (I) is the current increase over a 4-s interval (that is, current transient magnitude)
and n is the number of readings taken during Ai. For the data to be accepted into the
summation of the mean transient magnitude for anodic dissolution, the current transient must
have a positive slope and the potential transient must have a negative slope.
Conditions:
- - : +r e
~t
and
~e
m ~ - ve
~t
~ilgt is the current transient over 4 s, and ~c/~t is the potential transient over 4 s. I f the
transient continues over more than 1 s, the summation of current for Ai(n) is continuous, tri
is the standard deviation over the 1024 readings, and Irms is equal to the root mean square
of the current.
Resistance noise is equal to the EPN divided by the corresponding ECN value and is
analogous to polarization resistance (Rp) and the charge transfer resistance (R, ) obtained by
linear polarization resistance measurements and impedance spectroscopy, respectively [8].
Test Samples and Environments
Test samples were made from tubes extracted from PNGS A and PNGS B SG tubes. The
SG tubes were cut into 2. 5-cm lengths, and the samples requiring thermal processing were
given the heat treatment already outlined. This sample length gave an outside surface area
of 7.5 cm 2. The test samples were connect ed to the monitoring equipment by a stainless
steel wire attached to the inside surface of the tube. A pol ymer coating was shrunk onto the
stainless steel wire to prevent contact with the test environment. The ends of the tube samples
were sealed with epoxy resin. All samples were abraded with 320-grit silicon carbide paper
and swabbed with isopropyl alcohol j ust before testing. Testing was carded out in triplicate.
Figure 1 shows the electrode arrangement in the test cell. The test cells, which contained
1 L of DI water, were immersed in a water bath, which was held at a constant temperature
of 30~ ( + / - 2 ~ The DI water had a pH of 5. Exposure to DI water lasted 120 h. The
purpose of this initial exposure was to determine the response of the two alloys in a benign
environment. After 120 h, a 10-mL aliquot containing concentrated nitric acid (70%) and
acetic acid (99.8%) (HNO3/ HAC) in equal amounts was injected into the DI water. Two
additions to the DI water were made 24 h apart. The pH had decreased to one after the
second acid addition.
The HNO3/HAC mixture was used because it is commonl y used as a etchant for revealing
microstructural details in copper-containing alloys including UNS N04400 alloy and was,
therefore, believed to be an appropriate starting medium. Data acquisition was continued for
an additional 34 h after the second etchant injection.
Results
The results presented here are typical outputs for the three sample conditions. Onl y the
pitting function, resistance noise, DoL, and EPN outputs are presented because they best
show the behavior of the alloys examined during this study. The arrows in the pitting function
plots indicate when the HNO3/ HAC additions were made.
Precipitate and inclusion compositions are given in Table 2. Special boundary fractions
and information on boron segregation are also presented.
As-Received (AR) Samples
Figure 2 shows pitting function output for the A material in the AR condition. The pitting
function was initially quite high for both A and B samples with values for the latter being
much greater than the former. Hi gh values are a common observation at the start of moni-
toring and are attributed to increased corrosion associated with defects in the surface film
resulting from the sample preparation process. Bot h passivation charge and passivation cur-
rent density are observed to be significantly affected by residual surface deformation intro-
duced during sample preparation [I]. The initially high pitting function outputs diminished
FIG. l --Det ai l s of the test cell and sample arrangement used in this study.
TABLE 2- - Met al l urgi cal differences between A and B as received and heat-treated samples.
PNGS A PNGS B
Solution Treated Solution Treated
As Received CWQ FC As Received CWQ FC
Precipitate composition Cr23C 6 none none TIC" none none
Inclusion composition MgS MgS MgS CaSb CaS CaS
Boron at grain boundaries none none none extensive none some
% Special grain boundaries 47% . . . . . . . . . . . . . . .
Predominant precipitate composition Cr23C 6 w as also present.
b CaS inclusions al so contained t to 5% magnesium.
1E-04
1E-05
IE-06
O
1E-07
1E-08
IE-09
~, 11~ ~ ~ o 4~"
1E-10
0 50 100 150 200
Time/Hours
' A' ' B'
- - - , o, - -
FIG. 2- - Pi t t i ng f unct i on versus time f or AR A and B alloy N04400 tubes.
wi t h t i me. The B al l oy showed a cont i nuous decrease duri ng t he DI wat er exposur e until
the echant addi t i on was made. A reduct i on of appr oxi mat el y t wo orders of magni t ude was
seen. Fi nal pi t t i ng funct i on values ranged from 4 to 7 l 0 - l ~ A. A di fferent pat t ern was
apparent wi t h the A mat eri al . A decrease was first observed, f ol l owed by a gradual i ncrease
from 1 to 7 l 0 9 A. The i nt roduct i on of the et chant i nt o the test cel l resul t ed in an i ncrease
in the pi t t i ng funct i on of t he B mat eri al of mor e than t hree orders of magni t ude. Dur i ng t he
final hours of the HNOa / HAC phase of the exposure, t he pi t t i ng funct i on r anged from 1 to
4 10 -6 A. An i ncrease in the pi t t i ng funct i on of the A mat eri al was al so evi dent . However,
the i ncrease was not as l arge as was seen for the B mat eri al , and the pi t t i ng funct i on recov-
ered to previ ous levels short l y aft er et chant had been added. The second HNO3/ HAC addi t i on
appears as a sharp i ncrease in t he pi t t i ng funct i on for a br i ef per i od of t i me f ol l owed by an
equal l y r api d decay. Bot h the A and B al l oys r esponded in the same manner.
The DoL outputs (Fig. 3) exhi bi t some di fferences when compar ed wi t h t he pi t t i ng func-
tion data. At the start of t he exposure, the DoL was l owest for t he B mat eri al . The converse
was true wi t h the pi t t i ng funct i on results, wi t h the except i on of t wo l arge transients. The A
mat eri al di spl ayed a rel at i vel y hi gh and fluctuating out put duri ng the DI wat er part of t he
exposure. Etchant i nj ect i on into the t est cel l resul t ed in an i ncrease in the DoL for the B
mat eri al , then an i mmedi at e decrease, fol l owed by a further t ransi ent when the second ad-
di t i on was made. The general t rend was t oward an i ncrease in the DoL, suggest i ng i ncreasi ng
l ocal i zed attack. In the case of the A mat eri al , the t endency was al so t oward a decr ease in
t he degr ee of l ocal i zat i on aft er t he HNO3/ HAC addi t i ons, i ndi cat i ng general corrosi on.
Fi gure 4 shows the R, data. These plots, l i ke the pi t t i ng funct i on results, al so show a l arge
di fference bet ween t he A and B al l oys. The A mat eri al di spl ayed bet t er corrosi on resi st ance
BRENNENSTUHL ETAL. ON NUCLEAR HEAT EXCHANGER TUBES 273
IE+O0
1E-01
1E-02
1E-03 , I , ,
/
0 50 100 150 200
Time/Hours
I
- - ' A ' - 4 - ' B '
FIG. 3 - - Do L versus t i me f o r A and B al l oy N04400 AR tubes.
at the very start of the exposure. However, this qui ckl y decr eased to val ues si gni fi cant l y
bel ow t hose for t he B mat eri al . Further, the A mat eri al exhi bi t ed a rel at i vel y smoot h output
during this period, whereas the B signal was variable. R, values ranged from 200 to 500 kf~
for the A al l oy wi t h the pr eponder ance of dat a poi nt s bei ng in the 200- to 300-kl~ range.
This cont rast s wi t h t he B alloy, whi ch exhi bi t ed values rangi ng from 300 to 6000 kl-I wi t h
the average bei ng about 1000 kI~. When t he et chant was i nj ect ed into the t est cel l , a dramat i c
reduct i on in R, of appr oxi mat el y four decades was observed for the B alloy, and t he values
r emai ned at l ow levels for the rest of t he exposure. Resi st ance noi se val ues rangi ng f r om 60
to 300 f~ were t ypi cal . The A al l oy al so di spl ayed a reduct i on in R, but onl y by a factor of
t wo to five (values were in the 30 to 200- kf l range), and the out put seemed to be more
vari abl e than before the HNO3/ HAC i nt roduct i on. These dat a suggest t hat the A al l oy t ends
t oward general corrosi on whereas that for the B al l oy is l ocal i zed. Thi s conflicts wi t h the
pi t t i ng funct i on and DoL results.
The EPN outputs are shown in Fi g. 5. Before the addi t i on of the et chant in the DI water,
the EPN for the B mat eri al was gener al l y sl i ght l y hi gher than for t he A alloy, and appear ed
to fluctuate more. The aci d addi t i ons are cl ear l y evi dent in t hese plots. Af t er the aci d addi t i on,
bot h mat eri al s seem to behave in a si mi l ar manner. The ampl i t ude of the fluctuation was a
fact or of appr oxi mat el y five less t han bef or e the aci d addi t i on. These dat a al so seem to
conflict wi t h the pi t t i ng funct i on and DoL outputs for t he B alloy, whi ch show an i ncrease
in l ocal i zed act i vi t y aft er the et chant addi t i on was made. A concomi t ant i ncrease in EPN
was expect ed from our experi ence of passi vat i ng al l oys l i ke st ai nl ess steels.
Scanni ng el ect ron mi cr ogr aphs for the t wo bat ches of al l oy N04400 aft er the exposure
are shown in Fi g. 6. The A mat eri al di spl ays uni form corrosi on; grai n boundari es are evident,
1E+07
1E+06
1E+05
9
Z 1E+04
o
~ 1E+03
1E+02
IE+01
I
0 50 100 150 200
Time/Hours
_ _ ' A ' + ' B '
FIG. 4--Resistance noise versus time f or A and B alloy N04400 AR tubes.
but there was no appreciable ditching. This contrasted with the surface of the B samples in
which attack was mostly at grain boundaries with some localized corrosion in the grain
interiors. The localized corrosion took the form of numerous small pits all at the same
location and often extending across several grain boundaries.
The TEM/ STEM examination revealed precipitates at grain boundaries, and within the
grain interiors, predominantly at the dislocations of both materials. Cr 23C 6 precipitates were
found in the A alloy, and a combination of TiC and Cr 23C 6 wa s in the B alloy. The SIMS
imaging of boron indicated segregation of this element in many of the grain boundaries of
the B material and no segregation in the A alloy. No other elements were found with boron,
which seems to imply that it is likely in solid solution. Results from the grain boundary
misorientation measurements suggested a similar proportion of special boundaries 47 and
49% for the A and B alloys, respectively. Nonmetallic inclusion elemental analysis showed
that inclusions in the A alloy contained mostly magnesi um and sulphur; those in the B
material were essentially calcium and sulphur with a small amount of magnesi um (<5%).
In addition, the inclusions in the A alloy were small and uniformally distributed over the
entire surface, whereas these in the B alloy were larger and at isolated locations.
Col d- Wat er - Quenched ( CWQ) Sampl es
Pitting function results for the cold-water-quenched samples are shown in Fig. 7. Bot h the
A and B material start at similar levels and decrease together during the first 25 h. The
decrease is relatively smooth, showing little or no large fluctuations. The initial decrease for
the A material was followed by a relatively variable signal about 65 h into the test when a
BRENNENSTUHLETAL ON NUCLEAR HEAT EXCHANGER TUBES 275
1E+00
1E-OI
IE-02
1E-03
1E-04
1E-05
L
50 100 150 200
Time/Hours
_ _ ' A ' ~ ' B '
FIG. 5- - EPN versus time for A and B alloy N04400 AR tubes.
steady increase became evident, the increase ranging from 3 10 -9 to 4 x 10 -8 A. A
variable signal was also observed for the B material, but, unlike the A alloy, no major
increase was evident during the DI water exposure. The average pitting function value during
this phase of the test was 1 x 10 8 A. When the HNO3/ HAC addition was made to the cell,
both the A and B Al l oy N04400 responded in an identical manner - - t he pitting function
increased dramatically. The final pitting function levels were similar for both alloys. Average
pitting functions were 1.8 x 10 -6 and 3 x 10 -6 A for the A and B alloys, respectively. The
extent of pitting of these samples was like that for the AR B material.
Figure 8 gives the DoL data. The A material displayed numerous high amplitude fluctu-
ations during the DI water exposure; the trend was toward a gradual increase in DoL. A
similar tendency was observed with the B material except that the amplitude of the transients
was lower and of higher frequency. When the etchant was added to the test cells, the B
material exhibited a sharp increase whereas the A material showed very little change. After
the acid addition, the DoL for the A alloy was about twice that of the B sample. The pitting
function and DoL outputs suggest localized corrosion for both alloys.
Resistance noise results are given in Fig. 9. Bot h alloys show high R, values during the
DI water exposure. The A material exhibits decreasing R, with time, whereas the B material,
although fluctuating considerably, displays an increasing trend. R, values for the B material
range from 150 to 3500 kf~ and 200 to 900 kf~ for the A alloy. Once the acid was added
to the cells, the R, for both of the alloys decreased to very low values. The B material (60
f~) was consistently lower than the A (80 f~). The second etchant addition had little lasting
effect. These data contradict the pitting function and DoL outputs and suggest general
corrosion.
FIG. 6--(A) AR A sample after testing showing general corrosion (x2000). (B) AR B sample after
testing showing intergranular attack and corrosion in the grain interiors (x2000).
EPN results are given in Fig. 10. Both materials showed similar noise before and after
the acid addition. Large potential noise spikes were evident when the acid additions were
made. The amplitude of the outputs was greatly reduced after the acid addition and displayed
much less noise than was the case before the etchant was introduced into the cells. This
kind of response was also seen with the AR samples.
Scanning electron micrographs for the A and B materials after the exposure are shown in
Fig. 11. The attack in the B was much less concentrated at the grain boundaries than was
the case with the AR samples, and distinct pits were clearly evident. Etching of crystallo-
graphic features in the grain interiors was a major mode of corrosion. The corrosion mor-
phology of the A material is similar to that for the B alloy. Corrosion was localized and pits
were evident. This was in sharp contrast to the general corrosion observed for the AR
samples.
The TEM/ STEM examination indicated that the solution treatment had dissolved almost
all of the precipitates found in the AR samples. Only a small number of isolated large TiC
precipitates was detected in the B material. Results from the SIMS analysis showed no boron
segregation in the A or B alloys. No change was found to have occurred in the distribution
or morphology of the sulphur-beating intrusions as a result of the water quench.
1E-04
1E-05
1E-06
O
"gl
o
~. 1E-07
2
1E-08
IE-09
1E-10
0 50 100 150 200
Time/Hours
_ _ ' A ' ' B '
FIG. 7--Pi t t i ng function versus time f or A and B alloy N04400 after solution treatment f or 1 h at
900~C followed by a cold water quench.
Fur nace- Cool ed ( FC) Sampl es
Figure 12 shows pitting function plots for the furnace-cooled samples. The outputs for the
A and B samples were almost identical. The pitting function values for both materials started
at relatively high values and after 15 h of exposure had dropped by one to two orders of
magnitude to approximately 1 x 10 9 A showing little further change until the acid mixture
was added. Not e that during this "st abl e period" bot h alloys exhibited fluctuations of rela-
tively short duration; the B material was somewhat worse in this regard. The introduction
of the acid mixture resulted in a three-decade increase in the pitting function, Both alloys
showed a similar response, Values were typically in the 3 to 5 x 10 6 A range.
DoL results are shown in Fig. 13. The plots for the t wo materials were similar, except
that the fluctuations in the outputs for the B alloy were of a larger amplitude. After the acid
addition, some separation was evident, the A material showing significantly higher values
than the B alloy.
Figure 14 shows the R, results for the t wo alloys. The plots were similar, with the B alloy
displaying slightly higher values than the A sample during the DI water phase of the test.
Data obtained during the low pH exposure revealed almost no difference. Overall, the outputs
were generally slightly higher than those obtained from the cold-water-quenched samples,
EPN results are shown in Fig. 15. Again, during the higher pH phase of the test the noise
for the B alloy was greater than that for the case with the A, but after the acid addition the
outputs outs were similar.
1E+O0
1E-01
O
1E-02
i t 7 t
T
1E,-03 ' ' '
0 50 100 150 200
Time/Hours
' A' . . 4 - 'B'
FIG. 8--DoL versus time for A and B alloy N04400 after solution treatment at 900~ f or 1 h followed
by a cold water quench.
Scanni ng el ect ron mi cr ogr aphs for the A and B sampl es are shown in Fi g, 16. The A
al l oy exhi bi t s general at t ack wi t h some cr yst al l ogr aphi c et chi ng in the grai n interiors. Some
of the grai n boundari es were al so di t ched. Si mi l ar features were obser ved for the B mat eri al ;
however, a l arger number of the grai n boundari es were heavi l y di t ched. The grai n boundar y
at t ack obser ved on the B sampl e was not as l ocal i zed as was the case wi t h the AR B alloy.
The TEM/ STEM exami nat i on suggest ed that, even t hough t he cool i ng rat e had been
r educed by furnace cool i ng, t he rate was still t oo fast for preci pi t at i on to occur. The mi -
crost ruct ure appear ed to be si mi l ar to that seen aft er wat er quenchi ng. Resul t s from the SI MS
anal ysi s i ndi cat ed that boron had ret urned to some of the grai n boundari es. Agai n, no change
had occurred in the mor phol ogy and di st ri but i on of t he i ncl usi ons as a resul t of the heat
treatment.
Di s c u s s i o n
The reason for the poor per f or mance of UNS Al l oy N04400 in PNGS B SHX and SG
must be det er mi ned to i nt roduce r emedi al measures to ensure the cont i nued r el i abl e operat i on
of t hese syst ems for the r emai ni ng l i fe of the nucl ear units. Because t he HX t hat exhi bi t the
most pr onounced degradat i on ( SG and SHX) are subj ect ed to vast l y di fferent operat i ng en-
vi ronment s, attention was focused on the i nherent cor r osi on resi st ance of t he A and B al l oys.
Previ ous chemi cal and met al l urgi cal anal ysi s of the A and B al l oys reveal ed di fferences that
mi ght cause vari at i ons in corrosi on resi st ance. St andard accel er at ed cor r osi on tests were used
t o compar e the al l oys, but t hese fai l ed t o reveal any l arge di fferences bet ween t he t wo
BRENNENSTUHL E-I- AL. ON NUCLEAR HEAT EXCHANGER TUBES 279
IE+07
1E+06
1E+05
Z IE+04
~ 1E+03
1E+02
1E+01 r
0 50 100
Time/Hours
[
150 200
_ _ ' A ' + ' B '
FIG. 9- - Resi st ance noise versus time f or A and B alloy N04400 af t er solution treatment at 900~ f or
1 h and col d wat er quench.
materials [1]. The possibility that the accelerated tests selected were so severe that they
masked subtle but important differences in the corrosion resistance led to the ENM approach
being selected as a method for better defining the corrosion performance of the two alloys.
ENM was attractive because it is very sensitive, electrochemically nonintrusive, and can
provide mechanistic information [2,4].
As - Re c e i v e d A a n d B Tube Ma t e r i a l
The ENM results for the AR tube samples clearly revealed a difference in the corrosion
response of the A and B alloys. This was particularly noticeable after the etchant addition.
A much larger pitting function and lower R, were recorded for the B material, indicating
less corrosion resistance than the A alloy in the pH 1 environment. This result is consistent
with the field performance. Interestingly, the variation was clear with both the R, and pitting
function outputs; this is not commonl y the case. Generally, resistance noise is onl y useful
when corrosion is of an active nature (that is, general corrosion), and the pitting function is
only a practical parameter when attack is localized. Variations in t opography of the test
samples help to explain this unusual behavior. Local i zed corrosion was evidently occurring
in the B alloy but was very widespread; almost all the grain boundaries exhibited significant
corrosion together with some attack in the grain interiors. This increase in pitting function
is therefore likely the consequence of propagation at the grain boundaries, a process that is
relatively unstable because of significant crystallographic heterogeneities at these locations.
Because the process is widespread, the mean potential of the system and the EPN, as a
IE-01
1E-02
~ 1E-03
1E-04
IE-05 i J
0 50 100
Time/Hours
_ _ ' A ' _ . _ ' B '
L J
150 200
FIG. I O- - EPN outputs f or A and B alloy N04400 af t er solution treatment f or 1 h and coM water
quench.
consequence, is dr amat i cal l y lowered. In cont rast to t he B al l oy t opography, t he A surface
di spl ayed general corrosi on; grai n boundari es coul d be seen, but t hey were not heavi l y at-
t acked. The el ect rochemi cal outputs aft er the etchant addition, speci fi cal l y t he resi st ance
noise, refl ect ed a general corrosi on condi t i on at a low rate.
A compar i son of the grai n boundar y mi crost ruct ure of the t wo al l oys reveal ed di fferences
in preci pi t at e chemi st ry, Cr23C 6 and TiC for the A and B al l oys, respectively, wi t h the l at t er
al l oy al so cont ai ni ng some Cr23C 6. These preci pi t at es were al so seen at grai n i nt eri ors pre-
domi nant l y at di sl ocat i ons. Boron was al so found to be segregat ed at the grai n boundari es
of the B alloy. Because the degree of mi sori ent at i on of the grai n boundar i es of the t wo al l oys
was similar, it appears that t hese mi cr ochemi cal di fferences are a maj or fact or in t erms of
the i nt ergranul ar at t ack of the B alloy. The cause of the l ocal i zed corrosi on in the grai n
i nt eri ors is not as clear. The mode of at t ack suggest s that it may be segregat i on related.
Because t here was no evi dence of t her modynami cal l y possi bl e spi nodal decomposi t i on
[9- 11], whi ch mi ght account for l ocal changes in al l oy mi crost ruct ure, it is not possi bl e to
ci t e this as the cause. A possi bl e expl anat i on is the presence of sul phur-beari ng i ncl usi ons.
In addi t i on to chemi st ry di fferences, the si ze and di st ri but i on of t hese i ncl usi ons are mar kedl y
different. A previ ous SI MS exami nat i on of t he A and B al l oys suggest s that t hey were evenl y
di st ri but ed in the A al l oy and hi ghl y segregat ed in the B al l oy [12]. Thi s si t uat i on coul d l ead
to di fferences in the anode/ cat hode areas, wi t h the B mat eri al suffering the hi gher l ocal i zed
corrosi on because of its smal l er anode- t o- cat hode ratio.
FIG. 1 I--(A) Solution-treated and CWQ A sample after testing showing crystallographic attack
(x2000). (B) Solution treated and CWQ B sample after testing showing similar corrosion to the A
material (
Some interesting observations were also made during the D! water phase of the test. The
pitting function, R, and DoL outputs seem to indicate that the B material was more passive
in this relatively benign environment than the A alloy. This is also possibly due to the lower
concentration of sulfur-bearing inclusions. These inclusions act as sites for local protective
film breakdown.
Evidently, the noise parameters selected for assessing the corrosion resistance of the two
alloys examined in this investigation clearly highlighted the differences between them with
the exception of the DoL. Overall, the DoL for these samples followed the pitting function
-04
1E-05
IE-06
O
~ w 0 7
1E-08
IE-10 ' J '
0 50 100 150 ~.00
Time/Hours
_ _ ' A ' + ' B '
FIG. 12--Pitting function versus time f or A and B alloy N04400 after solution heat treatment at 900~
f or 1 h followed by a furnace cool.
outputs. However, the t ransi t i on bet ween t he DI wat er exposure and l ow pH condi t i on was
oft en less t han clear.
Sol ut i on- Treat ed and Col d- Wat er - Quenched A and B Tube
A sol ut i on t reat ment at 900~ fol l owed by a wat er quench l ed to a dramat i c change in
t he corrosi on response of t he A mat eri al . The A mat eri al agai n gener al l y showed sl i ght l y
hi gher act i vi t y than t he B mat eri al bef or e t he aci d mi xt ure addi t i on. Duri ng t he DI wat er
part of the exposure, the B sampl e out put s sl i ght l y depart ed from what was seen in the AR
exami nat i on. It was evi dent t hat the out put was now noisier. The reason for this is not cl ear
but does seem to suggest t hat the heat t reat ment has al t ered the corrosi on resi st ance of the
passi ve film. A very l arge i ncrease in the pi t t i ng function was evi dent when the HNO3/ HAC
was added to the t est cel l for bot h A and B al l oys. Results for the A al l oy i ndi cat e that the
ext ent of corrosi on was appr oachi ng that found for the B alloy. Al t hough the act i vi t y of the
B was not si gni fi cant l y great er than was obser ved for the AR B mat eri al , the mode of at t ack
was different. Corrosi on was pr edomi nant l y cryst al l ographi c. Grai n boundar y at t ack was
great l y reduced. Thi s absence of grai n boundar y corrosi on coi nci ded wi t h an absence of
preci pi t at es and boron at the grai n boundari es. Thi s support s the suggest i on that t here is a
rel at i onshi p bet ween grai n boundary chemi st r y and i nt ergranul ar corrosi on. Unfortunately,
however, t he pri ce for r educed grai n boundary corrosi on is great er corrosi on of the grai n
interiors. Cor r osi on was al so cr yst al l ogr aphi c in t he A al l oy but di d not appear to be as
pr onounced as was t he case wi t h the B mat eri al . The resi st ance noi se out put s were al so
1E+00
1E-01
O
1E-02
1E-03 ~ I 1
0 50 100 150 200
Time/Hours
_ _ ' A ' _ - r ' B '
FIG. 13- - DoL versus time f or A and B alloy N04400 af t er solution heat treatment at 900~ f or 1 h
f ol l owed by a f urnace cool.
si mi l ar for bot h A and B sampl es (that is, the resi st ance noi se dr opped in the same manner
as it di d wi t h the AR B al l oy when t he et chant was added. Agai n, the R, and EPN dat a
were not consi st ent wi t h t hose for the pi t t i ng function. Thi s confl i ct cannot be account ed for
by grai n boundar y at t ack because this was great l y r educed by t he heat t reat ment but can be
r at i onal i zed in t erms of the l ocal i zed cr yst al l ogr aphi c et chi ng and pitting.
The di fference bet ween the AR A sampl es and t he sol ut i on-t reat ed and col d- wat er -
quenched A is evi dent in the DoL pl ot s but is not as cl ear as was the case wi t h t he pi t t i ng
funct i on and R n plots. Further, t he t ransi t i on bet ween the DI wat er exposure and the et chant
addi t i on was not obvi ous. Al so, the results suggest that the degr ee of l ocal i zat i on of the A
mat eri al was great er than that for the B alloy.
Sol ut i on- He at - Tr e at e d a n d Fu r n a c e - Co o l e d A a n d B Tube
It seems from the results of this eval uat i on t hat reduci ng the cool i ng rate f r om 900~ by
furnace cool i ng does not al t er the cor r osi on resi st ance from t hat found with the col d wat er
quench. Agai n, the R, resul t s confl i ct wi t h t he pi t t i ng function dat a duri ng the HNO3/ HAC
phase of t he test. Before the et chant addi t i on, t he B al l oy was noi si er than the A alloy, but
the average pi t t i ng funct i on was appr oxi mat el y the same i ndi cat i ng an i mpr ovement in t he
passi vi t y of the A alloy. The DoL appeared, aft er an initial decrease, to i ncrease gr adual l y
wi t h exposure time. Before the aci d addi t i on, t he A sampl e seemed to be less active than
was the case wi t h the A sol ut i on-t reat ed and col d- wat er - quenched sampl es. Af t er the
HNOf l HAC i nt roduct i on, the A mat eri al di spl ayed the great est degree of l ocal i zat i on. These
1E+07
1E+06
~ 1E+05
O
Z 1E+04
8
1E+03
1E+02
1E+01 i L
0 50 100 150 200
Time/HourS
_ _ ' A ' ~ ' B'
FIG. 14--Resi st ance noise versus time f or A and B alloy N04400 af t er solution heat treatment at
900~ f or 1 h f ol l owed by a fi4rnace cool.
dat a appear to i ndi cat e that gener al l y the B al l oy has a great er t endency to passi vi t y than
the A mat eri al .
The reappearance of si gni fi cant grai n boundary at t ack especi al l y in the B mat eri al appears
to correl at e wi t h the segregat i on of boron at some grai n boundari es suggest i ng that this
el ement may be the reason for the sensi t i vi t y of grai n boundar i es to attack. Preferent i al grai n
boundary corrosi on was al so obser ved in the A alloy. However, it was not as preval ent as
was the case with the B sampl es, and it was not possi bl e to correl at e t he cor r osi on wi t h a
change in grai n boundary chemistry.
I m p l i c a t i o n s o f T e s t R e s u l t s
The results cl earl y show that in the envi ronment s used duri ng this study, pH 5 DI wat er
and pH I HNO3/ HAC, the as-recei ved (nonbeat -t reat ed) A and B UNS N04400 behave
differently. It appears that the B al l oy gener al l y has great er passi vi t y in the pH 5 DI wat er
than the A material. Thi s di fference can l i kel y be at t ri but ed to the di st ri but i on and compo-
sition of sul fur-beari ng i ncl usi ons. The i ncl usi ons in the A al l oy were uni f or ml y di st ri but ed,
whereas in the B al l oy they t ended to be l ocal i zed [12]. Sulfide i ncl usi ons are a maj or cause
of loss of passi vi t y in ni ckel al l oys and st ai nl ess steels [13,14]. Thi s great er passi vi t y of the
B al l oy duri ng the DI wat er phase of t he exposure was sl i ght l y affect ed by heat treatment.
Unfortunately, B al l oy does not retain the advant age associ at ed wi t h superi or passi vi t y in
the low pH envi ronment . Int ergranul ar at t ack occurs. The results appear to i mpl y t hat grai n
1E+00
1E-01
1E-02
1E-03
IE-04
1E-05
I I I
0 5O 100 15O 20O
Time/Hours
__ ' A' ~ ' B'
FIG. 15- - EPN outputs f or the A and B alloy N04400 af t er solution heat treatment at 900~ f or 1 h
f ol l owed by a f urnace cool.
boundary chemistry of the B is less corrosion resistant than the A in the pH 1 environment.
Based on the solution-treated and furnace-cooled results, boron appears have a significant
influence on the corrosion resistance of the grain boundaries. The intensity of the attack at
the grain boundaries was likely promot ed by the relatively good corrosion resistance of the
grain interiors of the B alloy. This resulted in a high potential existing between the grain
boundaries and grain interiors.
Some localized attack was observed in the grain interiors; the reason for this is not clear
but may be connected to the presence of isolated inclusions in the B alloy. The relatively
good corrosion resistance of the material surrounding the inclusions would lead to the de-
velopment of a relatively high potential difference between it and the sulphide inclusions in
the interface region between the alloy and the inclusion, thus promoting localized attack.
Therefore, although the B alloy generally shows greater corrosion resistance than the A,
which suffers from general attack, this superior corrosion resistance does not translate into
better localized corrosion performance. To the contrary, the performance of the B alloy is
diminished because of the microstructural weaknesses.
The solution heat treatment used during this study shows that the A material can be made
to behave like the B alloy at least in the pH 1 environment. This highlights the heat treatment
sensitivity of the A alloy. Whet her the corrosion resistance of the B alloy can be i mproved
by heat treatment has yet to be determined. Certainly, the limited number of thermal treat-
ments examined in this study did not appear to lead to a significant change.
FIG. 16--(A) Solution-treated and FC A sample after testing showing crystallographic attack and
some grain boundary ditching ( x2000). (B) Solution-treated and FC B sample after testing showing
similar corrosion to the A sample but greater grain boundary attack (X2000).
Electrochemical Noise Measurement Considerations
The results of this investigation suggested that the system under examination was one in
which the pitting function and resistance noise were both broadly applicable. This infers a
system that ties between general corrosion and localized attack, thereby making rate deter-
minations difficult. No attempt was made to obtain rate information during this investigation,
but an analysis of the test samples and the ENM outputs with the aim of determining whether
reliable rate information can be arrived at using the pitting function and R, is planned for
the future.
Conclusions
1. The ENM resul t s of this st udy cl earl y i ndi cat ed that the AR B al l oy has a l ower
corrosi on resi st ance than t he AR A t ubes when exposed to the hi ghl y oxi di zi ng l ow
pH ( appr oxi mat el y pH l ) condi t i ons used is this study.
2. Duri ng the DI wat er exposure phase ( appr oxi mat el y pH 5), t he B mat eri al gener al l y
di spl ayed great er passi vi t y than the A sampl e.
3. The corrosi on resi st ance of the A t ube mat eri al can be si gni fi cant l y r educed by a 900~
sol ut i on heat t reat ment to the ext ent that it had a si mi l ar corrosi on resi st ance to the B
alloy. UNS Al l oy N04400 is evi dent l y sensi t i ve to heat treatment.
4. The heat t reat ment used duri ng this eval uat i on l ed to a change in the mode of degra-
dat i on for bot h al l oys. Thi s seems to correl at e wi t h grai n boundar y mi cr ochemi st r y in
t he B alloy, wi t h boron bei ng the maj or factor. The A al l oy was not as sensi t i ve to
grai n boundary degr adat i on as the B mat eri al .
5. The hi gh pi t t i ng funct i on and unexpect ed r educed EPN and R, response at l ow pH are
expl ai ned in t erms of t he nature of attack, which, al t hough l ocal i zed, was ext ensi ve.
Acknowl edgment s
The authors woul d l i ke t o t hank M. Pri kryl and G. C. Weat herl y at McMast er Uni versi t y
for the TEM/ STEM studies and G. Mount at The Uni versi t y of West ern Ont ari o for t he
grai n boundar y SI MS i magi ng.
References
[1] Palumbo, G., Brennenstuhl, A. M., and Gonzalez, F. S., in Application of Accelerated Corrosion
Tests to Service Life Prediction of Materials, ASTM STP 1194, American Society for Testing and
Materials, West Conshohocken, 1992, p. 252.
[2] Hladky, K. and Dawson, J. L., Corrosion Science, Vol. 21, No. 4, 1981, p. 317.
[3] Eden, D. A., Rothwell, A. N., and Dawson, J. L., Paper 444, Corrosion 91, NACE, Cincinnati,
1992.
[4] Searson, E C. and Dawson, J. L., Journal of the Electrochemical Society, Vol. 135, No. 8, 1988,
p. 1908.
[5] De, P. K. and Bose, A., Corrosion, Vol. 49, No. 2, 1993.
[6] Brandon, D. G., Acta Metallurgica, Vol. 14, 1966, p. 1479.
[7] Palumbo, G., Aust, K. T., Erb, U., King, E J., Brennenstuhl, A. M., and Lichtenberger, E C.,
Physica Status Solidi (a), Vol. 131, 1992, p. 425.
[8] Lumsden, J. B., Kendig, M., and Jeanjaquet, S., Paper 224, Corrosion 92, NACE, Nashville, 1992.
[9] Srikanth, S. and Jacob, K. T., Materials Science and Technology, Vol. 5, 1988, p. 427.
[10] Vrijen, J. and Radelaar, S., Physical Review, Series B, Vol. 17, 1978, p. 409.
[11] Sachtler, W. M. H. and Dorgelo, G. J. H., Journal of Catalysis, Vol. 4, 1965, p. 654.
[12] Brennenstuhl, A. M., Doherty, E E., Bellamy, G., King, E J., and Dunstall, T. G., "The Corrosion
of Freshwater Cooled Nuclear Heat Exchangers at Ontario Hydro," in Canadian Nuclear Society
Proceedings of a Conference on Steam Generators and Heat Exchangers, Toronto, 1990, pp. 1-69.
[13] Marcus, E and Talah, H., Corrosion Science, Vol. 29, 1989, p. 455.
[14] Kesten, M., Corrosion, Vol. 32, No. 3, 1976, p. 94.
P. E. Dohert y, ~ M. J. Ps ai l a- Dombr ows ki , 2 S. L. Harper, 2
and W. G. Schnei der ~
The Use of Electrochemical Noise
Measurement in the Evaluation of
Materials for Steam Generators
REFERENCE: Doherty, E E., Psaila-Dombrowski, M. J., Harper, S. L., and Schneider, W.
G. , " Th e Us e o f El e c t r o c h e mi c a l No i s e Me a s u r e me n t i n t he Ev a l u a t i o n o f Ma t e r i a l s f o r
S t e a m Ge ne r a t o r s , " Electrochemical Noise Measurement for Corrosion Applications, ASTM
STP 1277, Jeffery S. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John
ABS TRACT: In the past ten years, there has been a progressive development in corrosion
monitoring technology [1-12]. Initial approaches to evaluate the performance of steam gen-
erator (SG) alloys were based on mass-loss coupons and polarization resistance measurements
of probes in SG environments or aggressive water chemistries. Corrosion rates and mechanisms
were characterized and quantified with data obtained from metallurgical examination of test
specimens. Several of these earlier autoclave tests were conducted over a number of years with
inconclusive results. Recent interest has focused on the application of modern electrochemical
techniques [6,7], such as current and potential electrochemical noise, for greater sensitivity in
the evaluation of localized and general corrosion behavior.
This paper reviews the progress to date of a multidisciplinary study to investigate the feas-
ibility of electrochemical techniques to evaluate steam generator materials. The primary tech-
niques investigated were electrochemical current noise measurement (ECNM), zero resistance
ammetry (ZRA), and electrochemical potential noise measurement (EPNM). Several applica-
tions, including monitoring localized and general corrosion of steam generator tubes and other
material combinations, with and without crevices, are discussed. Future developments and their
potential impact on plant reliability, integrity, and safety programs are reviewed.
KE Y WOR D S : Alloy 690, Alloy 600, steam generator, resistance noise, current noise, potential
noise, degree of localization, nuclear power, crevice corrosion
A coor di nat ed r esear ch pr ogr a m was i ni t i at ed t o expand our under s t andi ng o f st eam gen-
er at or ( SG) mat er i al s ' el ect r ochemi cal behavi or . The first phase o f t hi s pr ogr a m f ocus ed on
demons t r at i ng t he usef ul ness o f el ect r ochemi cal noi se me a s ur e me nt t echni ques in eval uat i ng
t he cor r os i on behavi or o f SG t ubi ng al l oys. In addi t i on, envi r onment s t hat woul d accel er at e
t he SG t ube cor r os i on pr oces s es whi l e al l owi ng t est i ng to be conduct ed in a r easonabl e
per i od o f t i me wer e r evi ewed.
Cor r os i on moni t or i ng o f Al l oy 690 and Al l oy 600 t est s peci mens was conduct ed usi ng a
mul t i t echni que appr oach t hat uses a c ombi na t i on of e l e c t r oc he mi c a l met hods. A mul t i t ech-
Supervisor of Chemistry and Metallurgy and manager of Nuclear Technology, respectively, Babcock
& Wilcox International, 581 Coronation Blvd., Cambridge, ON, Canada N1R 5V3.
z Research engineer and research chemist, respectively, Babcock & Wilcox Research and Development
Division, 1562 Beeson St., Alliance, OH 44601.
2 8 8
www.astm.org
DOHERTY ET AL. ON EVALUATION OF MATERIALS 289
nique corrosion monitoring system was connect ed directly to stressed and unstressed Alloy
690 and 600 SG tube C-ring specimens in various concentrations of deaerated sodium hy-
droxide (NaOH) at 300~ (0.01M NaOH, 0.5M NaOH, and 5M NaOH). Creviced Alloy 690
SG tube samples were also evaluated in 5M NaOH solution.
Small, spontaneously generated current and voltage signals originating from electrochem-
ical corrosion processes were recorded on a multiplexed multichannel data logger. The ab-
sence of external polarization eliminates the possibility of perturbing the natural corrosion
process. The data can provide information on the mechani sm and rate of corrosion occurring
on the Al l oy 690 and Al l oy 600 C-ring specimens. The nonperturbative electrochemical
potential and current noise monitoring techniques therefore can be appropriate for the eval-
uation of in-service corrosion, for example, during operation or chemical cleaning processes.
Muititechnique Corrosion Monitoring System
The multitechnique corrosion moni t or used a combination of four monitoring techniques
to evaluate the corrosion behavior of the Alloy 690 and Al l oy 600 SG tubes. These tech-
niques are described below:
1. Potential Measurement--Platinum wire was used as a reference electrode in this study
to give indications of overall potential change. A high-temperature reference electrode
was not used during the test program because the test temperature was too high (300~
for the electrodes currently used. Other electrodes for higher temperatures are being
evaluated. An Alloy 690 coupon is used as the worki ng electrode in this case.
2. Zero Resistance Ammetry ( ZRA) - - ZRA is normally used to determine the galvanic
current between two dissimilar electrodes, but may be effectively used to determine
the coupling current between two nominally identical electrodes.
3. Electrochemical Potential Noise Measurement ( EPNM) - - The term electrochemical po-
tential noise (EPN) is used to describe fluctuations in potential measured during a
corrosion. In this case, EPN was measured by monitoring the potential between two
nearly identical specimens. It may be possible to use EPN data (as well as ECN data)
to identify the mechani sm of corrosion attack [8,9]. For instance, the signatures of
pitting corrosion and stress corrosion cracking have been identified.
4. Electrochemical Current Noise Measurement (ECNM)--Electrochemical current noise
(ECN) can be described as fluctuations of current during the corrosion process. In this
case, the current flow between two nominally identical SG tube electrodes was recorded
and analyzed. The overall corrosion rate may be obtained from the ECN moni t or output
using a calibrated system and controlled environments.
Tests were performed on Alloy 600 SG tube and Al l oy 690 SG tube specimens from two
different tube vendors (A and B). C-ring specimens were machined from lengths of SG tubes
for testing. The chemical compositions of the three alloys used are provided in Table 1.
Three specimens were machined from each alloy to enable the ECN and EPN measurements
to be taken from a three-specimen probe configuration (Fig. 1). One C-ring specimen from
each set of specimens was fully loaded (until the legs touched). No quantitative measurement
of strain was performed, since it was not a test variable and the strain level was above yield.
These specimens were electrically isolated from the loading nuts and bolts, as shown in Fig.
2. No replicates were used during this initial test program. The bolt threads were removed
TABLE 1--Chemi cal composition of test alloys.
Species Concentration
Alloy C Mn S P Si Cr Ni AI Ti Fe N 2
A 690 0.017 0.21 0.000 3 0.007 0.15 30.26 59.36 0.41 0.28 9.26 0.0086
B 690 0.021 0.23 0.000 3 0.007 0.10 26.81 59.81 0.06 0.22 9.56 0.0070
600 0.048 0.31 0.005 0.009 0.10 15.5 73.0 . . . 0.24 8.2 0.018
in t he regi on in whi ch the speci men woul d nor mal l y cont act the speci men and a TFE-
fl uorocarbon sl eeve was pl aced in this regi on to i sol at e t he speci men f r om the bol t . Cer ami c
washers were pl aced bet ween the speci men and the l oadi ng nut.
A cr evi ced C- r i ng speci men was added to t he t est mat ri x in the 5M NaOH t est solution.
The speci men was const ruct ed of t wo C- r i ng speci mens nest ed together. The mat eri al used
for t he cr evi ced C- r i ng speci mens was Vendor B Al l oy 690 tubing. No at t empt was made
to i sol at e t he nest ed C-ri ngs from one another. The C-ri ngs were i sol at ed from t he l oadi ng
bol t and nuts as descr i bed above. The entire assembl y was used as a t est speci men in this
experi ment .
Tests were per f or med in a 7. 57-L (2-gal ) Hast el l oy | al l oy C-276 aut ocl ave. Before i ni t i al
testing, t he aut ocl ave was mechani cal l y cl eaned and flushed wi t h dei oni zed water. The t est
speci mens were mount ed in the aut ocl ave shown in Fig. 3. The speci mens in t he t hree
speci men pr obe were l ocat ed at the same l evel in the aut ocl ave. In addi t i on, a pl at i num wi r e
and an Al l oy 690 coupon were mount ed in the aut ocl ave head to gi ve an i ndi cat i on of
pot ent i al . Three test sol ut i ons were used duri ng t he t est program: 0. 01M NaOH, 0. 5M NaOH,
and 5M NaOH. Af t er the t est sol ut i on was pl aced in t he aut ocl ave and t he head seal ed in
pl ace, t he sol ut i on was deaerat ed overni ght and t he aut ocl ave was heat ed to 300~
Computer
Current Potential
Anal og t o Digital Anal og t o Digital
Converter Converter
ZRA
I
F
J
FIG. 1--Three-specimen probe configuration.
~ A
,p
- E
J _
Oo,a~ L
Washer ~ ~
i
D
Inconel
Wa s he r
/o
5
Al l oy- 690 Al l oy- 600
A 0 . 6 8 7 5 " A 0. 625"
B 0 . 3 4 3 8 " B 0 . 3 1 2 5 "
C 0 . 6 8 7 5 " C 0 . 6 2 5 "
D 0 . 2 5 0 " D 0 . 2 5 0 "
E 1. 750" E 1. 750"
HG. 2--Drawing of C-ring specimen used showing ceramic isolation washers.
Dat a were obt ai ned usi ng a CML DENNI S 9 (Version 4. 5) moni t or i ng syst em and a com-
put er was used to l og data. ECN and EPN dat a were t aken on each speci men pr obe once
every 8 h.
R e s u l t s
The results for the t hree tests are summar i zed below. In addi t i on, the st andard devi at i ons
of the ECN dat a are al so given. An i ncrease in the st andard devi at i on of t he ECN dat a (cri)
i ndi cat es l ocal i zed events. The resi st ance noi se (Ro) is cal cul at ed by tri/tr v (where ~r v is the
st andard devi at i on of the EPN data). R, provi des i nformat i on on the general corrosi on be-
havi or of the mat eri al s t est ed and is i nversel y pr opor t i onal to t he corrosi on rate. The degree
of l ocal i zat i on for the t est mat eri al s in each test envi ronment is al so provi ded. Thi s is cal -
cul at ed by ~i/IRMs, where IRMS is t he r oot mean square of t he current data. The degree of
l ocal i zat i on provi des some i ndi cat i on of t he occurrence of l ocal i zed events, al t hough this
may be mi sl eadi ng. However, when a l ocal i zed event occurs, t he val ue drifts t owards 1 [4].
Test 1 was conduct ed in 0. 01M NaOH sol ut i on usi ng Vendor A Al l oy 690, Vendor B
Al l oy 690, and Al l oy 600 C-ri ng speci mens. Tests were carri ed out for 320 h. ECN or EPN
dat a i ndi cat ed that no cracki ng had occurred. Typi cal ECN and EPN results are shown in
FIG. 3--Test specimens mounted in autoclave head.
Fig. 4. The measured coupling currents and potentials were low as shown in Fig. 5. The
standard deviations for ECN (~ri) were the smallest for Vendor A Alloy 690 and largest for
Alloy 600 (Fig. 6). There was no increase in ~r i, indicating that no significant activity had
occurred for any of the sample alloys. These alloys demonstrated relatively low levels of
general corrosion, as indicated by the relatively high resistance noise (R, ) as shown in Fig.
7. Vendor B Alloy 690 tubing had the highest noise resistance followed by Vendor A Alloy
690 tubing and then Alloy 600. The degree of localization was approximately one for all
materials, indicating a localized process [4], perhaps some grain boundary dissolution or
pitting.
Test 2 was conducted in 0.5M NaOH solution using the same specimens previously de-
scribed. These tests were terminated after approximately 100 h without indication of crack-
ing. The test was stopped to apply a more aggressive environment. Typical ECN and EPN
scans for this environment were not significantly different in appearance than those for the
0.01M NaOH, as shown in Fig. 3. Corrosion activity was general in nature, and there was
no indication of cracking in the electrochemical noise data taken. The measured coupling
DOHERTY ET AL. ON EVALUATION OF MATERIALS 2 9 3
2. 0E- 06
1. 0E- 06
Z O.OE+O0
O
uJ
- 1. 0E- 06
-2. OE-06
- 4. 0E- 04
--L---- J_
500 1000 1500
Time (secondS)
2000
- 5. 0E- 04
Z - 6. 0E- 04
O.
tr
- 7. 0E- 04
~. OE- 04 ~ r j
0 500 1000 1500
~me (seconds)
2000
FIG. 4a--Typical ECN and EPN data for specimens in O.O1M NaOH (Specimen A).
current ( Fi g. 8) wa s hi gher than t hos e meas ured in 0 . 0 1 M Na OH sol ut i on, cr i data f or al l
mat eri al s we r e al s o hi gher than t hos e meas ured i n the 0 . 0 1 M Na OH sol ut i on ( Fi g. 9). Al l
the al l oys had a l o we r R , and, f r om this, it was i nferred that t hey al s o had a hi gher corros i on
rate in thi s t est envi ronment as demons t rat ed by the l o we r R , (Fi g. 10). The res i s t ance noi s e
on Vendor B Al l o y 6 9 0 wa s hi gher than the Vendor A Al l o y 690. Al l o y 6 0 0 had the l o we s t
res i s t ance i ndi cat i ng the hi ghes t corros i on rate. The degree o f l oc al i z at i on decreas ed i n al l
cas es to approxi mat el y 0. 4, i ndi cat i ng that general corros i on wa s occurri ng. There was no
cl ear i ndi cat i on o f l o c a l i z e d attack. The t est wa s st opped and rei ni ti ated wi t h a mor e ag-
gr e s s i ve t est envi ronment .
Test 3 wa s carded out in a 5M Na OH s ol ut i on for approxi mat el y 500 h. In thi s test, a
crevi ced Al l o y 690 C- ri ng s pe c i me n was added t o the t est mat ri x. Typi cal ECN and EPN
scans for this envi ronment we r e not si gni f i cant l y di fferent in appearance than t hos e f or the
0 . 0 1 M Na OH as s hown in Fi g. 4. Duri ng t est i ng (after approxi mat el y 260 h), there was a
sudden change in the e l e c t r oc he mi c al outputs. Af t er the t est was c o mpl e t e , the s pe c i me ns
we r e e xami ne d, and it wa s f ound that areas o f the TFE- f l uorocarbon coat i ng on the ni c ke l
wi re l eads had cracked. Thi s i s the l i ke l y reason for the sudden c hange i n e l e c t r oc he mi c al
2 . 0 E - 0 6 i ~ I
1 . 0 E - 0 6 ~
~ f q " " " i ' 1 " r l ' ' r r l F " I " ' " r , " w t r I T 1
- 2 . 0 E - 0 6 ~ ' *
0
- 8 . 0 E - 0 4
5 0 0 1 0 0 0 1 5 0 0
" l i m e ( s e c o n d s )
2 0 0 0
> ~ - 9 . 0 E - 0 4
Z - 1 . 0 E - 0 3
O .
" ' t
- 1 . 1 E - 0 3
- 1 . 2 E - 0 3 J '
0 5 0 0 1 5 0 0
i
1000
T i m e ( s e c o n d s )
2000
FIG. 4b--Typical ECN and EPN data for specimens in O.O1M NaOH (Specimen B).
readings. The data obtained during the first 250 h of exposure compared with data from
Tests 1 and 2.
The mean coupling current and potential standard deviation for the uncreviced Vendor A
Al l oy 690 test material are shown in Fig. 11. The values did not significantly change between
the 0. 5M NaOH test solution and the 5M test solution. The measured coupling potential and
potential standard deviation for the other test materials was higher (the Alloy 600 specimens
coupling potential changed sign). The coupling current and the current standard deviation
(Fig. 12) was higher in all cases. The resistance was lower in all test materials, indicating a
higher corrosion rate (Fig. 13). The degree of localization, also shown in Fig. 13, was also
lower. This indicated that general corrosion was occurring [4].
The creviced Vendor B Alloy 690 specimen demonstrated significant differences in the
measured coupling potential and potential standard deviation from the uncreviced Vendor A
Al l oy 690 specimen. The creviced Alloy 690 specimen current standard deviation was sig-
nificantly higher than the uncreviced specimens. There was no significant difference between
the coupl i ng current measured in the creviced and uncreviced Al l oy 690 specimens (Fig.
l l ) .
DOHERTY El" AL. ON EVALUATION OF MATERIALS 295
2 . o E 6 l t l i
i I I a
A
<
- 1 . 0 E- 0 6
- 2 . 0 E* 0 6 i i i
0 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0
T i me ( s e c o n d s )
O,OE+O0
- 1 . 0 E- 0 4
A
>
Z - 2 . 0 E- 0 4
EL
UJ
- 3 . 0 E - O 4
- 4 . 0 E - 0 4 ~ r
0 5 0 0 1 0 0 0 1500 2 0 0 0
T i me ( s e c o n d s )
FIG. 4c--Typical ECN and EPN data for specimens in O.O1M NaOH (Alloy 600).
This degree of localization, shown on Fig. 13, was also significantly higher for the creviced
specimens (0.88 versus 0.28), indicating localized attack in the creviced specimen [4].
After testing was completed, the specimens were examined. There was no significant
evidence of localized attack in the creviced specimen. It would appear that the localized
corrosion events were masked by high levels of general corrosion. Figure 14 shows the
micrographs of each specimen.
Di s c us s i on
The main objective of this test program was to demonstrate that electrochemical noise
monitoring (ENM) techniques could be used to monitor the increased corrosiveness of an
environment and the different corrosion processes occurring on test materials in a nonper-
turbative manner. These goals were achieved. Differences in solution aggressiveness can be
clearly seen by compari ng R, values, as shown in Figs. 15 t hrough 17. The resistance noise
of all specimens decreased with increasing NaOH concentration, indicating an increase in
corrosion rates. The resistance noise of the alloys in the 0. 5M NaOH solution decreased with
O.OE+O _~
I.-
Z
LLI
0
,m
2. 0E- 7 - - 4. 0E- 3
2. 0E- 3
~ - 2. 0E- 7
0 B (cu~ent)
~2,OE~ 3
~7 600 (current)
/ --~-- A (potential)
B (potential)
600 (potent=al)
- 4. 0E- 7 : ~ i ' - 4. 0E- 3
0. 00 200. 00 400. 00
T I ME ( h o u r s )
FIG. 5 - - Me a n coupling current and pot ent i al f or test specimens in O.OIM NaOH.
5. 00E- 7 - -
Vendor A Alloy 690
( ~ Ve ndor B Alloy 690
~z Alloy 600
"~" 4. 00E- 7
Q.
E
Z
o_
I. -
~ 3. 00E- 7
I.U
121
121
n-
<
Z
CO 2 . 0 0 E- 7
1. 00E- 7
r 1 1 f r 1 T [ T - - - -
0. 00 100o00 200. 00 300. 00 4 0 0 . 0 0 500. 00
T I ME ( h o u r s )
FIG. 6- - St andar d deviation of current noise f or test specimens in O.O1M NaOH.
DOHERTY ET AL. ON EVALUATI ON OF MATERI ALS 297
FIG. 7--Resistance noise and degree of localization f or test specimens in O.01M NaOH.
time approaching the 5M NaOH R, values, indicating that the corrosion rates in 0.5M and
5M NaOH may not be that different, that is, high general corrosion rates.
Differences in alloy composition could also be seen in all environments. This could be
most clearly seen by examining the standard deviation of the ECN data for all environments.
In all cases, the ECN standard deviation was significantly higher for Alloy 600 than for
Alloy 690. This was expected, since Alloy 690 has a higher chromium content than Alloy
600.
The creviced Vendor B Alloy 690 tube specimen demonstrated significantly different be-
havior to the uncreviced Alloy 690 specimens. The degree of localization was higher, indi-
E
I.-
Z
ILl
r',,"
n,"
C3
r
6.0E-5
4.0E-5
2.0E-5
0.0E+0
8.0E-4
I
~ 4.0E-4
O. 0E+O --"~
I --
I z
i w
L
-4.01::-4
i
1
!
-2.0E-5 I I -8.0E-4
I I i '
0.00 40.00 80.00
TI ME (hours)
FIG. B--Mean coupling current and potential f or test specimens in 0.5M NaOH.
2.50E-5
O.
E
z
0
<
iii
C~
ra
r
<
t:)
z
<
Vendor A Alloy 690
C) Vendor IB Alloy 690
2.00E-5
1.50E-5
1.00E-5
5.00E-6
O.OOE+O ' ) ' I i I ' ) '
0.00 20.00 40.00 60.00 80.00 100.00
TIME (hours)
FIG. 9mSt andard deviation of current noise f or test specimens in 0.5M NaOH.
FIG. lO--Resistance noise and degree of localization f or test specimens in 0. 5M NaOH
E
j-.
z
uJ
n~
r~
0
3. 0E- 3
5 M NaOH
A (r
e (cu,ent~
600 (current)
A A ~ ~
t r e y ( p a t )
4.0E-4
0. 0E+0
v
-4. 0E-4 I j i ] r [ -1. 0E-3
0.00 100.00 200.00 300.00
T I M E ( h o u r s )
FIG. 11--Mean coupling current and potential f or test specimens in 5M NaOH.
2.0E-3
I .OE-3
O.OE+O
.,..,
O
v
. . I
<
F-
Z
u.I
I--
O
O_
cating that, as expected, there was localized corrosion in the creviced region. However,
further work is required to identify localized corrosion activity or to demonstrate that general
attack was greater than the local activity. The calculated resistance of the creviced Vendor
B Al l oy 690 specimen was not significantly lower than that of the uncreviced Speci men A.
The lack of evidence of localized attack is probabl y a function of relatively short test times.
Anot her objective of this test program was t o identify a test environment that would
produce cracking of Al l oy 690 within a reasonable period of time and to identify the initi-
ation of cracking using ENM. This has not been achieved, as yet, but work will continue t o
identify an opt i mum chemistry. It appears that general attack was high in Tests 2 and 3.
Future work will focus on: (1) using 0. 01M NaOH, (2) incorporating a SCC cracki ng agent
(for example, a lead compound) into the test solution, and (3) applying potential chemically
or electrochemically to a loaded specimen. Once this environment has been identified, testing
with mockups of specific steam generator component s will be initiated.
Co n c l u s i o n s
1. The corrosion behavior of Al l oy 690 steam generator tube material exposed to various
sodium hydroxi de environments was successfully monitored using online electrochem-
ical techniques. Activity was identified as being general and not severe f or the moni-
toring period.
1.00E.-4
0.
E
z
O
I -
<
UJ
C3
C3
0E
<
o
z
<
I -
o3
8.00E-5
6.00E-5
4.00E-5
2.00E-5
<~ Vendor A Alloy 690
C) Vendor B Alloy 690
[ ] Alloy 600
~)~ Creviced Vendor B Alloy 690
O.OOE+O I ' I ' I ' I '
0.00 100.00 200.00 300.00 400.00
TIME (hours)
FIG. 12--Standard deviation of current noise f or test specimens in 5M NaOIt.
FIG. 13--Resistance noise and degree of localization f or test specimens in 5M NaOH.
FIG. 14--Specimen micrographs taken at the apex of the C-ring specimen at a magnification of x lO0.
Upper left is Vendor A, upper right is Vendor B, lower left is Alloy 600, and lower right is the creviced
specimen.
160,00
E
r
o
ILl
(o
z
<
I -
o9
m
O9
LU
n"
Alloy A
I
!
, o o o _ /
I
~7 5 M NaOH f
40.00 ~ t
0,00 ' I , ! '
0.00 100.00 200.00 300,00 400.00 500.00
TIME (hours)
FIG. 15--Resistance noise for Specimen A in varying concentrations of NaOH.
160,00 L Alloy B
E
f-
U.l
c.)
z
(/)
UJ
oc
80.00
l (~ 001 M NaOH
C~ o 5 M NaOH
40.00 ( ~ ~7 5 M NaOH
0.00 ~ ~ = I
0,00 100.00 200.00 300.00 400.00 500.00
TIME (hours)
FIG. 16--Resistance noise for Specimen B in varying concentrations of NaOH.
120.00
"~" 80.00
E
l a , l
z
<
h-
6o
r 40.00
Alloy 60C
F
I ~ 0 01 M NaOH
( ~ 0 5 M NaOH
v ~7 5 M NaOH
0.00 ' I i I ' ! ' I r
0.00 100.00 200.00 300.00 400.00 500.00
TI ME ( hour s)
FIG. 17--Resistance noise for Alloy 600 specimen in varying concentrations of NaOH.
2. The data obtained demonstrated that the corrosion activity was episodic and differences
in the aggressiveness of the test environment were identified using the resistance noise,
Rn.
3. Differences in the ECN data between creviced and uncreviced Alloy 690 specimens
were observed. The degree of localization, DoL, of the creviced approached a value of
one.
4. Differences in alloy composition between Alloy 600 and Alloy 690 were remotely
observed using ENM. The standard deviation of the ENM data was higher for Alloy
600.
Re f e r e nc e s
[1] Doherty, E E., Moore, D. C. A., Cox, W. M., and Dawson, J. L., "An Application of Advanced
Electrochemical Monitoring to Corrosion of Heat Exchanger Tubing," in Proceedings of the Fourth
Symposium on Environmental Degradation of Materials in Nuclear Power Systems, 1989.
[2] Moore, D. C. A., Lindsay, P., Hewett, D., and Doherty, P. E., "Progress Towards On-Line Sur-
veillance in Service Water Systems," in Proceedings of the EPRI Service Water Reliability Im-
provement Seminar, 1989.
[4] Quirk, G. P., Mirzai, M., Doherty, P. E., and Bek, W., "Corrosion Surveillance for Reactor Materials
in the Calandria Vault of Pickering NGS A Unit 1," in Proceedings of the Sixth International
Symposium on Environmental Degradation of Materials, 1993.
[5] Quirk, G. E, Doherty, E E., Eden, D. A., and Cox, W. M., "Corrosion Monitoring Developments
for Steam Generators in Ontario Hydro," in Proceedings of the Steam Generator and Heat Ex-
changer Conference, 1990.
[6] Doherty, P. E., Moore, D. C. A., Quirk, G., Brennenstuhl, A. M., and King, P. J., "Corrosion
Surveillance Developments at Ontario Hydro," in Proceedings of the Fifth International Symposium
on Environmental Degradation of Materials, 1991.
[7] Damak, S., Doherty, P. E., Quirk, G., and Moore, D. C. A., "Continuous Monitoring of Corrosion
Behaviour in a Steam-Generator Tube-to-Tubeplate Crevice," in Proceedings of the International
Conference on Advances in Corrosion and Protection, 1992.
[8] Loto, C. A. and Cottis, R. A., "Electrochemical Noise Generation During Stress Corrosion Cracking
of High-Strength Aluminum AA 7075-T6 Alloy," Corrosion, Vol. 45, No. 2, 1989, pp. 136-141.
[9] Hladky, K. and Dawson, J. L., "The Measurement of Localized Corrosion Using Electrochemical
Noise," Corrosion Science, Vol. 21, No. 4, 1981, pp. 317-322.
[10] Flis, J., et al., "Impedance and Electrochemical Noise Measurements on Iron and Iron-Carbon
Alloys in Hot Caustic Soda," Corrosion Science, Vol. 32, No. 8, 1991, pp. 877-892.
[11] Metikis-Hukovic, M., Stupnisek-Iisac, E., and Loncar, M., "Electrochemical Noise Measurement
for the Evaluation of the Protective Properties of Organic Coatings in Marine Atmospheric Envi-
ronments," Bulletin of Electrochemistry, Vol. 7, No. 3, 1991, pp. 128-132.
Pi t t i n g
Shel don T. Pri de, 1 John R. S c u l l y , 2 and Jack L. Huds on ~
Analysis of Electrochemical Noise from
Metastable Pitting in Aluminum, Aged
AI - 2%Cu, and AA 2024- T3
REFERENCE: Pride, S. T., ScuUy, J. R., and Hudson, J. L., "Analysis of El ectrochemi cal
Noi se f rom Metastable Pitting in Al umi num, Aged AI-2%Cu, and AA 2024-T3," Electro-
chemical Noise Measurement f or Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns,
John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., American
Society for Testing and Materials, 1996, pp. 307-331.
ABSTRACT: We compare methods of analyzing electrochemical current (ECN) and potential
(EPN) noise data associated with metastable pitting and the transition from metastable to stable
pitting. Various analysis methods were applied to electrochemical noise data associated with
metastable pit events on aluminum, aged AI-2%Cu, and AA 2024-T3 ST. Two experimental
approaches were used. High-purity AI, roughly simulating copper-depleted grain boundary
zones in aged AI-Cu alloys, was potentiostatically polarized so that current spikes associated
with individual pitting events could be analyzed. Second, the coupling current between nom-
inally identical galvanically coupled A1, aged A1-2%Cu, and AA 2024-T3 ST electrodes was
recorded in conjunction with couple potential using a saturated calomel reference electrode.
Pit stabilization occurred when individual pits exceeded a threshold of l p i t l r p i t > 10 -2 A/ c m
at all times during pit growth as established from potentiostatic measurements. The magnitude
of this ratio is linked directly to the concentration of the aggressive solution within pits. Two
related statistical pit stabilization factors (Irms/rp, ,ota~ from ECN data and the mean of (l~ak-
lox)lrp, values from each pit current spike) were obtained from galvanic ECN data containing
a large number of pit current spikes. These parameters provided a better indication of the
transition to stable pitting than the pitting index or noise resistance but also had shortcomings.
Spectral analysis using current and potential spectral power density (SPD) data provided qual-
itative information on pit susceptibility. However, the transition to stable pitting could not be
accurately defined because of a lack of information on pit sizes in spectral data.
KEYWORDS: AA 2024-T3, aluminum, constituent particles, copper-depleted zones, maxi-
mum entropy method, metastable pitting, noise resistance, pitting index, pitting potential, spec-
tral power density, pit stabilization factor, repassivation, S' particles, stable pitting
Pr evi ous e l e c t r oc he mi c a l anal yses of met ast abl e pi t t i ng o f a l umi num (A1) base mat er i al s
can be cat egor i zed i nt o t hree gener al areas: char act er i zat i on of t he i nt ensi t y (rat e and am-
pl i t ude) o f met as t abl e pi t t i ng, and spect r al anal ysi s o f pi t t i ng. The r esul t s o f t hese st udi es
ar e s ummar i zed.
Formerly, Ph.D. candidate, Department of Chemical Engineering, University of Virginia; now, mem-
ber of technical staff, Rohm and Haas Chemical Co., Philadelphia, PA.
2 Associate professor, Materials Science and Engineering, University of Virginia, School of Engineer-
ing and Applied Science, Charlottesville, VA 22903-2442.
3 Full professor, Chemical Engineering, University of Virginia, School of Engineering and Applied
Science, Charlottesville, VA 22903-2442.
3O7
WW'vV.astIll.0r~
Hol l i ger and BOhni i nvest i gat ed t he met as t abl e pi t t i ng o f A1 in chl or i de sol ut i ons usi ng a
r ot at i ng di sk el ect r ode under pot ent i ost at i c condi t i ons [1]. Expe r i me nt s wer e c onduc t e d be-
l ow t he pi t t i ng pot ent i al . Met as t abl e pi t s pr oduc e d cur r ent spi kes r epr es ent i ng t he act i vat i on
and subsequent r epas s i vat i on pr ocess. The r at e o f spi ke occur r ence decr eas ed wi t h decr eas i ng
pot ent i al be l ow E p i t and i ncr eas i ng r ot at i onal speed. The rat e o f met as t abl e pi t i ni t i at i on,
P ( t ) , f ol l owed t he f unct i on P ( t ) = A * e x p ( - b * t) + C, wher e P ( t ) is t he pi t i ni t i at i on rat e,
t is t i me, A i s t he i ni t i al rat e, b is t he de c a y t i me const ant , and C is t he fitting par amet er .
Wi t h i ncr eas i ng pot ent i al , A b e c a me l ar ger and b b e c a me lower. A i ncr eas ed wi t h decr easi ng
r ot at i on speed. The spi kes gr ew l ar ger and l onger wi t h i ncr easi ng pot ent i al (and decr eas i ng
s peed o f r ot at i on) .
Nume r ous i nvest i gat or s have us ed t he spect r al anal ysi s appr oach. Typi cal l y, noi se cur r ent
s pect r a are obt ai ned by conver t i ng t he el ect r ochemi cal cur r ent ( ECN) ver sus t i me si gnal s
be t we e n t wo i dent i cal el ect r odes coupl ed t hr ough a zer o r esi st ance a mme t e r i nt o t he f r e-
quency doma i n usi ng a s pe c t r um anal yzer. ECN be ha vi or at cons t ant pot ent i al can al s o be
anal yzed. Pot ent i al fl uct uat i ons be t we e n t wo i dent i cal el ect r odes or wi t h r es pect t o a r ef er -
ence el ect r ode ( EPN) can al s o be r ecor ded. A t r end in t he dat a r esul t i ng f r om dr i f t in t he
pot ent i al t i me r ecor d is s ome t i me s r e mo v e d bef or e anal ysi s.
Ber t occi and Kr uge r i nvest i gat ed t he el ect r ochemi cal noi se f r om f l uct uat i ons in t he pas s i ve
cur r ent o f AI and a mor phous and cr yst al l i ne Fe- Cr - Ni al l oy el ect r odes under pot ent i ost at i c
cont r ol [2]. AA 6061 A1 was st udi ed in bor at e buf f er sol ut i on t o whi ch 0. 05M s odi um
chl or i de (NaC1) had been added. The pi t t i ng pot ent i al wa s r oughl y est abl i shed b y obs e r vi ng
t he si gni fi cant i ncr eas e o f spect r al cur r ent ampl i t udes t hat coi nci ded wi t h t he f or ma t i on o f
pits. The ECN s pect r um at t he pi t t i ng pot ent i al o f AI was mor e t han t wo or der s o f magni t ude
gr eat er t han t he ECN s pect r um f or a pot ent i al bel ow t he pi t t i ng pot ent i al . I s ol at ed cur r ent
bur st s wer e obs e r ve d in t he cur r ent t i me si gnal dur i ng t he i nduct i on t i me bef or e br e a kdown
wi t h spi ke de c a y t i mes t hat r anged be t we e n 0.5 and 1.5 s. The s e cor r es ponded t o t he ma x-
i mu m r epas s i vat i on t i mes t hat di d not r esul t in t he f or ma t i on o f st abl e pits. Thus, what t hey
des cr i bed as cur r ent bur st s wer e cur r ent spi kes as s oci at ed wi t h met as t abl e pi t t i ng event s.
Concer ni ng t he i r on- chr omi um- ni ckel ( Fe- Cr - Ni ) al l oys, t he cr yst al l i zed al l oy ga ve a hi gher
ECN ampl i t ude t han t he a mor phous mat er i al . I t wa s s ugges t ed t hat t he cr yst al l i zed al l oy has
a muc h gr eat er t endency f or l ocal i zed at t ack as a r esul t o f st ruct ural het er ogenei t y o f t he
pas s i ve film. Cr i mpr ove d t he r epas s i vat i on rat es f or Fe - Cr al l oys, whi ch pus hed t he r ol l - of f
f r equency o f cur r ent powe r s pect r a t o hi gher f r equenci es, i ndi cat i ve o f shor t er r epas s i vat i on
t i mes [3].
Spect r al p o we r ampl i t ude (SPA) dat a have been used t o a na l yz e cur r ent f l uct uat i ons be-
t we e n nomi nal l y i dent i cal pai r s o f Al - ba s e and si l i con- car bi de ( Si C) - r ei nf or ced Al - ba s e al-
l oys in neut r al chl or i de el ect r ol yt es [4]. SPA dat a f or A1 7075- T73 cor r el at ed wi t h pi t dept h
in t he cas e o f cupr i c i on- accel er at ed pi t t i ng in neut ral , aer at ed 0. 5M NaCI . Ma x i mu m pi t
dept h wa s near l y pr opor t i onal t o t he l ow- f r e que nc y SPA pl at eau r ai sed t o t he 0. 25 p o we r as
det er mi ned af t er l - h i mmer s i on. However , t he char act er i st i c r ol l - of f f r equency i ncr eas ed
exponent i al l y wi t h Cu 2 concent r at i on suggest i ng f ast er r epas s i vat i on wi t h Cu 2 Compa r i -
sons bet ween t he noi se s pect r a gener at ed f r om scr at ched el ect r ode pot ent i al f l uct uat i ons and
nat ur al open ci r cui t pot ent i al ( OCP) f l uct uat i ons as a r esul t o f pi t t i ng i ndependent l y con-
f i r med t hat t he t i me cons t ant associ at ed wi t h AI fi l m r epai r cor r el at ed wi t h t he r ol l - of f f r e-
quency o f t he vol t age SPA pl ot [5]. Mor eover , t he ampl i t ude s pect r um o f t he OCP fl uct ua-
t i ons was s i mi l ar t o t hat obt ai ned f r om t he scr at ch test. Vol t age SPA pl ot s have al s o been
used t o a na l yz e t he t r ansi ent be ha vi or o f pur e A1 in neut r al and al kal i ne sol ut i ons wi t h and
wi t hout CI - addi t i on [6]. Chavar i n st udi ed t he act i vat i on me c ha ni s m o f A1 in t he a bs e nc e
and pr es ence o f i ndi um i ons in a chl or i de- cont ai ni ng me d i u m or f or a l umi num- i ndi um (A1-
PRIDE ET AL. ON EN FROM METASTABLE PITTING 3 0 9
I n) al l oys by anal yzi ng t he f r ee cor r os i on pot ent i al usi ng vol t age SPA pl ot s [7]. A gener al
cons ens us wa s t hat i ncr eases in l ow- f r equency spect r al noi se ampl i t udes cor r el at e wi t h pi t t i ng
and t hat t he r ol l - of f f r equency ( f r equency at whi ch t he spect r al ampl i t ude begi ns t o decr eas e)
cor r el at es wi t h r epas s i vat i on rat e. The l at t er de c r e a s e d wi t h i ndi um i ons or I n al l oyi ng and
i ncr eased wi t h i r on- bas ed mat er i al s t hat wer e al l oyed wi t h Cr. I t has al so been concl uded
t hat shal l ow r ol l - of f sl opes o f - 2 0 d B/ d e c a d e or l ess ar e i ndi cat i ve o f pi t t i ng cor r osi on. The
r eas oni ng is t hat noi se event s gove r ne d by st ochast i c pr oces s es such as whi t e noi se shoul d
pr oduce spect r al pl ot s wi t h a sl ope o f zer o, wher eas a r ol l - of f o f mor e t han - 2 0 d B/ d e c a d e
in t he SPA ( - 4 0 dB in t he spect r al p o we r densi t y f or ma t ) r epr esent s gener al cor r os i on or a
pas s i ve st at e wi t h f i l m repair.
Ne i t he r st at i st i cal nor chaos anal ysi s me t hods have been br oa dl y appl i ed t o el ect r ochemi cal
noi se as s oci at ed wi t h t he pi t t i ng o f A1. For a r ecent r evi ew o f dyna mi c s o f el ect r ochemi cal
r eact i ons i ncl udi ng per i odi c and chaot i c osci l l at i ons and s pat i ot empor al pat t er ns, see Re f 8.
The el ect r ochemi cal cur r ent and pot ent i al noi se t i me r ecor ds ( EN) di s cus s ed a bove r ecor d
i nf or mat i on about pi t i ni t i at i on, pr opagat i on, and r epassi vat i on. However , little i s under s t ood
concer ni ng how EN can be used t o f or ecas t t he t r ansi t i on f o r m met as t abl e t o st abl e pi t t i ng.
The goal o f this st udy is t o ma k e t hat connect i on. Thi s st udy f ocus es on t he anal ysi s o f EN
si gnal s or i gi nat i ng f r om met as t abl e pi t t i ng pr oces s es on Al - ba s e mat er i al s. The capabi l i t y o f
var i ous si ngl e- event , st at i st i cal , and spect r al anal ys i s me t hods t o f or ecas t t he t r ansi t i on f r om
met as t abl e t o st abl e pi t gr owt h is i nvest i gat ed. I n t he cas e o f t he s i ngl e- event appr oach, t he
gr owt h rat e, anodi c char ge, and pi t cur r ent dens i t y f or i ndi vi dual pi t t i ng event s wer e det er -
mi ne d f or a l ar ge popul at i on o f pi t t i ng cur r ent spi kes obt ai ned pot ent i ost at i cal l y. Resul t i ng
pi t pr oper t i es are c o mp a r e d t o el ect r ochemi cal cr i t er i a f or pi t st abi l i zat i on wi t hout t aki ng
i nt o cons i der at i on t he exi s t ence o f any r el at i ons hi p be t we e n one pi t and t he next. I n t he cas e
o f t he st at i st i cal and spect r al anal ys es met hods , a l ar ge popul at i on o f met as t abl e pi t t i ng event s
det ect ed ove r a gi ven t i me per i od wer e anal yzed t o gai n i nsi ght i nt o t he pi t st abi l i zat i on
pr ocess. To achi eve t hese goal s, t he suscept i bi l i t y t o pi t t i ng cor r os i on wa s var i ed bot h t hr ough
cont r ol o f envi r onment al var i abl es ( hal i de concent r at i on, i nhi bi t or addi t i on, aerat i on), and
met al l ur gi cal f act or s ( pr ogr es s i vel y mo r e suscept i bl e mat er i al : hi gh- pur i t y A1, aged AI -
2%Cu, and AA 2024- T3) .
Experimental Methods
Materials
To var y pi t t i ng suscept i bi l i t y, (1) hi gh- pur i t y, c ol d- wor ke d AI, (2) art i fi ci al l y aged A1-
2%Cu, and (3) AA 2024 ( bal ance: A1, 4. 4 wt % Cu, 0. 6 wt % ma nga ne s e [Mn], 1.5 wt %
ma g n e s i u m [Mg], Fe, Si i mpur i t i es) o f shor t t r ans ver s e or i ent at i on in t he T3 condi t i on (So-
l ut i on heat t reat , col d wor k, and nat ur al l y aged) wer e i nvest i gat ed. Th e t hr ee f or ms o f hi gh-
pur i t y Al ( 99. 999%) used in t hi s st udy wer e 0. 25- r am di a me t e r anneal ed wi r e, 0. 25- r am-
t hi ck foi l , and s put t er - depos i t ed t hi n f i l ms ( - 1 - ~ m fi l m t hi cknesses) . The AI - 2 %Cu al l oy
wa s ma de f r om 99. 999% A1 and Cu. The agi ng condi t i ons f or t he A1-2%Cu wer e (1) hel d
at 510~ f or 2 h t o di s s ol ve t he Cu c ompl e t e l y i nt o t he A1 mat r i x, (2) quenched t o r o o m
t emper at ur e, and (3) hel d at 246~ f or 24 h. Tr ans mi s s i on el ect r on mi c r os c opy ( TEM) anal -
ys i s r eveal ed gr ai n bounda r y 0-A12Cu pr eci pi t at es, i nt r agr anul ar 0' and 0" pr eci pi t at es and
mos t l i kel y Al - r i ch ( Cu- depl et ed) zones at grai n boundar i es [9]. I t i s wel l known t hat me t -
ast abl e pi t t i ng i s i nduced by gal vani c coupl i ng be t we e n t he 0-AI2Cu pr eci pi t at es and t he A1-
r i ch mat r i x [9,10]. A1-2%Cu wa s used as a mode l al l oy t o st udy met as t abl e pi t t i ng i nduced
at such si t es. AA 2024- T3 o f ST or i ent at i on t ypi cal l y cont ai ns nume r ous mi cr os t r uct ur al
het erogenei t i es that may i nduce pi t t i ng. St rengt heni ng is pr ovi ded by Gui ni er-Prest on (GP)
zones, but undi ssol ved excess AI2CuMg (S or S' ) , A12Cu, as wel l as unreact ed (Mn, Fe)3SiAllz
and fine di sper soi d Cu2Mn3Al2o part i cl es are t ypi cal l y present.
Experimental Procedures
The bul k AI - 2%Cu and AA 2024 sampl es were pol i shed to a 600-gri t finish, ul t rasoni cal l y
cl eaned in et hyl al cohol , ri nsed wi t h dei oni zed water, and ai r-dri ed bef or e each experi ment .
Bul k and wi re A1 sampl es were cl eaned wi t h 50% HNO3-50%HzO for 1 mi n to pr oduce a
uni form oxi de film t hi ckness appr oxi mat el y equal to 2 nm [10]. The hi gh- pur i t y AI thin
films were not pol i shed but were cl eaned wi t h acet one, r i nsed wi t h dei oni zed water, and air-
dried. Dei oni zed wat er of 18 Mohm- cm resi st i vi t y and Amer i can Chemi cal Soci et y (ACS)
cert i fi ed reagent s were used to prepare t he el ect rol yt es. Pl at i num in mesh form was used as
the count er el ect r ode and a sat urat ed cal omel el ect r ode (SCE) was used as t he reference
el ect rode in bot h the anodi c pol ari zat i on and the pot ent i ost at i c experi ment s. Al l pot ent i al s
are report ed versus SCE.
Anodic Polarization and Potentiostatic Experiments
Anodi c pot ent i odynami c pol ari zat i on tests were used to det er mi ne pi t t i ng pot ent i al s usi ng
procedures t hat are di scussed el sewhere [11]. For pot ent i ost at i c experi ment s used to exami ne
met ast abl e pi t t i ng events, t he dat a were col l ect ed at a sampl i ng frequency of 30 Hz usi ng
hi gh-puri t y A1 l oop wi re el ect rodes of 0. 01-cm 2 areas to mi ni mi ze the backgr ound passi ve
current. The mi ni mum current resol ut i on was 0.6 nA.
Galvanic Coupling and Open Circuit Potential Experiments
Gal vani c coupl i ng exper i ment s consi st ed of a Kei t hl ey Inst rument s 485 pi coammet er to
measure the current bet ween t wo i dent i cal l y pr epar ed hi gh-puri t y A1, A1-2%Cu, or AA 2024-
T3 el ect rodes. A hi gh-i nput i mpedance vol t age f ol l ower was used to measure the open ci rcui t
pot ent i al (OCP) versus SCE. The vol t age f ol l ower was const ruct ed usi ng a hi gh-i nput i m-
pedance operat i onal amplifier. Bot h the zero resi st ance ammet er ( ZRA) and vol t age fol l ower
were bat t ery powered, and t he el ect r ochemi cal cel l , ZRA, and vol t age f ol l ower were con-
t ai ned in a Cu cage. Anal og current and pot ent i al dat a out put s were col l ect ed on t wo channel s
of the Kei t hl ey Met r aByt e dat a acqui si t i on system. The gai n was set on the dat a acqui si t i on
boar d such that the mi ni mum current and vol t age resol ut i ons were appr oxi mat el y 0.15 nA
and 1.5 mV, respect i vel y. Sampl i ng frequenci es of 166.6 Hz and 1 kHz were used on the
current and vol t age channel s, respect i vel y. Backgr ound current noi se in the measur ement
syst em was ascert ai ned by r epl aci ng the t wo-el ect rode, gal vani c cel l wi t h a 1-Mohm resistor.
Voltage noi se was est abl i shed by short i ng vol t age f ol l ower l eads together. The exposed el ec-
t rode areas were 0.01 cm 2 and were defi ned wi t h t he Whi t t aker 32R + Red Lacquer St op-
Off TM. The bul k AI - 2%Cu and AA 2024 sampl es were al so embedded in an epoxy. The NaCI
concent rat i ons ranged from 10 4 to 1M. The salt sol ut i ons were ei t her deaer at ed wi t h argon
gas before and duri ng each exper i ment or were l eft open to the l abor at or y ai r as specified.
Analysis Methods
Analysis of Single Pit Events
Far aday' s law was used to exami ne the el ect rochemi cal cri t eri a for the t ransi t i on from
met ast abl e to st abl e pi t t i ng as a function of appl i ed pot ent i al and hal i de concent rat i on. Thi s
PRIDE ET AL. ON EN FROM METASTABLE PITTING 311
approach was used onl y for potentiostatically polarized high-purity AI (simulating the Cu-
depleted grain boundary zone) and focused on the factors promot i ng stabilization of pitting
(for example, pit survival instead of repassivation). In addition, the cumulative number of
anodic current spikes corresponding to metastable pitting events was counted, and the de-
pendence of the nucleation frequency of metastable pits on applied potential, CI - concen-
tration, and exposure time was determined.
The charge passed over time (taken from metastable pit initiation to the peak pit current)
was determined for each current spike using Si mpson' s rule. Using the anodic charge for
each event, apparent metastable pit current densities at peak pit current and apparent meta-
stable pit sizes at peak pit current were calculated assuming a hemispherical pit geometry:
where
= ( 3 A W ~ , / 3 ( ~ . . . . \ 1 / 3
r p i t \ ~ . ] , ( / a p p - l o x ) d t )
( l )
rp~, = the pit radius,
AW = the atomic weight of A1,
z = the valence,
F = Faraday' s constant,
p = the density,
lapp = anodic current,
Io~ = the passive current,
t i = initiation time, and
tmax = the time at whi ch i p~ is reached.
A dissolution valence of +3 was assumed. Hemispherical pit geometries have been observed
by various researchers. However, internal pit surfaces are sometimes composed of crystal-
lographic corrosion facets and tunnels [12-14].
The term apparent is used to describe the pit current densities and sizes because of the
underestimation of the true anodic pit current. A portion of the anodic reaction is equaled
by cathodic H2 evolution inside of the pits and is not recorded in the applied current:
l a p p - - l o a : l ( p i t ) a . - - l ( p i t ) c a t h
(2)
where
l(pit),, = the true total anodic pit current and
I(pit)~,,h = the cathodic pit current.
The true anodic pit current can be as much as 16% larger than the measured anodic pit
current given by lap p -- lox, and the difference is observed t o be roughl y constant over a
several-volt potential range [15,16]. Resulting errors in pit size and current density have been
discussed elsewhere [11]. The ratio of the peak anodic current to the pit radius, (/peak --
lox)/rpi,, established from Eq 1 was used as the criterion for pit stability based on analysis
of individual pit current spike events.
Statistical Analysis o f Time Records Containing Many Pitting Events
Statistical and spectral methods were attempted to examine ECN and EPN containing a
large number of metastable pitting events with the goal of relating the resulting information
t o the t ransi t i on from met ast abl e to st abl e pi t t i ng. St at i st i cal anal ysi s met hods were appl i ed
t o the dat a generat ed from gal vani cal l y coupl ed i dent i cal el ect rodes because bot h t he current
and pot ent i al noi se coul d be measured and col l ect ed si mul t aneousl y. Previ ous studies have
col l ect ed dat a at 1 to 2 Hz for spect ral and st at i st i cal anal ysi s [ 1 7 , 1 8 ] . However, a sampl i ng
frequency of 166.6 Hz was used here to capt ure the ful l det ai l of the current spi kes for each
pi t t i ng event. Thi s was necessary because met ast abl e pits events oft en occur over 1 to 5 s
[ 1 1 ] . It was desi r ed to r emove the near DC basel i ne dri ft in gal vani c current and pot ent i al .
Basel i ne dri ft was di st i ngui shed from pi t events in t he fol l owi ng way. Basel i ne dri ft was
est abl i shed by appl yi ng a l ow-pass filter to current and vol t age t i me records wi t h a cut of f
frequency of 20 mHz. The resul t i ng signal (represent i ng the t i me- var yi ng gal vani c current
bet ween t wo passi ve el ect r odes in t he case of t he current -t i me record, l o x , and t he t i me-
varyi ng open ci rcui t pot ent i al of the oxi de- cover ed t wi n el ect rodes, V o f~ wi t hout capac-
i t i ve di scharge caused by pi t t i ng in the case of the vol t age- t i me record) coul d then be sub-
tracted from the ori gi nal raw dat a set at each t i me step. The current and vol t age dat um poi nt s
report ed hereaft er for the st at i st i cal anal ysi s met hods were prepared in this manner unless
ot herwi se stated. The f ol l owi ng equat i on, devel oped by the coaut hors, was used as a stabi-
l i zat i on cri t eri on for a t i me record cont ai ni ng many pits. Thi s equat i on is si mi l ar to I ~ , -
I o ~ / r p . used above for si ngl e pits but i ncl udes all pi t current spi ke dat a not j ust the peak
current:
n /~m~
Pit St abi l i t y Fact or = - (3)
( 3 A W " ] , , 3 i o x ) d , ) , / 3 r p i t t o t a l
\ 2 ~ z F ~ : ( f ( l l c o . o l -
where
n = t he number of dat a poi nt s in the t i me record and
Icouole = the gal vani c coupl e current measured wi t h the ZRA.
In addi t i on, the rat i o ( / p e a k - - l o x ) ] r p , t , est abl i shed from Eq 1, was det ermi ned from the
peak current associ at ed with each i ndi vi dual pit current spi ke aft er subt ract i ng t he basel i ne
dri ft in current. The mean of this rat i o for all current spi kes over an 1800-s t i me per i od and
the maxi mum were subsequent l y det ermi ned.
St at i st i cal paramet ers such as mean, r oot mean square (rms), vari ance, and st andard de-
vi at i on of vol t age or current el ect rochemi cal noi se (EN) have al so recei ved consi der abl e
at t ent i on [ 1 8 - 2 0 ] . Correl at i ons bet ween rms and st andard devi at i on of open ci rcui t vol t age
EN and steel di ssol ut i on rat e have been made [17]. However, the use of rms or st andard
devi at i on of vol t age EN al one can be mi sl eadi ng because passi ve el ect rodes are readi l y
pol ar i zabl e [ 1 8 ] . Passi ve el ect rodes are t herefore suscept i bl e to hi gher vol t age fluctuations
as a resul t of smal l pert urbat i ons of t he chemi st ry or t emper at ur e of t he syst em wi t hout
necessari l y si gnal i ng the enhancement of corrosi on. One suggest i on is that the rms or stan-
dar d devi at i on of current and pot ent i al noi se be combi ned as a noi se resi st ance (R, ) by t aki ng
t hei r rat i o to yi el d a par amet er that may bet t er correl at e wi t h act ual corrosi on behavior.
Rot hwel l and Eden defi ned the el ect r ochemi cal noi se resi st ance (R, ) as the st andard devi at i on
of vol t age di vi ded by the st andard devi at i on of the current [ 2 0 ] . The equat i on used in this
st udy to cal cul at e R, was:
n _ g r r a s
R. = I ~ (4)
n
where V~s is the root mean square of V c o u p l e - Vox c~ versus SCE for all the data points
in the voltage-time record and, similarly, l~ms is the root mean square of I~oup~e - lox. Vox ~~
and lox were established using the low-pass filter method as discussed above. This calculation
was performed for the total number of data points in 1800-s periods. In the case of localized
corrosion, the current should be normalized with the pit area to produce a current density.
However, this requires real-time information on the fraction of surface area actively pitting.
This normalization has not been performed, but its implications are discussed below.
Anot her statistical parameter is the pitting index (PI), which has been defined as the
standard deviation of current divided by mean current [20]:
eI = I s , d ( 5 )
m e a n
Here, ls,d and / m e a n a r e the standard deviation and mean of l~o.p~ - Io~ data for the total
number of data points in 1800-s time periods. PI values far less than one have been taken
to indicate general corrosion whereas numbers greater than or equal to one may indicate
localized corrosion processes [20]. A modified PI has been defined that does not approach
infinity as Imea. approaches zero [21].
PI = 1st___~d (6)
/~s
In this case, raw data were utilized and Iox was not subtracted.
Spectral Anal ysi s o f Time Records Containing Many Pitting Event s
Circumstantial evidence shows that changes in any one or some combination of three SPD
parameters obtained from EN data correlate with localized corrosion. The three spectral
parameters are (1) the slope of the high-frequency region, (2) the rol l -off frequency, and (3)
the level of the frequency independent plateau at low frequency. Increases in the low-fre-
quency EN for current SPDs [18] and a change in the slope of the high-frequency region of
voltage SPDs from - 4 0 to - 2 0 dB [17] have been argued to show a transition from general
to localized corrosion based on an assmnption that pitting is a stochastic white noise process
and should produce a l og- l og SPD slope approaching zero. However, note that an increasing
EN level on a voltage SPD does not necessarily correlate with higher corrosion rates because
a passive polarizable electrode can give rise to significant EPN without indicating accelerated
corrosion. Therefore, spectral analysis of both galvanic ECN and EPN was performed to
determine i f SPD information can indicate a transition to stable pitting, l~oup~e and Vcoup~e data
were filtered using a high-pass filter algorithm to remove low-frequency drift. The cut off
frequencies below whi ch all frequencies were removed were 20 and 5 mHz (AI-2%Cu and
AA 2024-T3). ECN and EPN data were then mathematically transformed from the time
domain to the frequency domain by using either the fast Fourier transformation (FFT) or the
ma x i mu m e nt r opy me t hod ( MEM) . I n t hi s study, bot h met hods wer e at t empt ed. The r esul t s
wer e si mi l ar. The MEM r esul t s are r epor t ed. The r esul t i ng dat a wer e anal yzed in t e r ms o f
spect r al p o we r densi t y ( SPD) pl ot s. Uni t s ar e si gnal a mpl i t ude 2/ Hz ( SPD) at each f r equency
whe r e each d a t u m poi nt i s di vi ded b y t he acqui si t i on frequency.
Re s u l t s a n d Di s c u s s i o n
Anal ysi s o f Si ngl e Pi t Event s
The pi t t i ng pot ent i al s (Ep, ) o f hi gh- pur i t y AI, sol ut i on heat - t r eat ed AI - 4%Cu obt ai ned f r om
t he l i t er at ur e [22], and AA2024- T3 in t wo di f f er i ng s pe c i me n or i ent at i ons ar e s hown in Fi g.
1 as a f unct i on o f CI - concent r at i on. The or i gi n o f t he di f f er ence i n Epi, ver sus [C1 ] sl ope
wi t h AI - 4 %Cu is unclear. Not e t hat a st at i st i cal di st ri but i on o f pi t t i ng pot ent i al s i s obs er ved
f or all mat er i al s. I t s or i gi n has been di scussed el s ewher e [11]. Mul t i pl e cur r ent spi kes wer e
obs e r ve d f or pur e AI wi r e el ect r odes at combi nat i ons o f pot ent i al and [ CI - ] be l ow t he mean
Epit f or A1 (Fig. 2) [11]. I n gener al , i ncr easi ng bot h [ CI - ] and pot ent i al s t r ongl y cor r el at ed
wi t h an i ncr eas ed i nt ensi t y and si zes o f t he cur r ent spi kes, wher eas i nt er gr anul ar as wel l as
i nt r agr anul ar st abl e pi t t i ng wer e s ome t i me s obs er ved at mor e posi t i ve pot ent i al s i n hi gh CI .
Th e pot ent i al - C1- r egi on be t we e n t he pi t t i ng pot ent i al o f hi gh- pur i t y A1 and t hat o f sol u-
t i oni zed AI - 4%Cu defi nes t he r egi on in whi ch i nt er gr anul ar cor r os i on mi ght be expect ed f or
a ge d A1- 4%Cu and AA 2024 al l oys i f t hey cont ai ned s ever el y Cu- depl et ed zones adj acent
t o Cu- r i ch pr eci pi t at es and 4 %Cu in sol i d sol ut i on at gr ai n i nt eri ors [22].
Equat i on 1 was used t o cal cul at e pi t si zes a s s umi ng t hat each cur r ent spi ke c or r e s ponde d
t o an i ndi vi dual met as t abl e pi t t i ng event . I n this case, t he char ge as s oci at ed wi t h t he ent i r e
anodi c cur r ent spi ke wa s us ed t o cal cul at e t he final pi t si ze as s umi ng hemi s pher i cal shape.
Th e act ual si zes wer e det er mi ned f r om me a s ur e me nt s o f pi t mout h by opt i cal mi cr os copy.
The val i di t y o f t he asser t i on t hat each spi ke r oughl y cor r es ponds t o a si ngl e met as t abl e pi t t i ng
event is evi dent f r om c ompa r i s on o f t he popul at i ons o f act ual and el ect r ochemi cal l y cal cu-
l at ed met as t abl e pi t si zes. Fi gur e 3 pr es ent s such a hi s t ogr a m f or hi gh- pur i t y AI foi l in
>~
eL
- 0. 2
- 0. 3
- 0. 4
- 0. 5
- 0. 6
- 0. 7
- 0. 8
l f f 4
t
~- I - <9- - 2024- T3 (Longi t udi nal )
~ - - o - - 2 0 2 4 - T3 (Short -t ransverse)
I
m AI - a%Cu ( Gal vel e and De MichelJ
~ . ~ o ~ . - - x - - Hi gh Puri t y AI ( 99. 999%)
x \
x "-, \ ~
x \ . 8
" ~ \
" . ~ o
" \
I ~ I I I i i i i . . . . . . . . I 1 i I . . . . . I . . . . . . . .
102 10 l i 0 ~ 101
NaCI Concentration (M)
i i I i , l l l l
10 .3
FIG. 1--Pitting potentials f or high-purity AI, aged AI-4%Cu [22], and AA 2024-T3 as a function of
chloride concentration in deaerated NaCI solutions at room temperature.
PRIDE ET AL. ON EN FROM METASTABLE PI'I-FING 315
40
35
g " 30
E
25
~ 20
~ ~5
e
r~ lO
105
, 2 E o p , i - - o 6 v i ~ ~ 1 7 6 I
(3) E pplie d = -0.65V Z ~1o ~ (2).~.~1
10-3MNaCI ~'~102~" I f ~ " l
0 1t25 2250 3375 4500
Time (s)
(3)
i i i I i i i I i ~ i I i i ~
1125 2250 3375 4500
T i me ( s)
FI G. 2- - Current - t i me records f or potentiostatically pol ari zed high-purity AI in deaerated 10 3 M
NaCI at - 0. 5, - 0. 6, and - 0. 65 V versus SCE showing multiple metastable pitting events and the
cumulative number of events per unit area. Note: Current density and cumulative event data have been
normalized to the total electrode area.
J
/ I
3.05
9 ~.~o 9.75 l~etastable Pit Radius (~tm)
i ' i
2
FI G. 3- - Hi st ogram showing a comparison of actual pi t sizes determined by optical microscopy and
calculated f rom the total charge associated with anodic current spikes9 Data taken f or high-purity Al
f oi l in deaerat ed 10 3 M NaCl at - 0 . 5 V versus SCE.
deaerated 10 3 M NaC1 at an applied potential of - 0 . 5 V [11]. Al t hough the specific pit site
associated with each current spike was not located, the distribution of the actual metastable
pit sizes is onl y slightly different from the distribution of sizes calculated from Faraday' s
law, and the total number of pits is similar. Therefore, it was reasonably concl uded that each
current spike corresponds to an individual metastable pit.
A large population of individual pitting transients in 10 4 M NaC1 was then analyzed
assuming that each current spike corresponded to a single pit. Individual metastable pits,
which were formed at potentials ( - 0. 5, - 0. 6, and - 0. 75 V SCE) less than the mean pitting
potential for high-purity AI ( - 0 . 3 0 V at 10 -4 M C1 ), have apparent current densities at the
peak current that range from about 0.05 to 1 A/ c m 2 (obtained from Eq 1). In contrast,
apparent current densities at the peak current of 1 to 10 A/ c m 2 were found for metastable
pits that formed in the pitting potential range ( - 0. 1, - 0. 35, and - 0 . 4 2 V SCE). Moreover,
more metastable pitting events were observed in the pitting potential range consistent with
the connection between metastable pitting intensity and the probability of pit stabilization in
the literature [23]. Stable pits formed at high potentials (0.1, 0.5, and 1.0 V) also have pit
current densities that range from 1 to 10 A/ c m 2 when determined at the same elapsed growth
times as metastable pit lifetimes (taken as the average of the times to reach the peak pit
current for metastable pits). Achi evement of higher peak current densities in roughl y equiv-
alent rise times requires a faster rate of rise in pit current or faster pit growth rates with
increasing potential.
One electrochemical criterion for pit stabilization maintains that the ratio / p i t / ? . p i t m u s t
exceed a value of approximately 4 10 -2 A/ c m [23]. Galvele determined that stable pit
growth woul d occur at d i -> 10 -2 A/ c m, where d is the pit depth and i is the pit current
density [24]. This relationship stems from the need to maintain a critical concentrated alu-
mi num chloride (A1C13) pit chemistry (for example, with corresponding high C1- concentra-
tion from migration and H + production from A1 hydrolysis) to maintain an active pit,
assuming the pit site is open to the more benign external solution [11,23,24]. When meta-
stable pit current spikes are plotted to give a relationship between peak pit current and
apparent pit radius, as calculated from pit charge (Eq 1), evidence of such a threshold in the
case of high-purity A1 is clearly revealed (solid line in Fig. 4). As the potential is increased,
the peak pit currents increase toward a threshold given by/pit/l'pit = l 0 -2 A/ cm. Pits below
this line will repassivate after a transport-limiting oxide cover over the pit site is ruptured
or removed by gas evolution because the 10- 2- A/ cm criterion is not met, and, consequently,
the pit solution would soon become t oo diluted to maintain an active corrosion state. Al so
shown in Fig. 4 are data points, at elapsed times equal to metastable pit lifetimes, from
stable pits that were grown at potentials within or above the pitting potential range. The ratio
of Ipi,/rpi , for these pits always remains above the 10- 2- Al cm threshold as illustrated in Fig.
5. The current from such stable pits increases at least with p.5 so that for hemispherical pits
?'pit Ot /O.5 and ip, ~ t -~ This is significant because the product of ipi, and rpi t is then constant
with time, meani ng that a constant pit chemistry can be maintained [11]. Metastable pits
growing at slower rates (see Fig. 5) produce a product that decreases with time, and it is
reasoned that a concentrated pit chemistry could not be maintained once a transport-limiting
oxide cover is ruptured. Such pits repassivate. In summary, a criterion has been established
that indicates the transition from metastable to stable pitting.
Statistical Anal ysi s o f Hi gh-Puri t y Al, Aged Al-Cu, and AA 2024-T3 S T
ECN and EPN data were obtained for galvanically coupl ed A1-2%Cu in (1) 10 3 M CrO4 -2
and (2) NaC1 concentrations ranging from 10 -3 to 1M. Not e that stable pitting of AI-2%Cu
is highly probable in aerated I M C1- based on comparison of OCPs to pitting potentials.
PRI DE ET AL. ON EN FROM METASTABLE PI TTI NG 317
<
10 2
10 ~
10 ~
10 "]
10-2
103
Stable Pits ~ 'c'li~
/ X g ~ x oO O Met ast abl ePi t s
%.
i i i i i i , I i , ~ i , , i i ~
A b o v e E p i t R a n g e
[] 1.0V
9 0 . 5 V
o 0. 3V
+ 0. 1V
x -O.05V
W i t h i n E c t R a n g e
o -0. 1V
9 -0. 35V
D -0. 42V
B e l o w E r a R a n g e
zx -0. 5V
[] -0. 6V
1 10
9 -0. 75V
Ap p a r e n t Pi t Ra d i u s at P e a k Pi t Cu r r e n t ( ~ m)
F I G . 4--Relationship between peak pit currents and apparent pit radii at peak pit current f or a large
population of metastable pits and stable pits on high-purity Al in 10 -4 M NaCI evaluated at similar
elapsed times [ l 1]. The electrochemical criterion f or pit stabilization of lpJrp. > 10 -2 A/cm is indicated
by the solid line.
Metastable pitting EN time records, before subtraction of baseline drift, are illustrated in
Figs. 6 through 9 for 1800-s exposure periods. Specimens that developed stable pits are not
shown. It is clear that both the rate of metastable pitting as well as the peak currents asso-
ciated with individual events increase with C1-. Figures 10 and 11 show the time records
for high-purity A1 and 2024-T3 in aerated 0.1M NaC1. It is clear from Figs. 6 through 11
that current spikes correlate in time with rapid decreases in potential. However, a slow rise
in potentials to the original baseline upon metastable pit death is observed. This slower rise
in potentials occurred over time periods that always exceeded pit repassivation times as
indicated by the period required for the current to decay to its baseline. This slower rise in
potential is attributed to the slow recharging of the oxide capacitance on the passive electrode
surfaces near the pit as well as on the repassivated pit surface [25]. The rapid decrease in
potential upon pit initiation supplies some of the cathodic current required to support pit
growth [25]. The potential mi ni mum in NaC1 (Figs. 6 through 10) is never more negative
than the OCP for pure A1 ( - 0. 85- V SCE mi ni mum) in concentration A1C1 a used to simulate
electrochemical conditions at a pit site. However, a potential lower than the AI pit repassi-
rat i on potential, found in a potentiodynamic scans always to be 0.05 V more negative than
the mean Epi t [I1], is often achieved consistent with the death of these pits.
Table l presents the results for the statistical analyses of galvanically coupled A1-2%Cu
as a function of C1- ion concentration. Table 2 presents the results for AI, A1-2%Cu, and
AA 2024-T3 exposed in aerated 0. 1M NaCI. The raw R, values decrease with increasing
3 1 8 E L E CT ROCHE MI CA L NOI SE ME A S URE ME NT
I 0 ~
10 -1
. ~ _
1 0 - 2
o
g
~ 10 3
"6
O
1 0 -4
1 0 5
Re l a t i o n s h i p b e t we e n I / r f a c t o r f or pi t s a n d pi t g r o wt h t i me
i ' ' ' ~ I , = i i i F
Pu r e AI i n 1 0 -4 M N a C I
1 v o l t
-
- 0 . 0 5 v o l t s
. - ~ - ; ~ - ~ - - - - . . . . . . . . . . . . .L . . . . , * - ~
~ " ' ~ Stabi l i zati on t hr eshol d - 10 -2 Nc m
- ~ - ~ - 0 . 5 v o l t s
- 0 . 6 v o l t s ~ ~ - ~ . ~ _
i I i , i I i i i i , , , ,
1 10
Time (seconds)
F I G . 5 - - R a t i o o f i n s t a n t a n e o u s p i t c u r r e n t ( c o r r e c t e d f o r p a s s i v e c u r r e n t d e n s i t y ) t o i n s t a n t a n e o u s
p i t r a d i u s a s s u m i n g h e m i s p h e r i c a l p i t s v e r s u s p i t g r o w t h t i m e .
C1- (see Table 1) and alloy susceptibility (see Table 2). Two versions of the pitting index
are shown in Table 1. The version of the PI given by Eq 5 actually decreases unexpectedly
with increasing C1- and does not indicate the known strong benefit of the chromate inhibitor
relative to I M NaC1. It is possible that lmea, approaches zero in chromate to produce a large
value of PI. To correct this deficiency, a pitting index given by I s , a / I r m s [ 2 1 ] was also used
(data in Table 1 in parenthesis). In this case, the modified PI for onl y the first 10 min of the
time record is reported. Here, a movi ng average of the current data was used without baseline
subtraction. There is a slight increase in PI toward one (pitting) with increasing CI - , but the
chromate case produces a PI of 0.71 instead of a number approaching 0 (for uniform passive
dissolution) [ 2 1 ] . The PI given by Eq 5 also decreases with increasing alloying content. This
produces an unexpected decreasing trend in PI with increasing pitting susceptibility for 2024-
T3 in compari son to high-purity A1 in aerated 0. 1M NaC1 (see Table 2).
The statistical parameter l , , s / r , o , ~ j provides some indication of an increased likelihood of
stable pitting with C1- especially in comparison to the chromate solution, which suppressed
all metastable pitting (see Table 1). Increased pitting susceptibility is also indicated by this
parameter in the case of the 2024-T3 alloy relative to high-purity A1 (see Table 2). The pit
stabilization factor increases by a factor of 18 when considering 2024-T3 in compari son to
high-purity A1. However, the results shown in Tables 1 and 2 are still unsatisfactory because
total pit radius and rms current are used and their ratio is orders of magnitude below 10 -2
A/ c m even for conditions that should approach stable pitting. Recall that the ability of such
a critical ratio to indicate the transition to stable pitting was established from potentiostatic
data. The rms current will be lower than the peak pit current, and the mean pit radius from
a number of pit events will be less than the total pit radius representing the sum of all pit
radii. A modification of this parameter that uses the mean of the ratio of peak pit current to
pit radius is expected to provide a better indication of pitting severity. Table 3 reports such
data. Here, the ratio of the peak anodic current to the pit radius, ( I ~ a k - l o x ) / r p , , established
1 0 0
8o
6o
40
<
v
o
r j ~o
-40
-60
-80
- 100
a
- 5 0
l I __( J- - ~ I ~ 1 r__ } } ~ i I I J
200 400 61~ 000 1000 7200 1400 1600 11300
T i m e ( s )
319
- . 55
-.60
- 65
?.
,~ - 75
0
C~
-.80
-.85
- , 90
b
( { ( f t f I - - - - - x - ~ . . _ I I _ _ L ~ _ _ I J I I I
200 400 600 800 1000 1200 1400 ~ 60,@ 1800
T i m e ( s )
FIG. 6--(a) Current and (b) potential versus time records f or galvanically coupled aged AI-2%Cu
exposed in aerated 10 -3 M Na2CrO4 f or 0.5 h. Baseline drift not removed.
3 2 0 100
80
6 0
2o
r j 20
40
6 0
8 0
- 1 0 0
a
2 0 0 4 0 0 6 0 0 8 0 0 1000 1200 1 4 0 0 1 6 0 0 1800
T i m e ( s )
- . 50
- , 55
- 60
~9
- . 6 5
>
- 70
. 75
o
- . 80
. 85
- . 9 0
b
i I i 1 I i I i I i I i I i I l I
200 400 6B0 800 1000 1200 1400 1600 1800
Time ( s )
FIG. 7- - ( a) Current and (b) potential versus time records f or galvanically coupled aged AI-2%Cu
exposed in aerated 10 3 M NaCl f or 0.5 h. Baseline drift not removed.
1oo 321
6 0
r..)
- 4 0
6 0
- 8 0
100 I I 111 I l l I I ] l i [ I I l l [ l l l &I t l l l l l I l ] i l l I I I l l l l l l l I t i l l l l I l l l l l
0 50 100 150 200 250 300 350 400 450 500 550 600
a T i m e ( s )
- . 5 0 F
r
E . A1
p t t
55 ~
- ( , 0
Q,) - . 6 5
~ - 70
- . 8 0
- . B5
i I i I i I i I i ~ i I i I i I I I
- . 90
200 400 600 800 1000 1200 1400 1600 1800
b
T i m e ( s )
F I G . 8 - - ( a ) Current and ( b ) pot ent i al versus time records f or galvanically coupled aged AI-2%Cu
exposed in aerat ed 10 2 M NaCl f or 0.5 h. Baseline drift not removed.
60
L)
- . 50
40
20
0
20
I40
-&O
-80
-100
0 200 400 600
a
I I [ I I I I I I I
8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0
Time ( s )
322 l OO
8 0
- . 55
. 6 0
- . 6 8
~ - . 70
- 75
o
- . 8 0
- . 85
AI
E p i t
r
- . 9 0 t I I I I I I I J I J I J I I I I I
0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0
b T i m e ( s )
F I G . 9--(a) Current and (b) pot ent i al versus time records f or galvanically coupled aged Al -2%Cu
exposed in aerat ed 1 M NaCl f or 0.5 h. Baseline drift not removed.
1oo 3 2 3
80
6 0
40
~ 0 ~'
Q) 20
- 40
- 60
- 80
- 1 0 0 t I i ( L ( J ( i l i I i ( J [ i l
200 400 600 800 1000 1280 1400 1600 1800
a
Time ( s )
- 7 5
- 8 0
- . 8 5
- . ' : ) 0
- 9 5
[ . L ] - 1 . 0 0
G,) I , 0 5
1 1 0
9 ~-~ - 1 . 1 5
1 2 0
1 . 2 5
- 1 i 3 0
1 . 3 5
- 1 . 4 0
- 1 . 4 5
0
b
I I i I F _ I r I J I t I t I l I I I
200 400 600 800 1000 1200 1400 1600 1800
Time ( s )
FIG. 1 0 - - ( a ) Current and ( b ) potential versus time records f or galvanically coupled high-purity Al
thin film exposed in aerated O. 1 M NaCl f or 0.5 h. Baseline drift not removed.
e
~

b
o

,
'
b

P
o
t
e
n
t
i
a
l

(
V

v
s

S
C
E
)

t
J
1

'
~
'
b
o

i
e
~

C
u
r
r
e
n
t

(
n
A
)

l
t
l
,
-
-

f

t
O

PRI DE ET AL. ON EN FROM METASTABLE PI TTI NG 325
TABLE l--StatisticaI analysis of metastable pitting of aged Al-2%Cu during 0.5-h exposure in
aerated chromate and sodium chloride, a
lrmslrtota~, R., Pit Index b Observation
Solution (A/cm) lO s Mohms
10-3M CrO4 -2 5.5 x 10 -2 15 51.9 very few metastable pits, or
(0.71) no pitting
10 3M NaCI 0.7 4.6 460. 9 infrequent metastable pitting
(0.91)
10-2M NaC1 1.1 2.2 175. 5 metastable pitting
(0.84)
10-~M NaCI 1.4 1.0 76.7 intense metastable pitting
(0.95)
1M NaC1 1.2 1.2 63.1 intense metastable pitting,
(0.85) stable pitting possible
0.01-cm 2 electrode areas.
b Pit index defined by l s t d / / r m s used for number in parentheses.
from Eq 1, was determined based on analysis of each individual galvanic current spike. The
mean of this ratio for all current spikes and the maximum value of the ratio were subse-
quently determined for 1800-s exposure periods in C1- (data in chromate is omitted because
current spikes did not occur). Both the mean and maximum increase with increasing C1-
concentration but are still significantly below the 10-2-A/cm ratio. Recall that Fig. 1 and
OCP data suggest that stable pitting should be very likely in 1M C1-. This underestimation
is of concern because some of the samples exposed to 1M CI- did experience stable pitting
and intergranular corrosion as shown visually after removal as well as during the test by
permanent shifts in galvanic couple potential to significantly more negative values (e.g.,
- 800- mV SCE). The question arises as to whether or not the peak current recorded in the
galvanic couple experiment might be significantly less than the true peak current.
The true anodic current for each pitting event is underestimated for several reasons, one
of which is related to the rapid potential decrease shown in Figs. 6 through 11. It should be
recognized that only a portion of the anodic current required by the pit site on the first
electrode during its growth period is actually measured by the ZRA. The measured ZRA
coupling current from the second electrode during a pitting event is given by
TABLE 2--Statistical analysis of metastable pitting of high-purity AI, Al-2%Cu, and 2024 T3/ ST in
aerated O.1M chloride during 0.5-h exposuref
Irms/ rtota I, e n,
Alloys (A/cm) 105 Mohms Pit Index Observation
Aluminum 0.1 58.7 306
(TF) b
A1-2% Cu 1.4 1.0 77
(aged)
2024-T3 ST t .8 3.4 28
none or few metastable pits
intense metastable pitting
intense metastable pitting,
stable pitting possible
a 0.01_cm 2 electrode areas.
b TF = sputter deposited 99.999% AI thin film.
TABLE 3- - I pe, kp, , / Rp, analysis o f metastable pi t t i ng o f
Al - 2%Cu and 2024 T 3 / S T in chloride solutions during
0.5-h exposure.
Sol ut i on lp,,Irpi , ( A/ c m) lpJrp, , ( A/ c m)
Expos ur e Ar e a Me a n Ma x i mu m
AI - 2%Cu
0. 001M NaC1 1.1 x 10 -4 8. 0 x 10 -4
0. 01 c m 2
0. 01M NaCI 1.5 x 10 4 1.2 10 -3
0. 0l c m 2
0. 1M NaCI 1.8 x 10 4 1.1 x 10 -3
0. 01 c m z
1M NaC1 2.1 x 10 4 1.2 x 10 -3
0. 01 c m 2
0. 1M NaCI 4.1 x 10 _4 1.7 x 10 -3
0.1 c m 2
0. 1M NaC1 9. 2 x 10 -4 3. 8 x 10 -3
0. 6 c m 2
AA2024 T3
0. 001M NaC1 9.1 x 10 5 4. 0 x 10 . 4
0. 01 c m 2
0. 01M NaCI 1.9 x 10 4 9. 7 x 10 4
0. 01 c m 2
0. 1M NaC1 1.8 X 10 -4 9. 8 X 10 -4
0. 01 c m 2
1M NaC1 4. 7 x 10 -4 1.5 x 10 -3
0. 01 c m 2
0. 1M NaC1 1.1 )< 10 . 3 4. 6 x 10 . 3
0. 25 c m 2
( 7)
wh e r e a s t h e t r u e a n o d i c c u r r e n t at t h e p i t i s
/ p i t = ( / c o u p l e - - l o x ) "~ I H 2 -~- / c a - ~ A , ~ , C o ~ - ~ ~ ,
( 8 )
wh e r e
Io~ = t h e g a l v a n i c c u r r e n t b e t we e n t wo p a s s i v e e l e c t r o d e s t h a t c a n b e s u b t r a c t e d b y
r e mo v a l o f a n y s l o wl y d r i f t i n g b a s e l i n e ,
l c, = t h e F a r a d a i c c a t h o d i c c u r r e n t o n t h e p a s s i v e s u r f a c e s ; t h i s r e a c t i o n ( s ) c a n o c c u r
o n b o t h e l e c t r o d e s ,
Cox = t h e p a s s i v e e l e c t r o d e i n t e r f a c i a l c a p a c i t a n c e ,
A~, , 2, d = t h e a r e a s p a r t i c i p a t i n g i n c a p a c i t i v e d i s c h a r g e ( n o t n e c e s s a r i l y e q u a l t o t h e t o t a l
e l e c t r o d e a r e a ) ,
In2 = c u r r e n t a s s o c i a t e d wi t h h y d r o g e n e v o l u t i o n i n t h e pi t , a n d
d E / d t = v o l t a g e t r a n s i e n t e x p e r i e n c e d b y t h e p a s s i v e e l e c t r o d e wh e n a pi t s i t e f o r ms a n d
t h e i n t e r f a c i a l p o t e n t i a l o f t h e p a s s i v e e l e c t r o d e i s s h i f t e d n e g a t i v e l y .
In cases in which (1) solution conductivity is high so that current distributions are uniform
and (2) In2 is negligible, the error resulting from not measuring the current from the first
electrode may only be a factor of two for identical size electrodes. This is not the case in
low-conductivity environments in which less current may be drawn from the second electrode
and effectively Als t > A2, d. The error introduced from the CdE/dt term may be lessened in
the potentiostatic case because the potentiostat attempts to maintain a constant applied po-
tential by supplying more current. However, in the galvanic case, if the CdE/dt term on the
first electrode is larger than the galvanic couple current from the second, then a large dis-
crepancy may be observed between potentiostatic and the galvanic results even for the same
general E-C1- conditions. A discrepancy between measured and actual pit current will affect
all of the analysis methods.
Several shortcomings also exist in the case of the use of R, for localized corrosion sus-
ceptibility. Some of these shortcomings are equally relevant to polarization resistance (LPR)
and electrochemical impedance spectroscopy (EIS), whereas other shortcomings are only
relevant to the galvanic couple arrangement discussed above. This distinction is a very im-
portant one. In the case of EIS and LPR, the following shortcomings exist when applied to
localized corrosion: (1) current response is not causal with the voltage excitation when local
current bursts occur and linearity requirements also may be violated; (2) real-time knowledge
of active pit area is required to calculate corrosion rate but is not known; (3) current non-
uniformity is often encountered, which further compromi ses impedance data; and (4) near-
DC impedances represent average resistances from adjacent passive oxides and pit sites
weighed by their respective areas; the latter is further complicated by the fact that intrinsic
resistance and capacitance values may change with time.
In the case of R, data, some additional complications arise: (1) raw R, data do not provide
impedance data at the zero frequency limit; transformation to the frequency domain is re-
quired to produce I z . I data; (2) R, data involve the series combination of the impedances at
two electrode interfaces in combination with a solution resistance; changes in solution re-
sistance will affect the raw R, values acquired; and (3) in the case of pitting, the increase
in the amplitude of current spikes for larger pits is often matched by an increase in the size
of corresponding voltage fluctuations (see Figs. 6 through 11). The result can be a roughly
constant noise resistance. Moreover, Eq 7 indicates that a portion of/couple is a direct con-
sequence of the last term on the right side, which relies on AE. In fact, Icoup~e can scale
linearly with (A2ndCox dE/dt) if this term dominates the right side of Eq 7. The validity of
an R, given by some statistical ratio of E/ I is then questionable because the result is a
division of a V~,s term by a n Irms term that itself is dominated by A2ndCox dE/dt. This ratio
does not give a measure of charge transfer resistance. We conclude that the noise resistance
may better apply to the case of passive electrodes, or uniform corrosion, but it is of ques-
tionable utility in the case of pitting.
Spectral Analysis of High-Purity AI, Aged Al-Cu, and AA 2024-T3 ST
Spectral analysis of current and potential time records for A1-2%Cu in chromate and C1
are shown in Figs. 12 and 13 (MEM method after low-frequency filtering). A large difference
between the low-frequency EN signal level for chromate and [C1-]-containing solutions is
observed in the cur r ent - SPD plot (Fig. 12). A similar trend with [C1 ] is observed in the
case of the pot ent i al -SPD plot, although the differences are not as great (Fig. 13). ECN data
are a better indicator of pit stabilization than EPN from OCP fluctuations. However, the
differences produced by the higher C1- levels are small in the case of the cur r ent - SPD plot
and do not clearly predict the transition to stable pitting. The reason for this is clear. The
1 0 ~
101
10 2
o,~ 10-3
10 -4
<
10 -s
10 .6
-.-._~.- . . . . . . . . ~_ . . . . . . . s
- - - - - I m M NazCrO 4 I " " " X " ~ , ~
- - ~ - - - l m ~ . C , I " " ' \ " !
- - ~ - o 0.01M NaO I "' A ]
- - >r -O. IM NaCI I ~ - ~
9 IM NaCI I
i n s t r u m e n t noise . . . . . . . . . . . . . . . . . . .
i k i i u n l i t t i i i i i i i I i i i i i i
0.1 1 10
Fr e que nc y (Hz)
FIG. 12--Current spectral power density for galvanically coupled aged Al-2%Cu in the indicated
aerated solutions.
ratio o f pit current to pit radius is a better indicator, as di scussed above, and no information
on pit s i ze i s provi ded by the current SPD.
The repassivation rate o f pits is best indicated by decay o f the current spi ke and not by
the EPN, whi ch is domi nated by oxi de capaci ti ve recharging. The rol l - of f frequency o f
current SPDs is, therefore, o f interest. It does not change in a consi st ent manner, wi th in-
creasi ng CI- suggest i ng that the cause o f pit stabilization is not progressi vel y sl ower repas-
si vati on wi th increasing C1- [26]. To underscore this observati on, si ngl e-pi t event anal ysi s
10 -6
10-7 ~ ~
~.~ - - - - - * - . . . . . . .~ . . . . . . - - ~ : - : ~ ~ . ~ . .
,0, [] 1M..O, I . . . . x. . . ~
- o - - O . O l M N . o I / ' ~ , . . " ~ " " - ?
-- -- - lmM Na2erO 4 instalment noise ".........
0.1 1 10 83
Fr e que nc y (Hz)
FIG. 13--Voltage spectral power density for galvanically coupled aged AI-2%Cu in the indicated
aerated solutions.
PRIDE ET AL ON EN FROM METASTABLE PITTING 329
also does not indicate a change in repassivation rate with bulk CI - concentration [11]. A
lack of change makes sense because pits in all solutions are expected to contain concentrated
C1 and might repassivate at the same rate independent of the bulk C1- level. Al so of interest
is the slope of the high-frequency region. A stochastic process, often suggested for pitting
[27], should have a l og- l og slope approaching zero i f it were white noise. No consistent
trend is observed with increasing Cl - level.
Al l oy susceptibility in aerated 0. 1M NaCI is also best indicated by increases in the low-
frequency EN signal level in the cur r ent - SPD plot (Fig. 14) as compared to vol t age- SPD
(Fig. 15). However, as mentioned above, information on pit size is lacking. The spectral data
are semi-quantitative in nature. Again, information of similar utility but with smaller differ-
ences is provided by potential SPDs.
Su mma r y
1. An electrochemical criterion for stabilization of a single pit site in A1 was defined. The
ratio of single pit current to the same pit radius must exceed l 0 -2 A/ c m at all times
during growth for pits to avoid repassivation.
2. Statistical pit stabilization parameters given by the ratio Irms/rtotaJ or the mean of (/peak --
lo~:)/rp, indicated increased metastable pitting with increasing C1- (or absence of meta-
stable pitting in chromate solutions).
3. The R. decreased whereas the pitting index (PI) changed unexpectedly with increasing
C1- and alloy susceptibility. The PI did not properly distinguish between the complete
absence of pitting in chromate and increased metastable pitting in high Cl - for A1-
based alloys.
4. The accuracy of the R. method was questioned in the case of pitting of A1 for a variety
of reasons. These reasons were in addition to the shortcomings conventionally held for
the application of polarization resistance and impedance techniques to localized
corrosion.
1 0 -1
l 0 -2
. ~ 1 0 .3
~ 1 0 . 4
.=
<
10 -~ A A 2 0 2 4 - T 3 ( S T ) I
. . . . . . . . . A I - 2 % C u
I
- - - - A I ( 9 9 . 9 9 9 % T F )
1 0 `6 i , , , , , , , , i , , , , , ~
0 . 1 1 1 0 8 3
Frequency (Hz)
FIG. 14- - Cur r e nt spect ral powe r densi t y f o r galvanically coupl ed high-purity Al, aged Al -2%Cu, and
AA 2024-T3 S T in aerat ed O. IM NaCl solutions.
i O -5
~'v 10 . . . . . . . . . . . . . . . . 9 ..... ~ ~ . "~.
rn~ 1 0 ~
< "'"'." "~
A A 2 0 2 4 - T 3 ( S T ) I
10"l~ " . . . . . . . . A I - 2 % C u [ . . . . . . . .
t - - - A !
0 . 1 1 10 8 3
Frequency (Hz)
FIG. 15--Voltage spectral power density for galvanically coupled high-purity AI, aged Al-2%Cu, and
AA 2024-T3 ST in aerated O.1M NaCl solutions.
5. The magni t ude of t he l ow- f r equency EN si gnal l evel f r om c ur r e nt - SPD pl ot s i ncr eased
wi t h t he i nt ensi t y of met ast abl e pi t t i ng. However, no i nf or mat i on was gi ven about pi t
size by this met hod. Hence, c ur r e nt - SPD dat a were not f ound to be as val uabl e as t he
st at i st i cal pi t st abi l i zat i on par amet er for pr edi ct i ng the t r ansi t i on to st abl e pi t t i ng.
6. Hi gh- f r equency SPD behavi or di d not i ndi cat e a whi t e- noi se- t ype st ochast i c process or
a process that appr oached whi t e noi s e wi t h i ncr easi ng C1 .
Acknowledgments
Thi s wor k was suppor t ed by gr ant s f r om NASA, ARPA( ONR) , and NSE The suppor t of
each of t hese agenci es is gr at ef ul l y acknowl edged.
Re f e r e nc e s
[1] Holliger, R. and B6hni, H., in Proceedings of the Symposium on Computer Aided Acquisition and
Analysis of Corrosion Data, PV 85-3, M. W. Kendig, U. Bertocci, and J. Strutt, Eds., The Electro-
chemical Society, 1984, p. 200.
[2] Bertocci, U. and Kruger, J., Surface Science, Vol. 101, 1980, p. 608.
[3] Bertocci, U. and Yang-Xiang, Y., Journal of the Electrochemical Society, Vol. 131, 1984, p. 1011.
[4] Kendig, M., Jeanjaquet, S, and Mahoney, M., "Electrochemical Noise Analysis of the Corrosion
of Aluminum Alloys and Composites," Paper 383, CORROSION 88, NACE, St. Louis, MO, 1988.
[5] Uruchurtu, J., in Advances in Localized Corrosion, H. S. Isaacs, U. Bertocci, J. Kruger, and S.
Smialowska, Eds., NACE, Houston, TX, 1990, p. 141.
[7] Chavarin, J. U., Corrosion, Vol. 47, 1991, p. 472.
[8] Hudson, L L. and Tsotsis, T. T., "Electrochemical Reaction Dynamics: A Review," Chemical
Engineering Science, Vol. 49, 1994, pp. 1493-1572.
[9] Scully, J. R., Peebles, D. E., Romig, J. A. D., Frear, D. R., and Hills, C. R., Metallurgical Trans-
actions A, Vol. 23A, 1992, p. 2641.
[10] Scully, J. R., in Critical Factors in Localized Corrosion, PV 92-9, G. S. Frankel and R. C. Newman,
Ed., The Electrochemical Society Softbound Proceedings Series, Pennington, NJ, 1992, p. 144.
PRIDE ET AL. ON EN FROM METASTABLE PI'B'ING 331
[11] Pride, S. T., Scully, J. R., and Hudson, J. L., "Metastable Pitting of Aluminum and Criteria for the
Transition to Stable Pit Growth," Journal of the Electrochemical Society, Vol. 141, No. 11, 1994,
pp. 3028-3040.
[12] Kaesche, H., in Localized Corrosion, R. W. Staehle, B. E Brown, J. Kruger, and A. Agarwal, Eds.,
NACE, Houston, TX, 1971, p. 516.
[13] Richardson, J. A. and Wood, G. C., Corrosion Science, Vol. 10, 1970, p. 313.
[14] Baumgartner, M. and Kaesche, H., Corrosion Science, Vol. 29, 1989, p. 363.
[15] Frankel, G. S., Corrosion Science, Vol. 30, 1990, p. t203.
[16] Beck, T. R., EIectrochimica Acta, Vot. 29, 1984, p. 485.
[17] Searson, P. C. and Dawson, J. L., Journal of the Electrochemical Society, Vol. 135, No. 8, 1988,
p. 1908.
[I8] Mansfeld, E and Xiao, H., Journal of the Electrochemical Society, Vol. 140, 1993, p. 2205.
[19] Eden, D. A. and Rothwell, A. N., "Electrochemical Noise Data: Analysis, Interpretation and Pre-
sentation," Paper 292, CORROSION 92, NACE, Nashville, TN, 1992.
Rates and Mechanisms," Paper 223, CORROSION 92, NACE, Nashville, TN, 1992.
[21] Eden, D. A., Journal of the Electrochemical Society, Vol. 141, No. 5, 1994, pp. 1402-1404.
[22] Galvele, J. R. and de De Micheli, S. M., Corrosion Science, Vol. 10, 1970, p. 795.
[23] Williams, D. E., Stewart, J., and Balkwill, P. H., in Critical Factors in Localized Corrosion, PV
92-9, The Electrochemical Society Softbound Proceedings Series, G. S. Frankel and R. C. Newman,
Eds., Pennington, NJ, 1992, p. 36.
[24] Galvele, J. R., Journal of the Electrochemical Society, Vol. 123, 1976, p. 464.
[25] Isaacs, H. S. and Ishikawa, Y., Journal of the Electrochemical Society, Vol. 132, No. 6, 1985, pp.
1288-1293.
[26] Bertocci, U., Koike, M., Leigh, S., Qiu, F., and Yang, G., Journal of the Electrochemical Society,
Vol. 133, No. 9, 1986, pp. 1782-1786.
[27] Gabrielli, C., Keddam, M., Krati, M., and Pallotta, C., in Computer Aided Acquisition and Analysis
of Corrosion Data, The Electrochemical Society Softbound Series, PV 83-3, M. W. Kendig, U.
Bertocci, and J. E. Strutt, Eds., Pennington, NJ, 1985, p. 210.
Do mi n i q u e Gorse, ~ Cl ai re Boul l er et , ~ a n d Be r n a r d Ba r o u x 2
Effect of Metallurgical Factors on
the Electrochemical Noise Measured on
AISI Type 430 Stainless Steels in Chloride-
Containing Medi a
REFERENCE: Gorse, D., Boulleret, C., and Baroux, B., "Ef f ect of Met al l urgi cal Fact ors
on t he El ect rochemi cal Noise Measured on AI SI Type 430 Stainless Steels in Chl ori de-
Cont ai ni ng Medi a, " Electrochemical Noise Measurement f or Corrosion Applications, ASTM
STP 1277, Jeffery R. }(earns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John
L Dawson, Eds., American Society for Testing and Materials, 1996, pp. 332-342.
ABSTRACT: Potentiostatic noise measurements are performed on a series of AISI 430 type
ferritic stainless steels containing controlled amounts of sulfur (from 8 up to 47 ppm) and
titanium (up to 0.37 wt%), in 0.02M sodium chloride (NaC1) aqueous solution (pH 6.6), in a
range of potentials below the pitting potential. We focus on the evolution of the shape of the
current transients, going from a titanium (Ti) free and 41-ppm sulfur-containing alloy to dif-
ferent Ti-bearing alloys with comparable amount of sulfur ( - 4 0 ppm). The results are com-
pared to the case of a Ti-free and low sulfur (8-ppm) containing alloy. The shape of the anodic
current transients obeys a power law, r'. We distinguish two different situations, with n either
less or larger than 1, which can be associated with the Ti and sulfur content in the steel. The
influence of the exposure time under polarization is also discussed. It appears that for the
manganese sulfide (MnS)-containing alloys, after prolonged polarization, the shape of the met-
astable pitting events evolves toward that found for MnS-free alloys (Ti-bearing), or low-sulfur-
containing alloys. Attention is drawn to the possible relationship between the shape of the
current transients and the metallurgical defects acting as pitting initiation sites.
KEYWORDS: potentiostatic electrochemical noise measurements, stainless steels, inclusions,
titanium, manganese sulfide, pitting
Thi s paper r el at es t he pot ent i ost at i c e l e c t r oc he mi c a l noi se gener at ed at s ome AI SI 430
t ype f er r i t i c st ai nl ess st eel el ect r odes to t he al l oy compos i t i on, es peci al l y t o t he t i t ani um (Ti)
and sul f ur ( S) cont ent . It is now gener al l y accept ed that t he pi t s i ni t i at e ei t her at s ome we a k
poi nt in t he pas s i ve fi l m, or at mi cr odef ect s in t he st ai nl ess st eel sur f ace. Thes e mi cr odef ect s
have been r ar el y i dent i f i ed wi t h pr eci si on. In s ome cases, t hey wer e r el at ed t o t he pr es ence
o f sul f ur in t he mat er i al under i nvest i gat i on, in t he f or m o f sul fi de i ncl usi ons. The nucl eat i on
of pi t s at ma nga ne s e sul fi de ( MnS) i ncl usi ons has been st udi ed on i ron wi t h var i ous addi t i ons
o f Mn and S [1], as wel l as on s ome aust eni t i c and ferri t i c st ai nl ess st eel s. Mn S i ncl usi ons
have been s hown t o be unst abl e in chl or i de- cont ai ni ng sol ut i ons [ 2- 4] .
I Research scientist and graduate student, respectively, CECM-CNRS, 15 rue Georges Urbain,
F-94407, Vitry sur Seine Cedex, France.
2 Professor, Institut National Polytechnique de Grenoble, LTPCM, URA CNRS 29, ENSEEG, BP 75,
38402, Saint Martin d' H~res, France.
332
Www.astIII.org
GORSE ET AL. ON EFFECT OF METALLURGICAL FACTORS 3 3 3
The presence of titanium, in the range of 0.40 wt%, as an alloying element in industrial
ferritic stainless steels improves the resistance t o pitting, because it prevents the formation
of manganese sulfides, which generally act as pitting sites [4]. It has been shown recently
that such an addition increases the pitting potential and reduces the electrochemical current
noise, that is, the intensity and nucleation frequency of the metastable pitting events [2,3].
Moreover, for Ti-bearing steels, the pitting potential in 0. 02M sodium chloride (NaC1) deaer-
ated aqueous solution was found independent of the solution pH, a situation contrasting
singularly with that observed on MnS-cont ai ni ng steels for which the pitting potential drops
abruptly with decreasing the solution pH below a critical value rangi ng between pH 4.5 and
pH 5, presumably a result of the MnS potential and pH-assisted dissolution [2]. However,
making the medi um more severe, namely increasing the chloride content from 0.02 up to
0.5M, the dependence of the pitting potential on solution pH is recovered, even for the
industrial Ti-bearing steels ( - 0 . 4 0 wt% Ti), suggesting that the titanium sulfides become
unstable in concentrated chloride aqueous solutions [4].
However, until now, it was rather unlikely to suggest that changi ng the titanium content
in the steel could modi fy significantly the shape of the metastable pitting transients. This
paper shows that the shape of the current transients can be correlated to the steel composition.
Attention will be paid to the role played by the inclusions on the metastable pitting activity
of the different steels studied, as a function of their respective sulfur and titanium content.
Moreover, we show that the shape of the anodic current transients generated at potentials
below the pitting potential depends also on the exposure time under polarization.
Experimental
I nvest i gat ed Mat eri al s
We study AI SI 430 type ferritic stainless steels, with various sulfur and titanium contents,
whose compositions are presented in Tables 1 and 2. Al umi num is used as a deoxidizing
agent, leading to the presence of some aluminum oxide (A1203) inclusions in the steel. In
the case of Ti-free steels, the metallurgical study shows that the A1203 inclusions may nu-
cleate the MnS or (Mn,Cr)S precipitation.
Ni obi um and titanium are addition elements used to trap the carbon and prevent local
chromi um (Cr) depletion around Cr carbides. The presence of Nb leads to the formation of
Nb carbonitrides, Nb (C,N), which have been shown to be also possible precipitation sites
for manganese sulfides (MnS) in the solid phase. The presence of Ti leads to the formation
of titanium nitrides (TIN) and carbides (TIC) either isolated or precipitated around the tita-
TABLE 1--Composition of the steels noted A through E in
Tables 2 and 3.
Element Wt%
Cr 17
Si 0.35
Mn 0.40
Nb 0.40
AI 0.03
C 0.02
N 0.02--0.03
O (ppm) 30-50
TABLE 2--Titanium and sulfur content of the steels.
Steels Ti, Wt% S, ppm
A 0 8
B 0 41
C 0.05 41
D 0.10 37
E 0.37 47
ni um ni t ri des [2]. A1 oxi des have been i dent i fi ed in the core of t i t ani um ni t ri des, pl ayi ng
pr obabl y t he rol e of nucl ei for the Ti N preci pi t at i on.
Sulfides are present in bot h Ti -free and Ti -beari ng al l oys. The Ti -free and hi gh sulfur (41-
ppm) cont ai ni ng al l oy cont ai ns compl ex i ncl usi ons, that is, manganese sulfides (in the form
of MnS or (Mn, Cr)S), pr eci pi t at ed ei t her around A1 oxi des or Nb carboni t ri des. I n contrast,
for t he Ti-free, low sulfur (8-ppm) cont ai ni ng alloy, onl y finely di sper sed i sol at ed NbC were
found. Ti -beari ng steels cont ai n t i t ani um sulfides gener al l y embedded in Ti car bi des sur-
roundi ng the Ti ni t ri des [2]; t hese t ypes of i ncl usi ons were al so found on t he t hree Ti -beari ng
al l oys.
Unt i l now, the t i t ani um sulfides were consi dered to be less chemi cal l y active than t he
manganese sulfides, whi ch are known to be active pi t t i ng sites in vari ous chl or i de aqueous
medi a.
Sampl e Preparation and El ect rochemi cal Conditions
The sampl es of exposed area equal to 0.785 cm 2 ( 10- mm di amet er) were mechani cal l y
pol i shed usi ng successi vel y finer grades of abrasi ve si l i con car bi de (SIC) paper (300 to 1200)
under runni ng water, and then r epol i shed on 3-1xm, then 1-1~m di amond paste. Af t er degreas-
ing wi t h al cohol , the sampl es were cl eaned for 2 mi n in ul t rasoni c bat hs of al cohol and
acetone, then exposed for 24 h in ai r bef or e the test. A l ow-noi se PAR 273 pot ent i ost at was
used wi t h comput er control. The el ect r ochemi cal arrangement consi st s of a cl assi cal three-
el ect r ode cel l (the wor ki ng el ect rode, a pl at i num [Pt] count er el ect rode, and a sat urat ed
cal omel el ect r ode [SCE] separat ed from t he wor ki ng el ect r ode compar t ment by a coar se
gl ass frit) and a separat e compar t ment for degassi ng t he solution. The cel l was pl aced i nsi de
a Far aday cage. Connect i ons to the ext ernal equi pment were made vi a coaxi al screened leads,
whi ch were kept as short as possi bl e. The 200- mL sol ut i on was prepared from anal yt i cal
grade sodi um chl ori de and di st i l l ed water, and deaer at ed with puri fi ed argon. Measur ement s
are carri ed out at r oom t emperat ure in t he deaer at ed 0. 02M NaC1 sol ut i on at pH 6.6. The
sol ut i on was kept st agnant over the t est duration. The sampl es were mai nt ai ned at open
ci rcui t pot ent i al for 30 min. Then t he pot ent i al was i mposed by st eppi ng up to one val ue
bel ow the pi t t i ng pot ent i al , and the unfi l t ered anodi c current fluctuations are recorded, the
sampl i ng t i me bei ng ei t her 0.2 or 0. 06 s, dependi ng on the speci mens.
For the Ti-free steels wi t h a hi gh sulfur content, a 0. 2-s sampl i ng t i me was used and is
consi dered sufficient wi t h respect to t he l i fet i me of the rather l arge anal yzed events, as wi l l
be seen below. For t he Ti -free 8- ppm sul fur-cont ai ni ng al l oy for whi ch the short er events
have been obser ved (0.8 s -< 9 -< 1.5 s), compar i son of results obt ai ned at the t wo di fferent
sampl i ng t i mes (0.2 and 0. 06 s) confi rm t hat the most frequent l y obser vabl e events are current
peaks wi t h t he intensity, shape, and l i fet i me report ed in t he fol l owi ng.
GORSE ET AL. ON EFFECT OF METALLURGICAL FACTORS 335
Resul t s
Pi t t i ng Probabi l i t y and Convent i onal Pi t t i ng Pot ent i al s
The elementary pitting probability (EPP) and conventional pitting potential, Vp, are deter-
mined by using the statistical potentiodynamic test and the experimental procedure described
in Ref 5. Raising the electrode potential potentiodynamically (scan rate = 100 mV/ mi n)
from its open circuit value up to pitting, a potential-dependent EPP can be defined as EPP
= - ( l / S) In ( i / N) , where i is the number of nonpitted samples (of area S) once reached a
given potential, among the N samples tested. Then a conventional Vp can be defined for an
arbitrary value of EPP, here taken equal to 0.1 cm -2.
The pitting potentials are reported in Table 3, as a function of the sulfur and titanium
content in the alloys. Compari ng the results obtained for the Ti-bearing alloys to the values
of Vp measured on the Ti-free alloys, containing either 8-ppm sulfur ( +0. 48 V/ SCE) or 41-
ppm sulfur ( +0. 40 V/ SCE) , there is a visible discrepancy between the results of this poten-
tiodynamic test, because the pitting potentials do not appear to be a monot onous function
of the Ti content. This point will be, in some aspects, enlightened by the potentiostatic
electrochemical noise measurements.
Pot ent i al De pe nde nc e o f t he Pot ent i ost at i c El ect r ochemi cal Noi s e
Anodi c current fluctuations are observed in a very limited potential range below the pitting
potential, for the three Ti-bearing alloys tested, as for the steel with low sulfur content (8-
ppm). We note AV = Vp . . . . . V~ the difference between the mean pitting potential measured
by potentiostatic testing and the applied potential, the corresponding values of which are
reported in Fig. 1 and in the captions of Figs. 2 to 5. For the three Ti-bearing alloys as for
the Ti-free low sulfur (8-ppm) containing alloy, the potential range over which metastable
pits are detected does not exceed a value of AV -- 50 mV. For example, for the 0.37 wt%
Ti and 47-ppm sulfur-containing alloy, rare events are scarcely observable 10 mV below the
pitting potential. Even for the 0.05 wt% Ti-bearing alloy, metastable pitting events can be
recorded onl y 20 mV below the pitting potential. For comparison, on the Ti-free and high
sulfur-containing ( - 4 0 - p p m S) alloy, the potentiostatic electrochemical noise can be studied
over a large potential range, AV ~ 200 mV, in the present experimental conditions.
Ef f ect o f the Pol ari zat i on Ti me on t he Pot ent i ost at i c El ect r ochemi cal Noi s e
In many cases, the number of the metastable pitting events seems to decrease when po-
larizing the sample below the pitting potential, for a prolonged period of time, of order 1 h
in the present testing conditions. On the other hand, pitting of industrial steels depends on
TABLE 3--Pitting potentials obtained during potentiodynamic
statistical tests f or the different steels [4].
Steels Ti, Wt% S, ppm Vp, V/SCE
A 0 8 + 0.48
B 0 41 + 0.40
C 0.05 41 + 0.45
D 0.10 37 + 0.40
E 0.37 47 + 0.46
4.
3.
~
2. ;
0. 2
0
4. 2
3. 2
" ~ 2 . 2
1. 2
0. 2
0
4.2
3.~
2.~
1.~
Ti : 0 wt.%
S : 41 ppm
Va= +300 mV/ SCE
Vp= +310 mV/ SCE
~ i , I ~ , L ~ I , J * J I L , ~ , I
100 200 300 400 500 600
Time (secs)
Ti : 0.05 wt.%
S : 41 ppm
Va= +360 mV/ SCE
Vp= +370 mV/ SCE
100 200 300 400 500 600
Time (secs)
Ti : 0.10 wt.%
S : 37 ppm
Va= +320 mV/ SCE
Vp= +350 mV/ SCE
100 200 300 400 500 600
Time (sees)
FIG. l a - - A n o d i c cur r ent me as ur e d wi t h i ncreasi ng 7~ cont ent at t he begi nni ng o f t he test.
--, 2
t i i I i i i 1 I i i I
100
Ti : 0 wt.%
S : 41 ppm
Va--- +300 mV/SCE
V = +310 mV/SCE
P
I : F ~ l ~ L f J ~ I i i i
200 300 400 500 600
Time (secs)
,<
9 3
~ 2
Ti : 0.05 wt.%
S : 41 ppm
Va= +360 mV/SCE
Vp= +370 mV/SCE
, , , ~ [ , ~ I i I I I ~ I I i I I I I I I I I [ I ~ i I
100 200 300 400 500 600
Time (secs)
- , 2
Ti : 0.I0 wt.%
S : 37 ppm
Va= +320 mV/SCE
V --- +350 mV/SCE
P
, , i ~ I L , t L I ~ i , J I . . . . t , , ~ i I , i i L
100 200 300 400 500 600
Time (secs)
FIG. l b- - Anodi c current measured after 10 min o f exposure to the O.02M NaCl solution at pH 6.6
under polarization.
their metallurgical properties, that is, on the steel composition and microstructure. However,
the phenomena can be rather complex, depending on the pitting stage under consideration.
This point is illustrated by Fig. 1 in which the current transients recorded on three alloys
differing by the Ti content are represented, at the beginning of the electrochemical test (see
Fig. l a), or after 10-rain exposure under polarization (see Fig. lb). Figure l a is in agreement
with already published results by Baroux and Gorse [2]. Goi ng from a Ti-free to a 0.05 wt%
Ti and then to a 0.10 wt% Ti-bearing alloy, the potentiostatic electrochemical noise decreases
significantly, as expected. However, after 10 min of exposure to the 0. 02M NaCI solution
under applied potential, the frequency of the fluctuations has decreased significantly for the
0.05 wt% Ti-containing alloy, whereas the 0.10 wt% Ti alloy becomes progressively more
"act i ve, " the nucleation frequency of the measurable pitting events increasing. This result is
in accordance with the measured values of the conventional pitting potentials collected in
Table 3.
Current Transients Anal ysi s
Accordi ng to Gabrielli et al. [6], there are mainly two types of current transients: the Type
I transients exhibit a smooth increase followed by a sharp decrease; the Type II transients
display a sudden increase followed by a smoot h decrease. Moreover, events of each type are
apparently characteristic of a particular class of materials or surface treatments for a given
material. Mainly, Type I transients have been generally associated to i ron-chromi um (Fe-Cr)
alloys, whereas Type II transients pertain to aluminum or various steels submitted to a
nonchemical depassivation treatment (laser illumination, scratching, bombardment with a flux
of abrasive particles). More recently, according t o Baroux and Gorse [2], for various AI SI
430 t ype Fe-Cr alloys, differing by the Ti or Nb content, rare events of Type II were found
for the 0.4 wt% Ti-bearing steels whereas an intense potentiostatic electrochemical noise,
with events of Type I, was observed for the Ti-free alloys.
In this study, the typical shapes of the transients obtained for the different alloys are
presented in Figs. 2 through 5, respectively. The metastable pitting events are distinguished,
according to the shape of the current transients, that is, the value of the exponent n, assuming
that over a certain time scale the anodic transients can be fitted to a power law i(t) ~ t".
We begin with the Ti-free alloy with a relatively high sulfur (41-ppm) content, for which
the greatest diversity of shapes is noted at short polarization times, as shown in Fig. 2, by
compari son with the three Ti-bearing alloys (Figs. 3 through 5). Mainly two different types
of transients are observed: some with an exponent n less than 1 (see Fig. 2a), the others
with n approaching 1 or larger than 1 (see Fig. 2c). In both cases, their life-time is rather
large ( - 3 s) and may attain about 8 s (Fig. 2b) or more.
This paper shows onl y transients observed at an applied potential close to the mean pitting
potential, that is, within 30 mV from stable pitting, as can be seen in Figs. 2 through 5.
However, note that for the Ti-free 41-ppm sulfur-containing alloy, coexistence of the t wo
different forms of transient depicted above have been observed over the whole applied po-
tential range, starting 200 mV below stable pitting. As concerns the three Ti-bearing alloys
or the Ti-free low sulfur (8-ppm) containing alloy, such a potential study cannot be performed
in the same conditions because of the restricted potential range over which a potentiostatic
current noise was measured. In these conditions, we suggest that the changes in the form
and frequency of occurrence of the transients of a given shape observed over a similar
potential range (AV = 30 mV) with respect to stable pitting, when changing the Ti and S
content of the alloy, are essentially dependent on the type of inclusions present in the steel.
Potentiostatic exposure simplifies drastically the shapes of the transients, because mainly
smaller events of shorter lifetime ( ~1 s) and lower intensity are detectable after 80-min
4 5 0
300
g
1 5 0
2 3 0
T i : 0 w t . %
41 p p m
I I L i i i i i i i L i , , ,
232
1 5 5 0
t 1 5 0
"~ 7 5 0
3 5 0
0
2 3 4 2 3 6 2 3 8 2 4 0 4 0 1
T i m e ( s e c s )
: T i : 0 w t . % / / ~ b )
)- :
4 0 3 4 0 5 4 0 7 4 0 9 4 1 1
T i m e ( s e c s )
6 0 0
4 5 0
g
~ 3 0 0
150
c) T i : 0 w t . %
, , , f , , i I i i i i J i ~ I
4 9 6 4 9 8 5 0 0 5 0 2
T i m e ( s e e s )
d)
200 F ~ i : o wt.'~
41 p p m
1 8 0
1 6 0
1 4 o ~-
I -
? o ~
8 0
i a i i I i i i I r i i , L
4 1 4 3 4 5 4 7
4 9 4 5 0 4
T i m e ( s e e s )
F I G , 2--Typi cal metastable pitting transients observed f or the Ti-free and 41 ppm sulfur-containing
alloy ( a , c : at short polarization time, b : typical multievent, d: at long polarization time [80 rain]). The
applied and mean pitting potentials are, respectively: V, = 300 mV/ SCE, Vp = 310 mV/SCE.
e x p o s u r e ( s e e F i g . 2 d ) . T h e e v e n t s w i t h n < 1 p r o g r e s s i v e l y d i s a p p e a r a s t h e e x p o s u r e t i m e
u n d e r p o l a r i z a t i o n i s i n c r e a s e d . It i s n o t i c e a b l e t ha t a f t e r s u f f i c i e n t p o t e n t i o s t a t i c e x p o s u r e ,
o f t h e o r d e r o f 1 h i n t h e p r e s e n t e l e c t r o c h e m i c a l c o n d i t i o n s , t h e b e h a v i o r o f t h i s M n S -
c o n t a i n i n g a l l o y r e s e m b l e s t hat o f t h e T i - f r e e a l l o y w i t h t h e l o w e s t s u l f u r c o n t e n t ( 8 - p p m ) .
I n d e e d , b y c o m p a r i n g F i g . 2 d w i t h F i g . 3 a a n d 3b, w e r e ma r k t h a t p o t e n t i o s t a t i c e x p o s u r e
y i e l d s t r a n s i e n t s w h o s e s h a p e i s c o m p a r a b l e t o t ha t f o u n d o n a l l o y s c o n t a i n i n g o n l y 8 p p m
1 0 0
"~ 5 0
- T i : 0 w t . %
7 S : 8 p p m
4 6 8 4 7 0
a )
. . . . . i l l i
4 7 2 4 7 4
T i m e ( s e e s )
1 0 0
5o
T i : 0 wt ~%
S : S p p m
b )
. . . . . . . . . I i i i i i i i i i I l l l l i i j ~ l
1 5 4 . 5 1 5 6 . 5 1 5 8 . 5 1 6 0 . 5
T i m e ( s e e s )
F I G . 3--Typi cal metastable pitting transients observed f or the Ti-free low sulfur (8 ppm) containing
alloy. ( a , b: Typical shapes obtained whatever the polarization time). The applied and mean pitting
potentials are, respectively: V~ = 380 mV/ SCE and Vp = 400 mV/ SCE.
180
175
170
- - 1 6 5
~ 160
155
150
76
Ti : 0.05 wt.%
S : 41 p p m
77 78 79
Time (secs)
a)
8 0
400
380
360
~ 340
320
30O
280
260
68
Ti : 0.05 wt.%
. S : 41 p p m
J
69 70 71
Time (sees)
b)
72
175
: Ti : 0.05 wt.%
170 - S : 41ppm
165
160
155
150
145
140
135 ' ' ' '
92
}
I i i i i i i J , ,
93 94
Time (sees)
420
c)
400
380
360
~ 340
320
300
280
168
Ti : 0.05 wt . % / d)
S : 41 p p m
95 96 169 170 171 172
T i m e (sees)
FIG. 4- - Ty pi c al met ast abl e pi t t i ng transients observed f o r the al l oy cont ai ni ng 0. 05 wt % T~. (a:
met ast abl e pi t t i ng event observed at short pol ari zat i on time, b, c, d: f requent l y observabl e shapes at all
exposure times). The appl i ed and mean pi t t i ng pot ent i al s are, respectively: V a = 360 mV / S CE and
Vp = 370 mV/ S CE.
of sulfur. In this case, onl y rare and short-lived events, the shape of which does not depend
on the polarization time, are present. The typical peak height is 100 nA, and the events
lifetime varies between 0.8 and 1.5 s, two examples of which are depicted in Fig. 3.
These are the two opposite situations. In between, a mixed behavior is observed, con-
cerning the shape of the transients. A 0.05 wt% Ti is sufficient to reduce the apparent
probability of appearance of the events of Type t ~ with n less than 1, mainly observable at
short polarization time (see Fig. 4a), as for the Ti-free steel. For this 0.05 wt% Ti-bearing
alloy, the most frequently observable shape, whatever the polarization time, is a narrow peak,
short-lived (0.5 s -< 9 -< 1.3 s) of rather low intensity (see Fig. 4b, c and d). Very few events
are observed. Besides, at all exposure times, transients typical of the low-sulfur alloy are
present at all exposure times besides few macro-events, increasing linearly with time.
Increasing the Ti content shortens the metastable pitting events, decreases their intensity,
and rarefies the events with exponent less than 1.
The 0.10 wt% Ti-bearing alloy exhibits an intermediate behavior, with respect to the low
(8-ppm) and high (41-ppm) sulfur Ti-free alloys. The two different shapes of the transients,
with n < 1 or -> 1, are observed at all exposure times (see Fig. 5). "Si mpl e" events, with
a well-defined profile, are visible at short and long polarization time. However, after a certain
exposure time, as already discussed for Fig. 1, the surface displays an intense and structured
potentiostatic electrochemical noise showing trains of events (see Fig. lb).
1 0 0 0
960
920
g80
K4 0
800
274
: sTi : 030 wt.% a )
: 37 p p m
276 278 7,80
Time ( s e c s )
250
210
170
130
90
50
266
Tl : 0.10 wt.% b )
S : 37 ppm
. . . . . . . . . . . . i l t l l l
268 270 272
Ti me ( s e c s )
6 4 0
620
600
u
-~ 580
560
250
Ti : 0.10 wt.% c )
S : 37 ppm
451 453 455
T i me ( s e c s )
Ti : 0.10 wt.%
S : 37 p p m
210
170
130
90
50
d )
5 4 0 i, ;. , ,, , , " 7 "
4 4 9 2 7 6 2 7 8 2 8 0 2 8 2
T i m e ( s e c s )
F I G . 5- - Ty pi c al met ast abl e pi t t i ng transients observed f o r the al l oy containing 0. 10 wt % Ti. ( a , c :
events observed at short pol ari zat i on time, b, d : events observed af t er prol onged pol ari zat i on time). The
appl i ed and mean pi t t i ng pot ent i al s are, respectively: V a = 320 mV / S CE and Vp = 350 mV/ S CE.
Discussion
The above results can be anal yzed as fol l ows. Let us consi der a hemi spher i c pit. The
current densi t y flowing t hrough its surface (2 arr 2) obeys the power l aw J ~ t -m, so that the
current i nt ensi t y is gi ven by 1 ~ t 2-3m. The t hree fol l owi ng l i mi t i ng cases have been observed:
(1) The st at i onary case (m = 0, J = const ant ), whi ch yi el ds 1 ~ t z, al r eady obser ved for
macro-event s (1 ~ ~A) in i ndust ri al MnS- cont ai ni ng steels [2];
(2) The case m = 1/ 3 gi vi ng I oc t, mor e t ypi cal of l ong- l i ved events (superposi t i on of
i ndi vi dual events), apparent l y not charact eri st i c of a gi ven composi t i on or mi crost ruc-
ture, because t hey have been obser ved not onl y in this wor k but al so for al l t ypes of
steels; and
(3) Di ffusi on or ohmi c- cont r ol l ed current t ransi ent s t hrough a corrosi on layer, that is, t he
case m = 1/ 2, gi vi ng I ~ X/t, onl y obser ved in this wor k for the MnS- cont ai ni ng
steels, but di sappear i ng aft er l ong pol ari zat i on t i me.
As concerns t he met ast abl e pi t t i ng events exhi bi t i ng a narrow peak, in some cases even
symmet ri c, further wor k is needed to rel at e this shape to a part i cul ar mi crost ruct ure or fi l m
het erogenei t y: the pi t t i ng si t e can be l ocat ed ei t her on some met al l urgi cal defect , or on some
weak poi nt of the passi ve film.
As obser ved in this wor k in all cases, t he decl i ne of t he current t ransi ent is slow, occurri ng
over few tenths of a second. It coul d suggest that the repassi vat i on st ep is not cont r ol l ed by
t he sudden reformat i on of a prot ect i ve passi vat i ng layer, but by the cat hodi c react i on [7].
Because the apparent t i me scal e cor r espondi ng to the i ndi vi dual repassi vat i on event s varies
wi t h t he al l oy composi t i on, it is suggest ed that, even under the pot ent i ost at i c condi t i ons used
in this study, the cat hodi c process is not compl et el y cont r ol l ed by react i ons occurri ng at the
count er-el ect rode, and coul d be at l east par t i al l y di st ri but ed bet ween the count er-el ect rode
and t he wor ki ng el ect rode, dependi ng on the t ype of the i ncl usi ons act i ng as pi t t i ng sites or
l ocat ed cl ose to the pit.
Conclusion
El ect rochemi cal current noi se varies si gni fi cant l y as a funct i on of the sulfur and t i t ani um
cont ent in steel. The shape of the current t ransi ent s depends on the t ype of i ncl usi ons at
whi ch the met ast abl e pi t s are i ni t i at ed. It is not i ceabl e that transients of the form I ~ r ' with
n < 1 are most l y found on the MnS- cont ai ni ng al l oys. The shape and frequency of occur-
rence of the met ast abl e pi t t i ng t ransi ent s change wi t h pr ol onged pot ent i ost at i c exposure.
Af t er l ong enough exposure under pol ari zat i on, of the or der of 1 h in the present el ect ro-
chemi cal condi t i on, narrow peaks cor r espondi ng to short -l i ved met ast abl e pi t t i ng events of
low i nt ensi t y are observed, i ndependent of the t i t ani um and sulfur cont ent in the steel.
References
[1] Janik-Czachor, M., Szummer, A., and Szklarska-Smialowska, Z., British Corrosion Journal, Vol. 7,
1972, pp. 90-93.
[2] Baroux, B. and Gorse, D., in Modifications of Passive Films, Vol. 12, E Marcus, B. Baroux, and M.
Keddam, Eds., European Federation of Corrosion Publications, 1994, pp. 300-307.
[3] Baroux, B. and Gorse, D., in Modelling Aqueous Corrosion, NATO ASI Series E, Vol. 266, K. R.
Trethewey and P. R. Roberge, Eds., 1994, pp. 161-182.
[4] Baroux, B., "Further Insights on the Pitting Corrosion of Stainless Steels," in Corrosion Mechanisms
in Theory and Practice, E Marcus and J. Oudar, Eds., Marcel Dekker, Inc., New York, Basel, Hong
Kong, 1995, pp. 265-309.
[5] Baroux, B., Corrosion Science, Vol. 28, No. 10, 1988, pp. 969-986.
[6] Gabrielli, C., Huet, E, Keddam, M., and Oltra, R., Corrosion, Vol. 46, No. 4, 1990, pp. 266-278.
[7] Isaacs, H. S., Corrosion Science, Vol. 34, No. 3, 1993, pp. 525-528.
P Chris Pi st ori us 1
The Effect of Some Fundamental Aspects
of the Pitting Corrosion of Stainless Steel
on Electrochemical Noise Measurements
REF ERENCE: Pistorius, R C., " Th e Ef f ect o f S o me Fu n d a me n t a l As pe c t s o f t he Pi t t i ng
Corros i on o f St ai nl es s St eel on El e c t r oc he mi c al Noi s e Me as ur e me nt s , " Electrochemical
Noise Measurement for Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R.
Scully, Pierre R. Roberge, David L Reichert, and John L. Dawson, Eds., American Society
ABSTRACT: Features of metastable pit growth on stainless steel that affect the possibilities
to predict stable pit growth from electrochemical noise measurements are examined. To this
end, the behavior of AISI type 304 stainless steel in chloride solutions has been studied. It is
confirmed that the electrode capacitance plays a major role in fluctuations of the corrosion
potential during metastable growth. This means that the size of these potential fluctuations
depends primarily on the size of metastable pits and not on the peak current nor the current
density during growth; this means that fluctuations in electrode potential will have little value
to predict stable pitting. Electrochemical current noise from twin-electrode noise probes holds
more promise. However, it is shown that the direct relationship between electrochemical current
noise and pitting susceptibility breaks down when the pitting behavior is altered by a change
in surface condition (heat tinting).
KEYWORDS : stainless steel, pitting corrosion, metastable pit growth, stable pit growth, ca-
pacitance, twin-electrode probe, heat tint
Electrochemical noise results from variations in the rate and distribution of corrosion
processes on the surface of a metal. One possible use of electrochemical noise measurement
is to predict the survival probability [1 ] of a structure that is susceptible to localized cor-
rosion. Such a prediction is more likely to be accurate if it is based on an understanding of
the fundamental processes that underlie the observed noise. The purpose of this paper is to
examine the possibility of applying the available knowledge on the pitting corrosion of
stainless steel to the use of electrochemical noise measurements for pitting corrosion pre-
diction. To this end, a brief summary of the relevant information follows.
Potentiostatic study of the pitting corrosion of AISI type 304 stainless steel in neutral,
acidic, and alkaline chloride (C1-) solutions [2-4] has shown that the formation of a stably
growing pit is preceded by a period of metastable pit growth. A quantitative analysis [4] of
the conditions necessary to maintain the aggressive anolyte required for sustained pit growth
indicated that, for an open pit, these conditions are met if the product of the current density
inside the pit and the pit depth exceeds a certain value. This value is not attained during
metastable growth, suggesting that the some cover (perhaps a remnant of the passive film)
is present over the mouth of the (roughly) hemispherical pit during metastable growth. It
Associate professor, Department of Materials Science and Metallurgical Engineering, University of
Pretoria, Pretoria, 0002, South Africa.
3 4 3
www.astm.org
was suggested that this cover maintains the aggressive anolyte within the pit by providing
the necessary barrier to diffusion. Accordi ng to this model, metastable growth can cease by
repassivation at any time if the cover is lost, and stability is only achieved when the pit is
large enough to grow without a cover [4].
It appears that pits that eventually progress to stable growth originally start by growing
metastably [4 ]. Hence, the rate at which stably growing pits form on a metal surface should
be equal to the product of the rate at which metastably growing pits are nucleated and the
probability that a metastably growing pit, once nucleated, will grow large enough to achieve
stable growth [5]. I f these fundamental observations are to be applied to the analysis of
electrochemical noise measurement, ways of extracting information on the rate of nucleation
of metastably growing pits and on the probability of these pits growing to become stable,
need to be found. It does appear that a simple measure for the latter is available: it was
concluded from potentiostatic tests that a higher current density inside the metastable pit
increases the chances that a metastably growing pit will progress to stable growth [4]. The
peak current during metastable growth (that is, just before repassivation), which is more
readily measurable, is roughl y proportional to the current density, because the average size
to which metastable pits grow is approximately the same for pits growing at different current
densities [4].
Hence, measurement of the peak currents from metastable pit growth, together with the
frequency of occurrence of metastably growing pits, should serve as a useful predictor of
pitting corrosion, under potentiostatic conditions. The standard deviation of the electrochem-
ical current noise (ECN) will increase both with higher rates of formation of metastably
growing pits and with higher peak currents during metastable growth; therefore, the standard
deviation of the ECN [6] should have some predictive value. This paper includes a test of
whether this simple measure does indeed predict pitting behavior by compari ng stainless
steel specimens with different surface conditions. Electrochemical noise measurements were
carried out on these specimens by monitoring the current between two nominally identical
electrodes, an approach similar to that used by others [ 6 , 7 ] .
Not onl y electrochemical current noise, but also fluctuations in the corrosion potential
(electrochemical potential noise) result from and, hence, reflect the fundamental pitting pro-
cesses. During metastable pit growth under open-circuit conditions, these excursions of the
corrosion potential are in the form of a relatively rapid drop in potential, followed by a
relatively slow recovery. This behavior appears to result from the dominant role of the
electrode capacitance [ 8] - - i n the absence of other oxidizers, oxygen reduction is t oo slow
to provide the current for metastable growth, and a major part of the current is drawn from
the charge stored within the double layer and the passive film of the corroding metal (the
electrode capacitance quantifies the effect of the electrode potential on this amount of stored
charge). The slow recovery of the electrode potential reflects recharging of the capacitance
by the slow cathodic reaction, following repassivation [8]. Recent work on the effects of
capacitance have focused on the measurement of repassivation transients under potentiostatic
control [9]. Here, results from experiments on the effect of electrode capacitance during
open-circuit metastable growth are presented.
The experimental configuration used to investigate the role of electrode capacitance is
shown in Fig. 1. A circular stainless steel electrode with a 50- ~m diameter was constructed
by casting an epoxy resin support around a 50- ~m diameter wire of AISI-t ype 304 stainless
steels (supplied by Advent Research Materials, Halesworth, UK). The outer diameter of the
epoxy support was 6 mm. The stainless steel electrode was kept small to keep its own
PISTORIUS ON EFFECT OF SOME FUNDAMENTAL ASPECTS 345
air
/ 1 o ~ ~ I IIIIl~reference
~ ' , I I I 1 electrode
I1~ ~ ~ ~ - - ~ p l a t i n u m
~ / ~ ~ electrode
- - - ~ . ~ ~ 5 0 ~ x m stainless
steel electrode
~Luggin probe
FIG. 1--Experimental conf i gurati on used to measure potenti al and cur r ent transi ents duri ng open-
ci rcui t pi tti ng corrosi on.
cont ri but i on to the cat hodi c current (drawn from el ect rode capaci t ance or from a Far adai c
react i on) small. Duri ng nat ural pi t t i ng corrosi on, the passi ve surface around the pit suppl i es
t he cat hodi c current that sustains pi t growth. The effect of t he passi ve surface was si mul at ed
by a surroundi ng r i ng- shaped pl at i num (Pt) el ect r ode whi ch was coupl ed to t he smal l stain-
l ess st eel electrode. The Pt el ect rode was const ruct ed from 0. 5- mm- di amet er br i ght wi re, and
was bent into a ri ng wi t h a di amet er of 7 mm, gi vi ng a surface ar ea of about 0.34 cm 2 for
the ri ng-shaped part; the rest of the el ect rode was covered wi t h st op-off lacquer. The Pt ri ng
was pl aced in the pl ane of the surface of t he downward faci ng st ai nl ess steel el ect rode,
whose surface was ground wi t h 1200-grit si l i con car bi de (SIC) paper before each experi ment .
Pt was used for this ri ng el ect rode, rat her than st ai nl ess steel, to el i mi nat e the possi bi l i t y of
pi t t i ng corrosi on occurri ng on t he ri ng itself, whi ch woul d di st urb observat i on of the cor-
rosi on of the smal l cent ral el ect rode. Some measurement s were conduct ed wi t h a passi vat ed
AI SI - t ype 316L ring el ect r ode i nst ead of the Pt; the results were si mi l ar over the short t erm,
but l ong- t er m measurement s were di srupt ed by pi t t i ng of the st ai nl ess steel ring, and hence,
Pt was used for al l t he exper i ment s report ed here. The el ect rol yt e, I M hydrochl ori c aci d
(HC1), was aerat ed bef or e and duri ng the measurement s, usi ng l aborat ory ai r suppl i ed by a
di aphr agm pump at a rate of 1 dm3/ mi n. Experi ment s were conduct ed at the ambi ent t em-
perat ure of 26 -+ I~
The cel l was pl aced i nsi de a Far aday cage. The current bet ween the st ai nl ess st eel el ect r ode
and the pl at i num ri ng was measur ed by means of a Kei t hl ey 428 current ampl i fi er (sche-
mat i cal l y shown as "A" in Fi g. 1). Thi s i nst rument is in pri nci pl e a zero-resi st ance ammet er
( ZRA) , and offers bot h a l ow i nput offset vol t age (l ess than 0.2 mV) and ful l -scal e current
ranges from 10 -~~ to 10 -2 A. A Kei t hl ey 614 el ect r omet er ( " V" ) served as a hi gh- i mpedance
vol t met er to measure t he pot ent i al of t he st ai nl ess-pl at i num coupl e with r espect to a silver-
si l ver chl ori de ( Ag/ AgC1) el ect rode 2 (filled wi t h sat urat ed pot assi um chl ori de). The outputs
of the current ampl i f i er and el ect r omet er were recorded on a 14-bit di gi t al r ecor der ( Yoko-
2 Please note that all electrode potentials in this paper are quoted relative to the Ag/AgC1 electrode.
3 4 6 E L E C T R O C H E MI C A L NOI SE M E A S U R E M E N T
gawa AR1100A) , usi ng a readi ng rate of 100 Hz in most cases. Thi s di gi t al recorder al l ows
the si mul t aneous recordi ng of up to four channel s. In al l cases, el ect rochemi cal pot ent i al
noi se and el ect r ochemi cal current noi se were r ecor ded si mul t aneousl y. The 100-Hz readi ng
rate was sel ect ed because the ent i re met ast abl e growt h per i od is much short er than a second
in many cases [4]. The dat a were t ransferred from the di gi t al recorder to a personal comput er
for subsequent anal ysi s. The i nst rument al noi se on current and pot ent i al readi ngs was ap-
pr oxi mat el y 1 nA and 0.2 mV, respect i vel y. The i nst rument al noi se was measur ed as the
peak- t o- peak val ues of the current and pot ent i al signals aft er the el ect rodes had been exposed
to the el ect r ol yt e for several hours, by whi ch t i me al l met ast abl e pi t t i ng act i vi t y had ceased.
The capaci t ance of the Pt el ect r ode was det er mi ned from i mpedance measurement s carri ed
out over a frequency range from 1 t o 1000 Hz. A cat hodi c pol ari zat i on curve for the Pt
el ect r ode was measured at a cat hodi c scan rate of I mV/ s . The Pt capi t ance i ncreases sharpl y
at pot ent i al s of 0.3 V and bel ow (Fig. 2), pr obabl y refl ect i ng a change in the surface of the
Pt el ect rode; evi dence of this is al so vi si bl e in the pol ari zat i on di agr am (Fi g. 3) as a definite
i ncrease in current bel ow 0. 4 V. These capaci t ance values are si mi l ar to t hose of AI SI - t ype
316 st ai nl ess steel [10]. The pot ent i al of the Pt el ect rode dri ft ed gr adual l y in t he negat i ve
di rect i on duri ng experi ment s; t he dri ft amount ed to less than 1 mV duri ng each compl et e
measurement , whi ch was much smal l er than the measured pot ent i al fluctuations. The causes
of the pot ent i al dri ft were not i nvest i gat ed further; the dri ft was si mpl y count ered by cl eani ng
the Pt el ect r ode occasi onal l y by anodi c pol ari zat i on in a separat e cel l .
The t wi n- el ect r ode measurement s were carri ed out wi t h wi re l oop el ect rodes [11 ] to avoi d
crevi ci ng. The el ect rodes were const ruct ed of 0. 5- mm- di amet er anneal ed- t ype 304L st ai nl ess
steel wi re bent into the shape shown in Fi g. 4. The ar ea of each el ect r ode exposed to the
el ect rol yt e was about 0.3 cm 2. The el ect rodes were suspended 10 mm apart in a pl exi gl ass
support. A reference el ect r ode was pl aced 15 mm to one si de of el ect r ode 1, wi t h its tip 10
mm bel ow the bot t om of el ect rode 1. The current and pot ent i al s were measur ed wi t h the
combi nat i on of current amplifier, el ect romet er, and di gi t al recorder ment i oned above. When
30
I I
C"
v
0
C
0
0
0
t7
0
2 0
1 0 , I , I ,
0 . 0 0 . 2 0 . 4 0 . 6
P o t e n t i a l ( V v s . A g / A g C I )
FIG. 2--Capacitance of Pt ring electrode in aerated 1M HCI.
1 0 .5
10 .6
10 .7
10 "8
I 0 g
-0.1
Cur r ent
( A )
10 .4
0.1 0, 3 0, 5 0. 7
Pot ent i al (V vs. Ag/ AgCl )
FIG. 3--Polarization curve of Pt ring electrode in aerated I M HCI; scan rate - 1 mV/s, electrode
area 0.34 cm{
the switch S (Fig. 4) was closed, current could flow between the electrodes. The switch was
opened occasionally to moni t or the corrosion potentials of the t wo electrodes. To this end,
bot h the electrode potential of electrode 1 relative to the reference electrode (using V, in
Fig. 4), as well as the potential of electrode 2 relative to electrode 1 (using V2) were recorded
continuously and simultaneously. Cycl i ng the position of the switch did not appear to intro-
duce artifacts into the electrochemical noise measurement: the magnitude and appearance of
the current and potential fluctuations appeared unaffected when the switch position was
changed rapidly from closed to open and back. The electrodes were immersed in an 0. 1M
solution of ferric chloride (FeCl3) which was stagnant and not deaerated. The temperature
was 26 +- I~ Measurements started a few seconds before immersion of the electrodes.
This approach was followed to capture the initial activity (metastable pit growth) of the
electrodes. Because the system simply measured the coupling current and corrosion poten-
tials, and did not include a potentiostat, no detrimental effects were caused by starting the
measurements before immersion.
Pairs of electrodes with three different surface conditions were tested in the configuration
of Fig. 4. One condition was obtained by wet grinding to 600 grit with silicon carbide (SIC)
paper. The others involved wet grinding to 600 grit, passivating in 15% nitric acid at 60~
FIG. 4--Twin wire loop configuration f or electrochemical noise measurements. Broken lines indicate
the electrolyte level.
for 30 min, and heating in air to different peak temperatures for 20 s in a weld simulator.
Peak temperatures of approximately 400 and 800~ were used. This treatment causes the
formation of a thermal oxide film, heat tint, on the stainless steel surface. No microstructural
changes (for example, sensitization) occurred during heating, as confirmed by testing the
pitting behavior of wire which had been heated, and then reground to a 600-grit finish: the
behavior of these heated-and-ground specimens was the same as ones which had not been
heated. Pitting corrosion, electronoptical, and surface analysis results on the behavior of heat-
tinted-type 304 stainless steel have been presented elsewhere [12,13]; the specimens heated
to 400~ are covered by a relatively iron-rich oxide film, while the 800~ treatment yields
a thicker, more chromium-rich film. This difference in film properties changes the pitting
behavior: the 400~ specimens develop a profusion of metastably growi ng pits, each of which
tends to repassivate at a relatively small size. The 800~ specimens develop far fewer me-
tastably growing pits, but each of these tends to grow to a larger size before repassivating.
The result is that both the 400 and the 800~ specimens appear to be more susceptible than
ground specimens to the onset of stable pitting in 0. 1M FeCI3. The surface conditions were
used here to test the ability of electrochemical noise measurements to predict pitting behavior
for a wide range of pitting conditions.
A few of these wire loop specimens were also individually tested under potentiostatic
control in an electrolyte containing 0. 28M sodium chloride (NaC1) and 0. 02M HC1; this
electrolyte has the same pH (1.3) and chloride concentration as the 0.1M FeCI 3 solution.
The potential was controlled with a specially constructed battery-powered potentiostat [14 ].
Open-Circuit Potential Fluctuations
Figure 5 shows a typical train of anodic current transients (reflecting metastable pit
growth), with the corresponding potential transients, for the experimental configuration of
Fig. 1. The anodic current transients have the familiar shape of a comparatively slow rise,
followed by a rapid current decrease, the latter indicating repassivation of the pit. Simulta-
neous with the current increase, the electrode potential falls. It is evident that the local
mi ni mum in every potential fluctuation corresponds to the point of repassivation. The slow
recovery of the potential does not result from repassivation: no current flows to the pitted
stainless steel surface during potential recovery. The potential increase, rather, reflects re-
charging of the capacitance of the passive surface by reduction of oxygen [8].
These potential changes are not expected to affect the current density during metastable
growth, since this growth apparently proceeds at a constant current density under diffusion
control [4 ]. Because metastable growth proceeds at an approximately constant current density
and results in approximately hemispherical pits, the current is proportional to the square of
the growth time (t) [3]. The transients drawn out on an expanded time scale (Fig. 6) show
that there is little or no departure from the t 2 shape, even for a potential change of more
than 70 mV in the case of the larger transient, in support of diffusion control; i f the pits did
grow under activation or ohmi c control, this potential change would be expected to cause a
strong change in the current density, which is not observed.
The decrease in electrode potential that accompanies metastable growth allows at least
part of the pit growth charge to be drawn from the capacitance of the surrounding surface.
To determine what fraction of the pit charge is supplied by the capacitance, the size of each
potential decrease was compared with the pit growth charge (Fig. 7). The size of the potential
decrease was measured from the local maxi mum in the potential-time curve (at the start of
4 - - , - - - 9 - - ~ -
Cur r ent
( , A )
3
2
1
0
0. 4
Pot ent i al
( v )
0. 3
0. 2 . . . . . . . .
0 20 40 60 80 100
T i me (s)
FIG. 5--Typical train of current and potential transients from open-circuit pitting.
metastable growth) to the local mi ni mum which corresponds to pit repassivation; the cor-
responding pit growth charge was obtained by integration of the current-time transient.
I f the complete pit growth charge is drawn from the capacitance, and if the capacitance
is constant, one expects the electrode potential decrease to be proportional to the pit charge.
The broken line in Fig. 7 shows this expected behavior, with 13 p~F taken to be the constant
capacitance. 3 Clearly the actual potential decrease is smaller than the expected value; on
average, the ratio between the actual and expected potential changes is 0.63 +-- 0.07. One
possible reason why this ratio is smaller than unity is that the capacitance is larger at more
negative potentials (Fig. 2). The other possible reason is that part of the pit growth charge
is supplied by the faradaic cathodic current. As a test of the importance of the change in
capacitance with potential, the capacitance can be determined from the current and potential
transients, as follows. The total current from the Pt ring (Ipt) is the sum of the capacitive
and faradaic (IF) cathodic currents:
where
I p, = I F + Cd~ld, (1)
C = capacitance of the Pt ring, F, and
E = electrode potential of the couple, V.
3 The rationale behind the use of this value is presented in the following discussion.
Cur r ent 1
( , A )
0.31
0. 29
Pot ent i al
(V) 0.27
0.25
0.23
0
T
h i L
2 4 6 8
Ti me (s)
FIG. 6 - - Th e decrease in electrode pot ent i al during metastable growth does not affect the I ~ t 2 shape
of the current transient.
The current given by Eq 1 is the current that is measured by the ammeter in the circuit
of Fig. 1. In this equation, both IF and C are functions of the electrode potential, E. Just
before and just after repassivation of the metastably growi ng pit, the potential is the same
because repassivation is so rapid. Just after repassivation, no net current is supplied by the
Pt, and the full Faradaic current goes towards recharging the capacitance. By applying Eq 1
to the situations just before and just after repassivation, an expression for the capacitance is
found:
where
ma x
d E
C = d E + - ~
b e f o r e a f t e r
( 2 )
/ m a x = the peak current (I~) just before repassivation, A,
]dE/dtIb~fo~ = the absolute slope of the E - t curve j ust before repassivation, V/ s, and
I d E / d t l a f t o r -- the absolute slope of the potential-time curve just after repassivation, when
the net current is zero, V/ s.
A plot of the experimental data according to Eq 2 is given in Fig. 8. It is evident that the
experimental data scatter around a single line, with the exception of the three points for the
highest peak currents. The results indicate that the electrode capacitance was approximately
P I S T O R I U S O N E F F E C T O F S O M E F U N D A M E N T A L A S P E C T S 3 5 1
>
v
0
0
0
0
0
- 6
~
c-
O
1 , , . . . . . . i
0 . 1
0. 01
/ o q b
0
z d
0 . 0 0 1 ,d~
0
0 . 0 0 0 1 . . . . . . . . . . . . . . . i
0 . 0 0 . 1
' ' ' ' ' ' " l , , , . . . . . I / ' . . . . . "
/
, z
/
/
/
/ O O o
/
o
4b~ o
i i i . . . . . ~ i , , , , , i l l
1 l O
P i t c h a r g e ( / z C )
, , , , , ,
oo
FIG. 7- - The effect of pit charge on the size of decreases in electrode potential f or transients such as
those in Fig. 5. The broken line is the expected behavior i f the entire pit charge is drawn from a
capacitance of 13 ixE
1 0
,<
v
e 3
k -
k . .
( J
a 0 . I
n
/
0 . 0 1
0 . 0 0 1
' ' ' ' ' ' ' r l ' ' ' ' ' ' " 1
/
/
. . . . ~ . , - , , :
/
@ /
/
f
j
/ 0
/
o
/ 0
p,
/
t i , , , , , , I i , , , , , t J l i , i i i l l
0 . 0 1 0 . 1
T I d E / d t J p e a k ( V / s )
FIG. 8- - The correspondence between the peak current density before repassivation and the sum of
the slopes of the potential transient j ust before and j ust after repassivation; the broken line is the expected
behavior f or C = 13 ~F.
the same for all the transients except those three. The average value of the capacitance
(represented by the broken line) was found to be 13 _+ 1 txE This value of 13 IxE which
agrees well with the measured values for the more positive potentials in Fig. 2, is the one
used in Fig. 7. The three points that lie at the top of Fig. 8 are for the largest current
transients, which polarized the Pt electrode into the range where its capacitance increases
sharply (Fig. 2).
The conclusion to be drawn from Figs. 7 and 8 is that some part of the pit growth charge
is supplied by the faradaic current, but the capacitance supplies on average about 60%.
Obviously, this value is not expected to be constant for all cases of metastable pit growth.
For example, in the present experimental configuration, changes in ring size and solution
conductivity are expected to affect the fraction of the pit growth charge supplied by the
electrode capacitance. However, these experiments do serve to demonstrate the strong role
of capacitance for these conditions, and their mathematical analysis serve as a foundation
for evaluating the effect of capacitance during actual cases of open-circuit corrosion. Ex-
amination of published potential transients [for example, Refs 8,13,15] indicates that the
capacitance does indeed play a major role during the natural pitting corrosion of stainless
steel: from Eq 1 it can be shown that the ratio ] d E / d t l b e f o r e / ( l d E / d t l b e f o r e ~ t - [ d E l d t l a f t e r ) gives the
fraction of the pit growth current supplied by the capacitance at the peak current. Hence, i f
the potential curve is much steeper before repassivation than thereafter, most of the current
is supplied by the capacitance; the transients in the cited references do show this.
Because of the major role of the electrode capacitance, the size of each potential fluctu-
ation depends primarily on the size (dissolution charge) of the pit, and not on the peak
current (Fig. 9). In this figure, the metastably growing pits that repassivated close to 4 and
9 s, respectively, have very different peak currents, yet they result in approximately equally
large potential fluctuations, because their growth charges are similar (147 and 158 nC,
respectively).
The results of the analysis of open-circuit potential fluctuations thus show that variation
in the corrosion potential (electrochemical potential noise) will be a poor predictor of stable
pitting: the fluctuations in the open-circuit potential are sensitive to the physical size of
metastable pits, whereas, as was argued earlier in this paper, they need to be sensitive to the
peak current from metastable pits to be useful as a predictor.
As a final note, the situation for stable pit growth is considered briefly. No stable pits
were observed during the experiments where the stainless steel electrode was coupl ed directly
to the Pt ring through the current amplifier, in line with the observation that stable pits onl y
form at very positive potentials on these 50-txm electrodes [4]. To obtain stable pits, the
stainless steel electrode had to be biased positively relative t o the Pt ring; this is equivalent
to inserting a battery in series with the ammet er in Fig. 1. The result from such a measure-
ment is given in Fig. 10. Once a stably growi ng pit has formed, the current increases in
rapidly fluctuating, possibly chaotic [16] fashion, approximately proportional to X/t, as re-
ported before [2-4]. The potential falls persistently when a stable pit is present [15]; the
fluctuations in potential are in phase with the current fluctuations, indicating that the Faradaic
current now plays a major role.
Twin Electrode Electrochemical Noise Measurements
Representative portions of the potentiostatically measured anodic polarization curves for
the three surface conditions are reproduced in Fig. 11. Zero time was taken as the point in
which the potential reached 0.11 V on the anodic scan at 2 mV/ s for all three curves. A
larger amount of smaller current fluctuations take place on the 400~ surface (Curve a), also
Current
(nA)
Pot ent i al
( v )
300
200
100
0
0.310
0. 305
0.300
I
0. 295
0
r r E
3 6 9 12
Ti me (s)
FIG. 9 - - A pair of transients that illustrate that the change in potential is determined by the pit charge,
not the peak current.
r esul t i ng in a hi gher aver age current , bef or e t he ons et o f st abl e pi t t i ng at 3 s. Fewer , but
larger, f l uct uat i ons ar e pr es ent on t he 800~ s ur f ace ( Cur ve b); t he gr ound sur f ace has in-
t er medi at e behavi or . Thi s agr ees wi t h t he pr evi ous l y pr es ent ed r esul t s on heat - t i nt ed s ur f aces
[12, 13]. Whi l e not enough s pe c i me ns wer e avai l abl e f or s ys t emat i c i nvest i gat i on o f t he
pi t t i ng pot ent i al , t he pot ent i al s in whi ch st abl e pi t s f o r me d dur i ng t he anodi c scans wer e as
f ol l ows: 400~ sur f ace, 0. 116 and 0. 090 V; 800~ sur f ace, 0. 2, 0. 15, and 0. 16 V; and gr ound
sur f ace, 0. 3, 0. 3, and 0. 22 V. The s e i ndi cat e t he s a me r el at i ve pi t t i ng suscept i bi l i t y f ound
be f or e f or s i mi l ar s pe c i me ns [12, 13], n a me l y 400~ s ur f ace > 800~ s ur f ace > gr ound
surface. Th e s e s pe c i me ns can t hus s er ve as a t est f or t he pr edi ct i ve p o we r o f e l e c t r oc he mi c a l
noi se me a s ur e me nt s , whi ch mus t at l east rat e t he s pe c i me ns in t he s a me or der t o be
successf ul .
A t ypi cal r ecor d f or a noi se me a s ur e me nt ( exper i ment al conf i gur at i on o f Fi g. 4) on t wo
gr ound s pe c i me ns is gi ven in Fi g. 12. The per i ods wi t h t he swi t ch S open al l owed t he
r es pect i ve st at es o f t he t wo el ect r odes t o be r ecogni zed, t hat is, st abl e pi t gr owt h ( pot ent i al
f al l i ng wi t h t i me; Fi g. 10), or onl y met as t abl e pi t gr owt h ( pot ent i al r i si ng er r at i cal l y wi t h
t i me) . Expa nde d por t i ons o f t he cur r ent and pot ent i al noi se f r om Fi g. 12 f or t he t hr ee pos s i bl e
combi nat i ons o f met as t abl e and st abl e gr owt h ar e pr es ent ed in Fi g. 13.
Whi l e met as t abl e gr owt h pr oceeds , t he fl uct uat i ons o f bot h t he cur r ent be t we e n t he t wo
el ect r odes and o f t he cor r os i on pot ent i al o f t he c oupl e ar e r el at i vel y l ar ge (Fig. 13a). Whe n
a st abl e pi t f or ms first on one of t he el ect r odes (Fi g. 13b) and l at er on bot h (Fig. 13c), t he
f l uct uat i ons o f t he coupl i ng cur r ent and o f the cor r os i on pot ent i al b e c o me r el at i vel y smal l er ,
al t hough s o me l ar ge l ow- f r equency var i at i ons ar e s ome t i me s pr e s e nt when st abl e pi t t i ng is
30
20
Current
(I~A)
10
0
0.6
0.5
Potential
( v )
0.4
0.3
0 10 20 30 40
Ti me (s)
FIG. l O- - Format i on o f a stable pit, wi t h the st ai nl ess steel electrode at a posi t i ve bi as o f 0.3 V
relative to the Pt ring.
present on both. The decreasi ng pot ent i al that charact eri zes stable pi t t i ng is al so evident. It
thus appears qui t e st rai ght forward to di st i ngui sh bet ween met ast abl e and stable pi t growt h
on the t wi n el ect rodes of such an el ect r ochemi cal noi se probe. Unfortunately, this is unl i kel y
to be of much val ue in the corrosi on moni t ori ng of l arge structures. Because the noi se probe
is l i kel y to have a much smal l er area than the structure, stable pi t t i ng is l i kel y to occur on
the structure before it afflicts the probe. Thus it woul d be unsafe to rel y on the devel opment
of st abl e pi t t i ng on t he probe as an i ndi cat or of a danger of pi t t i ng on t he structure; it is
necessary to use the measurement s from the probe bef or e stable pi t t i ng sets in to predi ct the
l i kel i hood that the l arger structure is suffering st abl e pitting. Thi s means that predi ct i ve
measures must be ext ract ed from the noi se resul t i ng from me t a s t a b l e pi t growt h on the t wi n
el ect rodes of the probe. In the rest of this section, t wo such measures are bri efl y consi dered.
As can be seen in Fi g. 13a, t here is no correl at i on bet ween l arge fluctuations in the current
signal and fluctuations in the pot ent i al signal. Thi s is onl y to be expect ed, since, as shown
earlier, the fluctuations in the el ect rode pot ent i al reflect the response of the el ect r ode capac-
i t ances to the t ot al met ast abl e pi t growt h charge, whi l e the current si gnal is t he r andom
di fference in met ast abl e pi t t i ng activity. Hence, a measure such as the rat i o of the st andard
devi at i on of t he el ect rochemi cal current noi se to the st andard devi at i on of the el ect r ochemi cal
pot ent i al noi se cannot be expect ed to yi el d meani ngful resul t s for the case of l ocal i zed
corrosi on.
Current
(. A)
25
23
21 =
6.5
4.5
0 5 10 15
Ti me (s)
FIG. 11--Portions o f pot ent i odynami c pol ar i z at i on cur ves on 0. 3- cm 2 wi re l oop el ect rodes in 0. 28M
NaCI + O. 02M HCI. Scan rat e 2 mV/ s ; zero t i me at E = 0. 11 V. Cur r ent s cal es hav e t he s ame sensitivity.
Surf ace condi t i ons: (a) 400~ tint; (b) 800~ tint; and (c) ground.
As discussed earlier, based on the fundamental nature of pitting corrosion of stainless
steel, the standard deviation of the current noise during metastable pitting is expected to be
a useful predictor of stable pitting, for a given surface condition. However, this relationship
breaks down i f the surface condition changes (and similar changes mi ght be brought about
by changes in electrolyte composition). This is clear from Fig. 14, which shows current and
potential noise with metastable growth on both electrodes with an 800~ surface (Fig. 14a)
and with a 400~ surface (Fig. 14b). The differences in current noise largely reflect the
differences which are apparent in Fig. 11: larger fluctuations of lower frequency are observed
on the 800~ couple, while more, generally smaller, fluctuations are found for the 400~
couple. I f the standard deviation of the current noise were used as a predictor, one would
predict that the 800~ surface is more susceptible to pitting than the 400~ surface, the
opposite of the actual behavior.
These results indicate that the standard deviation of the electrochemical current noise may
not give an unambiguous indication of the danger of pitting, under certain conditions. It may
be argued that the conditions chosen here are rather artificial, but the results do serve to
sound a cautionary note: the utility of any electrochemical noise measurement as a predictor
of pitting needs to be tested both against the fundamental nature of the corrosion process
and against actual corrosion behavior.
Finally, an interesting aspect of Fig. 14 is that the potential fluctuations of the 800~
couple (Fig. 14a) are disproportionately greater than those of the ground (Fig. 13a) or 400~
0.5
Potential 0.3
( v )
0.1
40-
Current
(.A)
Potential
difference
( v )
20
-20
-40
0.3
0.2
0.1
0
, , , , i , , , , I , , , , - -
0 250 500 750
Time (s)
FIG. 12--Typical record from twin-electrode noise measurements with ground specimens in O.]M
FeCI 3. Zero current readings correspond to the periods when the switch was open.
(Fig. 14b) couples, given the relative sizes of the metastable current transients (Fig. 11).
This probably results from the lower capacitance of the 800~ specimens, which are covered
by a much thicker thermal oxide film; this observation serves to emphasize the strong effect
of electrode capacitance on electrochemical potential noise measurements during metastable
pit growth.
Conc l us i on
Electrode capacitance plays a major role in the fluctuations in corrosion potential that
result from metastable pit growth with the result that electrochemical potential noise (fluc-
tuations of the corrosion potential) is a poor predictor of stable pitting. Based on previous
experimental observations on the fundamental nature of pitting corrosion of stainless steel,
the standard deviation of electrochemical current noise from a simple twin electrode config-
uration holds more promise. However, this too fails when the surface condition of the metal
changes drastically. The implication is that the standard deviation of the electrochemical
current noise should be used with caution when large and especially unknown changes in
the corrosion environment can occur.
Acknowl edgment
Thanks are due to Pieter Pistorius for the preparation of the heat tint specimens.
PISTORIUS ON EFFECT OF SOME FUNDAMENTAL ASPECTS 3 5 7
Current
(~A)
Potential
3
2
1
0
0.45
a )
O 4 4 ,
20 25 30 35
-33
-34
-35
-36
0.22
0.21
0.20
b)
1 4 - -
13
12
11
0.16
0.15
0.14
c)
0.1 , , 0.13 ' '
200 205 210 215 580 585 590 595
Ti me (s)
FI G. 13- - Expanded portions of Fig. 12 showing typical current and potential noise with." (a) meta-
stable growth on both electrodes, (b) metastable growth on one, stable on the other, and (c) stable growth
on both. Current axes have the same sensitivity throughout, as do the potential axes.
C u r r e n t
(~A)
a )
b )
- - r
Pot ent i al
O4
0 . 2 6 5
0. 255
0. 245
0. 18
0. 17
0. 16
280 285 290
0. 235 0. 15 ' '
275 32 37 42 47
Ti me (s)
FI G. 14- - Current and pot ent i al noise during metastable pi t growth on both wire loop electrodes f or:
(a) 800~ surface and ( b) 400~ surface.
References
[1] Shibata, T. and Takeyama, T., Corrosion, Vol. 33, 1977, pp. 243-251.
[2 ] Stockert, L., "Metastabile Lochfrasskorrosion," Dissertation ETH 8632, ETH H(inggerberg, Ziirich,
Switzerland, 1988.
[3] Frankel, G. S., Stockert, L., Hunkeler, E, and Boehni, H., Corrosion, Vol. 43, 1987, pp. 429-436.
[4] Pistorius, P. C. and Burstein, G. T., Philosophical Transactions of the Royal Society of London,
Series A, Vol. 341, 1992, pp. 531-559.
132, 1985, pp. 1796-1804.
[6] Dawson, J. L., Farrell, D. M., Aylott, P. J., and Hladky, K., "Corrosion Monitoring Using Electro-
chemical Noise Measurements," Paper 31, Corrosion '89, National Association of Corrosion En-
gineers, Houston, 1989.
[7] Roberge, P. R., Beaudoin, R., and Sastri, V. S., Corrosion Science, Vol. 29, 1989, pp. 1231-1233.
[8] Isaacs, H. S. and Ishikawa, Y., Journal of the Electrochemical Society, Vol. 132, 1985, pp.
1288-1293.
[91 lsaacs, H. S., Davenport, A. J., and Frankel, G. S., "Simulations of Surface Capacitance Effects
on Potentiostat Response Following Disruption of Passivity," in Critical Factors in Localized Cor-
rosion, G. S. Frankel and R. C. Newman, Eds., The Electrochemical Society, Pennington, NJ, 1992,
pp. 232-239.
[10] Ferreira, M. G. S. and Dawson, J. L., Journal of the Electrochemical Society, Vol. 132, 1985, pp.
760-765.
[11] Stockert, L., Hunkeler, E, and B6hni, H., Corrosion, Vol. 41, 1985, pp. 676-677.
[12] Von Moltke, T., Pistorius, P. C., and Sandenbergh, R. E, "The Influence of Heat-Tinted Surface
Layers on the Corrosion Resistance of Stainless Steels," INFACON 6, Proceedings of the 1st In-
ternational Chromium Steel and Alloys Congress, Vol. 2, 1992, SAIMM, Johannesburg, pp.
185-195.
[13] Pistorius, P. C. and Von Moltke, T., "Pitting Corrosion of Heat-tinted Stainless Steel," in Proceed-
ings of the European Symposium on Modifications of Passive Films, The Institute of Materials,
London, 1994, pp. 316-321.
[14] Pistorius, P. C., "Stability and Metastability of Corrosion Pits on Stainless Steel," Ph.D. thesis,
University of Cambridge, 1991.
[15] Daufin, G., Pagetti, J., Labbe, J. P., and Michel, E, Corrosion, Vol. 41, 1985, pp. 533-539.
[16] Corcoran, S. G. and Sieradzki, K., Journal of the Electrochemical Society, Vol. 139, 1992, pp.
1568-1573.
Met hods
Rol and Oltra, 1 Bri gi t t e Chapey, 1 Frangoi s Huet , 2 and
Li onel Re naud 3
Coupling of Acoustic Emission and
Electrochemical Noise Measurement
Techniques in Slurry Erosion-
Corrosion Studies
REFERENCE: Oltra, R., Chapey, B., Huet, E, and Renaud, L., "Coupling of Acoustic Emis-
sion and Electrochemical Noise Measurement Techniques in Slurry Erosion-Corrosion
Studies," Electrochemical Noise Measurement f or Corrosion Applications, ASTM STP 1277,
Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson,
ABSTRACT: This study deals with the measurement and the subsequent signal analysis of
acoustic emission and current noise recorded during continuous slurry erosion of a metallic
target in a corrosive environment. According to a phenomenologic model, the localized cor-
rosion results from the repetitive damage caused by particle impacts. The fluctuations of the
acoustic signal and of the electrochemical signal both can be modeled as a shot-noise-like
process.
The main purpose of this work is to compare two processing techniques for the fluctuating
signals: time analysis (mean value) and spectral analysis (power spectral density [PSD] spec-
trum) to determine the more suitable signal treatment. Another purpose is also to quantify the
balance between the mechanical wear and the corrosive damage of the abraded metallic target.
It will be shown that the mean value of the RMS acoustic signal, A(t), and also the PSD of
A(t), are related to the mechanical wear of the target and allow real-time measurement of the
actual mechanical perturbation in terms of the mass of the ablated material.
KEYWORDS: slurry erosion-corrosion, stainless steels, acoustic emission, sulfuric acid,
power spectral density, data analysis techniques
Mat er i al f ai l ur es caus ed by sl urry er os i on- cor r os i on pr oces s es in aqueous t wo- phas e f l ows
ar e not t ot al l y under st ood, despi t e many exper i ment al and mode l i ng st udi es to eval uat e t he
i nt er act i ons bet ween mechani cal and cor r os i ve da ma ge [1].
Usual l y, t he mat er i al behavi or is def i ned by car r yi ng out exper i ment al i nvest i gat i ons yi el d-
i ng t he i nt egr al da ma ge ( mechani cal and el ect r ochemi cal ) as f unct i on of t he nat ur e o f t he
fluid. The s e t est s ar e conduct ed wi t hout t aki ng i nt o account basi c par amet er s t hat char act er i ze
t he mechani cal def or mat i on or t he ki net i cs o f t he e l e c t r oc he mi c a l r eact i ons [2].
Recent l y, wi t h t he de ve l opme nt o f c omput e r pr ogr ams, s i mul at i on o f t he phys i cal and
chemi cal pr oces s es has al l owed pr edi ct i on o f t he chemi cal i nt er act i on o f a f l owi ng fluid wi t h
Directeur de Recherches au CNRS and Ph.D. student, respectively, UMR 5613 CNRS R6activit6 des
Solides BP 138 21004 Dijon, France.
2 Directeur de Rechercbes au CNRS, UPR 15 CNRS Physique des Liquides et Electrochimie, Paris
VI, 75252 Pads, France.
3 Research engineer, Creusot-Loire Industrie, BP 56 71200 Le Creusot, France.
361
Www.astIII.or~
or without solid particles with a corrodi ng surface [3]. These simulations, deduced from
numerical flow predictions, were extended by erosion and corrosion models, taking into
account corrosion processes controlled by mass transfer (for example, general corrosion and
formation of a corrosion product layer). Nevertheless, experimental parameters have to be
defined from advanced experimental studies before being introduced into simulation codes.
Devel opment of such models for investigating the behavior of passive materials (for ex-
ample, stainless steels) in two-phase flows has been limited by the lack of experimental data.
Slurry erosion-corrosion of passive materials is characterized by the mechanical perturbation
of the passive film, that is, localized impacts of small abrading particles in suspension in a
flowing corrosive fluid, whi ch induce passive film breakdown leading t o transient corrosion
phenomena.
Electrochemical investigations of locally depassivated metal by abrading particles have
been tentatively performed in previous work, and electrochemical model s have been devel-
oped for analyzing the corrosion current [4]. To complete such studies, the overall damage
induced by slurry erosion-corrosion has to be defined. This damage is the result of t wo
factors:
(1) Mechanical wear (ablation of metal) and
(2) Mass loss as a result of the transient corrosion depending on the balance of bare metal
dissolution and rebuilding of the protective film.
With respect to the lack of data for simulation models, the main problem is experimentally
how to determine these quantitative values to establish the synergistic effect as a function
of metallurgical and chemical (pH, temperature of the corrosive media) parameters. For
example, measure of the t wo contributions for an individual impact cannot be individually
achieved. For a stainless steel target in a 1M sulfuric acid (H2SO4) solution at 60~ the
order of magnitude of the damage resulting from the impact of a SiC particle (size 500 ixm)
with an average velocity of 9 m 9 s - ' is about:
9 impact area: 50 I. m 2,
9 ablated material: 0.2 ng, and
9 corroded material: 50 pg.
These values cannot be measured for an individual impact, but can only be obtained by
averaging the damage (mechanical and corrosive) for continuous abrasion conditions at a
high rate. In the above-ment i oned example, the rate of erosion was estimated to be approx-
imately 3000 impacts per second.
The knowl edge of the abrading regime, which appears to be an important parameter, is
not sufficient to analyze the balance between mechanical and corrosive damage. On the other
hand, this parameter is difficult to follow during a slurry erosion test. For example, para-
meters such as the concentration of the abrading particles were tentatively used t o establish
the same kind of relation without success, because numerous factors (kinetic energy, angle
of impact, and so forth) contribute t o the mechanical damage.
Anot her experimental approach has been chosen that combines electrochemical and me-
chanical transient measurements. In a previous study [5], acoustic emission (AE) techniques
were used to measure the frequency of the mechanical impact of particles in slurries flowing
in aqueous solution. The energy distribution of the slurry particle impacts and the total
mechanical wear was characterized. AE signals (burst emissions) as a result of each impact
of an abrading particle were detected with a broad bandwidth piezoelectric transducer
positioned on the opposite face of the target. The measurement of the acoustic energy of
OLTRA ET AL. ON SLURRY EROSION-CORROSION STUDIES 363
the burst signal generated continuous voltage transients at a high rate (1000 to 5000
impacts / s).
In this work, a more detailed experimental approach has been achieved by coupl i ng the
two kinds of sensors (acoustic and electrochemical) for measuring mechanical and corrosion
damage and performing signal analysis in a manner that is a synergy of the t wo components.
The signal analysis was done in the time and frequency domains.
Local i zed corrosion results from the repetitive damage caused by the particle impacts. The
fluctuations of the acoustic and the electrochemical signals both can be modeled by a shot-
noise-like process. This means that the mean value of the cumulative signals is proportional
to the rate of impact and to the average "si ze" of the events (mechanical or electrochemical).
On the other hand, spectral analysis of the fluctuations of the signals can provide compl e-
mentary information on the rate of erosion, and also on the synergy between the mechanical
and corrosive damage.
The main purpose of this work was to compare these t wo processing techniques, that is,
averaging and spectral analysis, to define a more suitable method of characterizing and
quantifying the balance between mechanical wear and the corrosive damage.
First, the development of the mechanical sensor is presented and, second, the various
expressions of the synergy between mechanical and corrosive damage of Type 316L stain-
less steel (SS) in acidic media that can be obtained from the different signal processings
are compared.
Erosion-Corrosion Apparatus
The j et slurry apparatus used in this study is based on an "i mpi ngi ng j et " device using a
peristaltic pump. The flow velocity of the electrolyte (9 m 9 s - ' ) was stabilized by a com-
pressor in the loop, A more detailed description can be found in Ref 6. The impinging j et
was designed so the angle of the particle impact of the abrading particle (silicon carbide
[SIC], mean size 500 ~m) was 90 ~ (Fig. 1).
Materials and Fluids
The slurry erosion-corrosion experiments were performed on various stainless steels, but
in this paper only the behavior of Type 316L SS is described. All the slurry erosion exper-
iments in corrosive environment were conduct ed in a H2SO4 1M solution at 25~ and the
mechanical wear in absence of corrosion was calibrated in a sodium sulfate (Na2SO4) 0. 1M
solution (pH = 7) at 25~ under cathodic polarization.
Development of the Acoustic Emission Device
The use of acoustic sensors is not widespread for erosion experiments involving a flowing
slurry suspension. Some attempts have been made to characterize the abrasive wear in lu-
bricated sliding contacts [7].
Acoust i c emission (AE) has also been proposed as a method of monitoring hard particle
impacts on metallic surfaces by analyzing burst emissions with a broad bandwidth, piezoe-
lectric transducer positioned on the opposite face of the target. Quantitative analysis of the
AE signals allowed sizing of the particles [8].
Mechanical stresses induced by the impact of a particle in suspension in the flowing fluid
generate an ultrasonic wave. Then for each particle impact, the AE signal consists of a single
, ~176176
e l e c t r o c h e mi c a l
cel l
FFT analyzer
digital oscilloscope
(transient response)
PC486 ~hannel 2 S ~
(mean energy and
number of events) / L potentiostat j )
output input
FIG. 1 - - S c h e ma t i c sket ch o f t he erosi on- corrosi on l oop bas e d on a j e t sl urry appar at us [6]. The
di ame t e r o f t he t arget in cont act wi t h t he el ect rol yt e is 43 mm and t he di ame t e r o f t he i mpi ngi ng area
is 8 mm. RMS = RMS i nt egrat or devi ce; DAT = di gi t al audi ot ape recorder.
burst emission. During erosion experiments, the summation of the "count s, " that is, the
number of times the AE signal crossing a preset trigger level voltage, can be correlated to
the erosion rate [8].
As erosion can also be considered as a pseudocontinuous phenomenon, the mean value
of the time variation of the energy of the AE signal might be expected to provide information
about the total mechanical damage.
A Europhysical Acoust i c Inc., (bandwidth 350 to 1200 kHz) sensor was coupled with
PTFE grease to the stainless steel target (see Fig. 1). The output signal, which could be
amplified i f necessary, was transformed by an RMS integrator device whose output was
connected to a digital audiotape (DAT) recorder (sampling rate 48 kHz). In addition, the
signal can also be transmitted directly to a digital oscilloscope to trigger the electrochemical
transient response (as shown in Fig. 5).
Later, the DAT recorded acoustic signal (maxi mum 2 h duration) was processed
(1) By a 486 comput er to calculate the mean value of the acoustic energy and the number
of events and
(2) By a Fourier analyzer to calculate the power spectral density (PSD) of the spectrum.
E l e c t r o c h e mi c a l Me a s u r e me n t s
In the abrading cell, the target was polarized in the passive range with a potentiostat. The
anodic current fluctuations induced by the passive film breakdowns were simultaneously
recorded on the second channel of the DAT and later they were processed with either the
digital oscilloscope or the Fourier analyzer.
Experimental Results
A c o u s t i c S i g n a l
The frequency range used to measure each acoustic burst, Vae( t ) , was around 1 MHz (Fig.
2a). During a continuous slurry erosion test whose rate of impacts is in the kiloHertz range,
the initial AE signal emitted by the sensor could not be continuously recorded.
Calculating the RMS value, A ( t ) , of the initial AE signal, Vae( t ) , is a conventional tech-
nical solution for the continuous recording of the signal whose frequency range is 10 KHz.
Compared to previous applications of AE techniques [7], the time constant 9 of the RMS
integrator device was reduced to 100 i~s.
A ( t ) = V2ae u d( u) (1)
- - ' r
Figure 2b shows a characteristic fluctuating RMS acoustic signal A ( t ) caused by the su-
perposition of consecutive impacts.
For a single impact, we can define the acoustic energy [9]
E , = VZae(t)dt (2)
where t, is the duration of the acoustic burst. As the integrated circuit operated with a time
constant ~ slightly higher than ts, the RMS response at time ~, A('r), to a single impact was
proportional to the root mean square of the acoustic energy
A(T) = V2aE t d ( t ) = 9 (3)
In practice, the amplitude of the RMS acoustic signal can be measured easier than A(T).
To ensure that this amplitude was also proportional to the square root of the mechanical
impact energy, particles leading to well-controlled damage were used. For impacts caused
by glass beads, the amplitude of the RMS acoustic signal was found to be proportional to
the square root of the kinetic energy o f the particle [lOJ.
P S D o f t h e R M S A c o u s t i c S i g n a l - - T h e PSD of the RMS acoustic signal fluctuations was
comput ed for various conditions of erosion. The evolution of the spectra as function of the
abrasion conditions is presented in Fig. 3. The cut off frequency in the high-frequency range
was due to the time constant of the RMS integrated circuit, whereas the low cut off frequency
was related to the fluctuations of the rate of particles pulsed by the peristaltic pump; a similar
effect on the PSD of the electrochemical signal has been found for another flowing device
[4]. The spectra have been characterized by the values of the t wo plateaus at 100 and 0.5
Hz, to establish a relationship between the erosion rate and the PSD.
From a physical point of view, the PSD of the RMS acoustic signal contains information
on the amplitude of the time fluctuations (due to the distribution of the energy of the impacts)
and also on the rate of erosion (see Fig. 2b). The distribution of the occurrence times of the
elementary RMS acoustic transients can be assumed to follow a doubl y stochastic Poisson
3 6 6 ELECTROCHEMI CAL NOISE MEASUREMENT
m V
80
40
0
- t ' A E ( t )
!
I L I l
0 40 80 120 ti me l~S
200
m V
(b)
0 I I
10 20 t i me ms
FIG. 2- - Typi cal acoustic sensor responses. (a) Burst and RMS acoustic signals f or one impact. (b)
RMS acoustic signal as f unct i on o f time f o r a continuous slurry erosion.
process. This means that the number of impacts per unit time is a random quantity that has
a mean value h and a PSD defined as xt'~(D. These fluctuations in the rate of impacts were
due to the fluctuations of the pump.
Therefore, the PSD of the acoustic signal (proportional to the root mean square of the
energy of the impacts) can be written [4]
~ ' A ( f ) = { k + ~,,(j-r)} I A O [ 2 ( 4 )
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where A(f) is the fast Fourier transform (FFT) of the RMS elementary transient. This ex-
pression assumes that all the impacts give the same RMS elementary transient, that is, it
does not take into account the distribution of the impact energy. Simulations of such random
signals have shown that this assumption has a small but insignificant influence on the shape
of the PSD spectra.
Rel at i on Be t we e n R MS Acous t i c Si gnal and Mechani cal Wear
Erosion tests in a noncorrosive electrolyte (1-h duration) were conduct ed in the following
conditions:
9 Abrading particles: SiC 500 ~m and
9 Electrolyte: Na2SO4 0. 1M pH = 7 (E = - 1 . 2 V/ SSE) .
The total mechanical wear was defined at the end of the erosion experiment by measuring
the mass loss. To correlate the mechanical wear to the RMS acoustic signal, t wo processings
of the RMS data have been compared: the calculation of the mean value ( A( t ) ) and the
calculation of the PSD ~A of the signal fluctuations. The results of this compari son are
shown in Fig. 4.
Me an Value o f t he Acous t i c S i g n a l - - As shown by other authors for abrasive wear [ 7], the
mean value of the RMS acoustic signal (for 1 h of erosion) was proportional to the mass
loss, as measured after the erosion test was carried out with various concentrations (g 9 L- ' )
of abrading particles (see Fig. 4).
PS D o f the Acous t i c Si gnal - - I n practice, the mean value (A(t))= cannot be obtained from
the PSD ~a( f ) , which is measured after elimination of (A(t )). Nevertheless, as shown in Fig.
4, a linear relationship was also found between the wear of the target and the PSD in the
low-frequency (0.5-Hz) regime. The value of the low-frequency plateau ~A (0.5 Hz) is a
,-.I
!
H
e ~
In
0
m
ra
~w
0
1 0 - 3
10 - 4
1o -5
10 - 6
10 - 7
10 3
.- C] 1 0 2
I 0
A
4a
V
II
1
. . . . . . . i . . . . . . . . i . . . . . . . .
.0 -I 1 i0 1 0 2
m e c h a n i c a l w e a r / m g h -x
FIG. 4- - Mean value of the RMS acoustic signal <A(t)> and PSD tO a of its fluctuations at 0.5 Hz as
function of the mechanical wear rate (rag 9 h-J). Same abrasion conditions as in Fig. 3.
function of the mean rate of erosion and of the mean value ( E) of the elastic energy of the
impact, which is assumed to be proportional to the damage. Even i f there is, a priori, no
relation between (A(t)) and ~a (0.5 Hz), these two values are proportional to the elastic
energy transmitted to the acoustical sensor, and, consequently, this can explain the observed
linear relationships between these values and the mass loss of the target by mechanical wear.
Electrochemical Measurements
Erosion experiments in corrosive environment were carried out on the Type 316L SS target
instrumented with the AE sensor. During the test, the sample was under potentiostatic control
at a passive potential ( +0. 2 V/ sat urat ed sulfate electrode) in 1M H2SO4.
From previous experiments [6], it has been found that the main probl em to obtain accurate
data is the validity of the charge measurement to define the mass loss caused by corrosion,
which seems to depend on the erosion rate. In low abrasion conditions, the corrosion rate
can be estimated by applying the Faraday law; in contrast, for high abrasion conditions, a
discrepancy has always been found between the corrosion rate estimated by the Faraday law
and the mass loss measured after the experiment corrected for the mass loss as a result of
the mechanical erosion obtained from Fig. 4. To clarify this unexpected behavior, the synergy
between the mechanical damage and the electrochemical response has been studied by look-
ing for a correlation between the RMS acoustic and current noises in the t wo characteristic
regimes of low- and high-abrasion conditions.
Individual Impacts--Figure 5 shows the acoustic signal (high frequency) caused by con-
secutive particle impacts and the corresponding electrochemical response of the material; it
clearly illustrates the correlation between the mechanical and the corrosive damage in the
case of individual impacts.
Low Regime of Continuous Slurry Erosion--For low-abrasion conditions (3 g 9 L ~) a
reasonable correlation was found between the faradaic estimation and the corrosion mass
loss (Table 1). Typical PSD of the current and RMS acoustic signal fluctuations have been
plotted for these low-abrasion conditions (Fig. 6a).
High Regime of Continuous Slurry Erosion--For high level of erosion (particle concentra-
tion higher than 15 g 9 L i), the corrosive mass loss cannot be estimated by calculating the
faradaic charge involved (see Table 1). Typical PSD of the current and the acoustic signal
have been plotted for these high-abrasion conditions (Fig. 6b).
Correlation Between Acoustic and Electrochemical Response
The correlation between the RMS acoustic and electrochemical signals can be put forward
by studying either the time recordings or the spectra. This correlation concerns the times of
the occurrence of the RMS and current transients or the energy involved in these transients,
provided that a relationship between the electrical charge and the acoustic energy can
be found.
Onl y a time analysis allows an investigation of the times of the occurrence of the tran-
sients, whereas the correlation between the energies of the transients may be proved by
measuring the ratio of the values of the low-frequency plateaus of the acoustic and electro-
chemical spectra. Because of the doubl y stochastic law of the time distribution of the impacts,
this latter analysis was rather complicated, and a first approach can be achieved by taking
the ratio of the two values of the PSD at 100 Hz
Hz)=I/ Hz)=l (5)
3 7 0 E L E C T R O C H E M I C A L N O I S E M E A S U R E M E N T
1 6 0
m V
8 0
0
- 8 0
( a )
- 1 6 0 i i I
1 2 3 t i m e m s
3 0 _
/ I A
2 0
1 0
0
1 I I
1 2 3 t i m e m s
FIG. 5--Burst acoustic emission (a) and electrochemical transients (b) f or two consecutive impacts.
Abrasion conditions: Type 316L SS IM H2SO4--E = +0.2 V/SSE--SiC 500 t~m.
TABLE 1--Experimental results f or slurry erosion-corrosion experiments as a function of the
abrasion conditions. Influence of the erosion rate (estimated by the concentration of SiC particles g 9
L -~) upon the mean value of the signals. Abrasion conditions: Type 316L SS IM H2SO4--E = +0.2
V/SSE--SiC 500 p.m.
Mechanical Wear Mass Loss Calculated
from (A(t)) Total Mass Loss Corrosive Mass Loss from Faraday Law
SiC (A(t)) (mg 9 h ~) (mg 9 h ') (mg 9 h- ' ) (rag 9 h -~)
(g 9 L -~) (mV) (_0.01 mg) (_+0.01 mg) (_+0.01 mg) (_+0.01 mg)
3 7 2.20 2.32 0.12 0. I0
4 13 3.60 3.80 0.20 0.20
5 12 3.27 3.50 0.23 0.18
15 70 23.50 31.30 7.80 1. ! 8
25 130 43.40 59.60 16.20 2.34
O L T R A E T A L . O N S L U R R Y E R O S I O N - C O R R O S I O N S T U D I E S 371
I N
0,1
.<
o N
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0,1
t O 4 _ _
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t o - L -
t o L :
t o - ' _
t o - U -
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uL I " " ~
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to ~
L O "
io-t~
~0-~:
i0-?:
t 0 - J :
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iO 4 i
a
i i i i I i i i i i i i i 1 1
~ , J J ~ - , . J t ~ . b 9 J ' . . ~ L ' t I ' L L L , L . I . m
i ~ - " ~ - m L I .
i J i I
) t t0 z
F R E Q U E N C Y
I 1 I n I
\ ,
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tO 3 10'
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tO e
i i i i
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' . . . . I | , , . .
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illl.
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i i i i
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i i i I i I i i i i i i i ! i i i i i i i
) I 0 I0 10 10
FREQUENCY / H z
F I G , 6 - - PS D o f the fluctuations of acoustic and electrochemical signals. ( a ) Low concentration o f
abrading particles (3 g 9 L-I). ( b ) High concentration of abrading particles (15 g 9 L-J). Abrasion
conditions: Type 316L S S - - 1 M HeSO4--E = +0.2 V/ SSE Si C 500 i~m.
corres pondi ng t o the hi gh- f requency pl ateaus, whi c h do not depend on the X fl uctuati ons
( s e e Eq 4) .
The e vol ut i on o f thi s rati o as a f unct i on o f the rate o f e r os i on enabl es an i nves t i gat i on o f
the correl at i on be t we e n the me a n el ect ri cal charge and the me an acous t i c energy (propor-
ti onal t o the me c hani c al damage) .
As s hown i n Tabl e 2, t hi s rati o i s larger f or hi gh- eros i on rate, that i s, for a gi ve n me -
chani cal wear, the l e ve l o f c or r os i ve damage i ncreas es whe n e r os i on rate i ncreas es . It c o n-
TABLE 2--Comparison of the PSD at 100 Hz of the acoustic and electrochemical signals as function
of the erosion rate (estimated by the concentration of SiC particles g 9 L-t).
~a (100 Hz) xlr t (100 Hz) Wa/xlr l
SiC (g 9 L - l ) (10 -7 V 2 9 Hz- ' ) ( 10 -9 V 2 9 Hz- ' ) ( 10 -4)
3 1.0 6 10 4 6. 10 -2
4 2.0 8 x 10 -4 4. 10 -2
5 2.5 5 10 -2 2
15 8.0 4 x 10 -~ 5
25 20.0 1 5
firms t hat the l evel of t he abradi ng r egi me appears to be an i mport ant par amet er that cont rol s
t he rate of t he corrosi ve damage for passi ve mat eri al s [6,11].
Thi s is confi rmed by compar i ng the t i me recordi ngs for l ow and hi gh rates of erosi on
(Fi g. 7). Onl y for l ower osi on rate, a correl at i on can be found bet ween t he t i mes of occur-
rence of t he acoust i c and el ect rochemi cal transients. For hi gh rat es of erosi on, the current
cannot be consi der ed as cumul at i ve (superposi t i on of all the el ement ar y current t ransi ent s)
as i f t he depassi vat i on-repassi vat i on events were i ndependent .
Thi s feature can be expl ai ned by the nonl i near behavi or of t he passi ve surface subj ect ed
to hi gh rat es of consecut i ve mechani cal damages: a mean state of depassi vat i on can be
assumed because of t he over l appi ng (in t i me and space) of the t wo compet i t i ve react i ons of
depassi vat i on and repassi vat i on [6]. In that case, the el ect rochemi cal response of the di st ur bed
surface to one part i cl e i mpact depends on the el ect rochemi cal state of t he surroundi ng passi ve
surface. Paral l el experi ment s (pul sed l aser act i vat i on of passi ve el ect rodes) have demon-
strated the exi st ence of t ransi ent current coupl i ng bet ween l ocal i zed act i vat ed ar ea and pas-
sive surface [12]. Under slurry erosi on, the i mpedance of the passi ve surface around each
i mpact cannot be consi dered l i ke a pure capaci t ance [13]. The ohmi c component of the
i mpedance l eads to a short ci rcui t bet ween t he i mpedance of t he i mpact ed area and that of
the surroundi ng surface, whi ch expl ai ns that part i al current s can flow di rect l y f r om depas-
si vat ed areas to passi ve surfaces wi t hout flowing in t he pot ent i ost at i c l oop [6].
For hi gh regi mes of erosi on, the ohmi c part of the i mpedance of t he surroundi ng surface
i mpedance is smal l er and i ncreases the short circuit. In that case, the measured current has
a smal l er mean val ue and fluctuation ampl i t ude than the l i near sum of all the i ndi vi dual
current transients i nvol ved in the l ocal i zed corrosi on of the active areas i f the depassi vat i on-
repassi vat i on events were assumed to be i ndependent .
Consequent l y, this nonl i near behavi or can be consi der ed as a val i d expl anat i on for the
di scr epancy bet ween the val ues of the corrosi on rate obt ai ned from the Far aday l aw and
from the t ot al mass l oss correct ed for t he mechani cal wear; it al so expl ai ns that the corre-
l at i on bet ween the power spect ral densi t i es of the RMS acoust i c and current fluctuations
depends on t he rate of erosi on.
Co nc l us i o n
A new t echni que based on acoust i c emi ssi on was devel oped and al l owed the quant i fi cat i on
of the erosi on rate in slurry erosi on-corrosi on experi ment s. The mai n pr obl em encount ered
in the use of AE in erosi on experi ment s was rel at ed to t he accumul at i on of t he i ndi vi dual
burst emi ssi ons at hi gh-frequency rates. Thi s pr obl em has been sol ved by measuri ng the root
mean square funct i on of t he AE signals duri ng all the erosi on experi ment s. It has been shown
that t he frequency domai n anal ysi s ( PSD measur ement of the RMS acoust i c signal at l ow
.<
.<
60
40
20
0
-20
40
30
20
tO
0
-i0
0
a
5 tO 15 20 25 30 35 40 45 50
t i me / ms
[ . 0 b
4, 0
400 _
200 AA
*~ tOO
<1
0 . . . . . . . . . . . - . . . . . . . . . . . . . . . - - - r . . . . . - " - r . , . r
.2
-tOO
, ~ , i , , , i , , , I , ~ , 1 , 1 , i , , , L , , , I , ~ ' 1 ' ~ ' 1 ~ , ~
0 5 tO 15 20 25 30 35 40 45 50
t i me / ms
FI G. 7- - Ti me recording o f the fluctuations of acoustic and electrochemical signals. ( a) Low concen-
tration of abrading particles (3 8 9 L-t ). ( b) High concentration of abrading particles (15 g 9 L-t ). Same
abrasion conditions as in Fig. 6.
frequencies) can be compared to the time domain analysis (RMS mean value measurement).
They both give a linear relation between the RMS acoustic signal and the mass-loss rate
related t o the mechanical wear, which allows studying the synergy between the corrosive
damage and the abrasive wear.
Anot her interest in regard to the spectral analysis is characterizing the abrading regime
and especially determining the low-frequency fluctuations of the mean value of the erosion
rate. The analysis of electrochemical noise measurement data confirms the nonlinear behavior
of the corrosion current, which cannot be considered as the linear superposition of elementary
current transients caused by each impact, as if the depassivation-repassivation events were
independent. Consequently, the mean corrosion current does not yield the corrosion mass
loss with the Faraday law at high-erosion rates. This is corroborated by the simultaneous
analysis of the acoustic and corrosion signals, which shows that the corrosive damage is
larger at high-erosion rates for a given degree of mechanical damage.
Acknowledgment
This work has been financially supported by the "Conseil R6gional de Bourgogne" and
Creusot-Loire Industrie.
Re f e r e nc e s
[1] Heitz, E., "Chemo-Mechanical Effects of Flow on Corrosion," Corrosion, Vol. 47, No. 2, 1991,
pp. 135-145.
[2] Schumacher, W. J., "Ball Mill and Hub Test Methods for Slurry Erosion Evaluation of Materials,"
in Slurry Erosion--Uses, Applications and Test Methods, ASTM STP 946, J. E. Miller and F.
Schmidt, Eds., American Society for Testing and Materials, West Conshohocken, PA, 1987, pp.
5-17.
[3] Zeisel, H. and Durst, F., "Computations of Erosion-Corrosion Processes in Separated Two-Phase
Flows," in Flow-Induced Corrosion Fundamental Studies and Industry Experience, K. J. Kennelley,
R. H. Hausler, and D. C. Silverman, Eds., National Association of Corrosion Engineers, Houston,
1991, Paper 9.
[4] Oltra, R., Gabrielli, C., Huet, F., and Keddam, M., "Electrochemical Investigation of Locally De-
passivated Iron. A Comparison of Various Techniques," Electrochimica Acta, Vol. 3, No. 12, 1986,
pp. 1501-1511.
[5] Oltra, R., Bosson, J. C., Chapey, B., Renaud, L., and Charles, J., "Abrasion-Corrosion of Passive
Stainless Steels in Acidic Media: An Experimental Study of the Role of the Rate of Abrasion,"
Corrosion Science, Vol. 35, No. 1-4, 1993, pp. 641-646.
[6] Oltra, R., "Electrochemical Aspects of Localized Corrosion During Abrasion of Passive Iron-Based
Alloys in Acidic Media," in Wear-Corrosion Interactions in Liquid Media, A. A. Sagues and E. I.
Meletis, Eds., The Minerals, Metals & Materials Society, Warrendale, 1991, pp. 3-18.
[7] Bonness, R. J. and McBride, S. L., "Adhesive and Abrasive Wear Studies Using Acoustic Emission
Techniques," Wear, Vol. 149, 1991, pp. 41-53.
[8] Buttle, D. J. and Scruby, C. B., "Characterisation of Particle Impact by Quantitative A.E," Wear,
Vol. 137, 1990, pp. 63-90.
[9] Clough, R. B., "The Energetics of Acoustic Emission Source Characterization," Materials Evalu-
ation, Vol. 45, No. 5, 1987, pp. 556-563.
[10] Chapey, B., "Ph6nom6nes de synergie entre endommagements m6canique et corrosif dans les cas
d'abrasion-corrosion des aciers inoxydables. Mise au point d'une technique de quantification de
l'endommagement m6canique reposant sur l'6mission acoustique," Thesis, Universit6 de Bour-
gogne, Dijon, 1993,
[11] Lotz, U., Schoilmaier, M., and Heitz, E., "Flow-Dependent Corrosion. II. Ferrous Materials in Pure
and Particulate Chloride Solutions," Werkstoffe und Korrosion, Vol. 36, 1985, pp. 163-173.
[I2] Oltra, R., Indrianjafy, G. M., and Roberge, R., "Effect of Electrical Transient Coupling Phenomena
on the Initiation of Pits by a Pulsed Laser," Journal of the Electrochemical Society, Vol. 140, No.
2, 1993, pp. 343-347.
[13] Isaacs, H. S. and Ishikawa, Y., "Current and Potential Transients During Localized Corrosion of
Stainless Steel," Journal of the Electrochemical Society, Vol. 132, No. 6, 1985, pp. 1288-1293.
F ranfois Huet, l Michel J drOme, 2 Panagiotis Manolatos, 2 and
F ranfois Wenger 2
Influence of Hydrogen Absorption on the
Electrochemical Potential Noise of an Iron
Electrode Under Corrosion with
Gas Evolution
RE F E RE NCE : Huet, E, J6r6me, M., Manolatos, R, and Wenger, E, "I nf l ue nc e o f Hy d r o g e n
Ab s o r p t i o n o n t he El e c t r o c h e mi c a l Po t e nt i a l No i s e o f an I r o n El e c t r o d e u n d e r Co r r o s i o n
wi t h Ga s Ev o l ut i o n, " Electrochemical Noise Measurement for Corrosion Applications, STP
1277, Jeffery R. Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L.
Dawson, Eds., American Society for Testing and Materials, 1996, pp. 375-386.
ABSTRACT: Using the electrochemical permeation technique and a model for hydrogen dif-
fusion in a metal, the fluctuations of the concentration, AC(t), of hydrogen absorbed in the
first atomic layers of an Armco iron membrane, under cathodic polarization and at the corrosion
potential in sulfuric acid solution, were measured. The fluctuations of the electrode potential,
AE(t), and of the electrolyte resistance, ARe(t), induced by bubble evolution were also simul-
taneously recorded. Under cathodic potential, AE(t) and AC(t) are clearly induced by the
evolution of big hydrogen gas bubbles. However, at the corrosion potential, another source of
AE(t) and AC(t) must be proposed. It has been shown that this difference is related to the
influence of an intermediate reaction species which partly blocks the hydrogen absorption under
cathodic polarization and disappears at the corrosion potential.
KEYWORDS: hydrogen, adsorption, absorption, permeation, galvanostatic electrochemical
noise measurement, electrolyte resistance, iron, bubble
The growth and departure of gas bubbles at an electrode polarized under galvanostatic
conditions induces fluctuations of the voltage, AV(t), between the reference and the working
electrodes. These fluctuations, also called electrochemical potential noise (EPN), can be
separated into two terms, the ohmic drop fluctuations IAR~(t), and the electrode potential
fluctuations, AE(t) related to faradaic processes [1,2]:
AV(t) = IARe(t ) + AE(t)
( 5 )
In a previous investigation concerning hydrogen embrittlement of steel electrodes under
cathodic polarization in sulfuric acid [3], the EPN generated by hydrogen bubble evolution
was studied. The results were in agreement with the assumption that the electrode potential
fluctuations, AE(t), were related to fluctuations of hydrogen concentration, AC(t ), in the first
UPR 15 du C.N.R.S. Physique des Liquides et Electrochimie, Universit6 Pierre et Marie Curie, Tour
22, 4 place Jussieu, 75252 Paris Cedex 05, France.
2 Laboratoire Corrosion-Fragilisation-Hydrogbne, Ecole Centrale de Paris, Grande Vole des Vignes,
92295 Chhtenay-Malabry Cedex, France.
3 7 5
Www.astIII.OFg
atomic layers of the metal. These fluctuations of hydrogen concentration were induced by
gas bubble evolution. A subsequent work carried out on iron membranes with the permeation
technique [4] showed that a correlation exists between the permeation flux fluctuations and
the electrode potential fluctuations, due to the evolution of hydrogen bubbles. The local flux
of hydrogen into the membrane gradually decreases under a growing attached bubble and
quickly increases when the bubble departs. The aims of this research are, first, to correlate
the permeation flux fluctuations to hC(t ), and second, to extend this study to the free po-
tential of iron at which hydrogen evolution occurs simultaneously with iron dissolution. To
this purpose, electrochemical permeation tests were performed with simultaneous electro-
chemical noise measurements, and a model was developed to deduce AC( t ) from the per-
meation data.
Techniques
The electrochemical permeation technique, designed by Devanathan and Stachurski [5],
is generally used to study hydrogen transport in metals. The metallic sample is a flat sheet
(a disk) on one side of which hydrogen evolution occurs ("ent rance side"), as a result of a
cathodic polarization in an electrolytic solution. Some of the adsorbed hydrogen atoms pro-
duced by the proton discharge (Volmer reaction) are absorbed (ingress reaction) at the en-
trance side, diffused through the sheet, and are oxidized by a suitable polarization of the
exit side in 0. 1N sodium hydroxide (NaOH) solution. The flow of diffusing hydrogen is
measured by the resulting anodic current, lp(t). This flow is related to the concentration of
absorbed hydrogen in the first layers of metal at the entrance side. At this side of the iron
membrane, hydrogen evolution occurs according to the global reaction scheme:
H + , Ha d s ~ Ha b s
H2
I f diffusion is assumed to occur mainly in the x direction (across the sample, see Fig. 1),
the concentration, C(x, t ) , of absorbed hydrogen obeys Fi ck' s equation
OC(x, t ) OW(x, t )
O - - ( 2 )
Ot Ox 2
and the boundary condition [6]:
C(d, t) = 0 (3)
where D is the diffusion coefficient of hydrogen in the metal.
The steady concentration, C(x), is obtained for OC/Ot = 0 in Eq (2); so, with Eq (3)
HUET ET AL ON INFLUENCE OF HYDROGEN ABSORPTION 377
\ - " I
" k I ~ e te c 1
l si(; ~ [ s i d e J
O a , v a ; o s t a t
[ Generator [
[Control Vol!age I
~REF.
" R '
C.E.
Audio
% AV Tape
Recorde
AVRe=
a z~LR e
FIG. 1--Experimental arrangement used f or the measurement of the fluctuations of the hydrogen
permeation current, the electrode voltage and the electrolyte resistance.
where the concentration, C(0) = C, at the entrance side is related to the steady permeation
current, lp, as measured at the exit side:
~=,, -~ ( 5 )
where F is the Faraday constant and S is the area of the entrance side.
Because of hydrogen bubble evolution on the entrance side, the concentration of adsorbed
hydrogen fluctuates, inducing fluctuations of the concentration of absorbed hydrogen in the
first layers of metal, AC( t ) = AC(0, t), and, therefore, fluctuations of the permeation current,
AIp(t) [4]. For calculating the time fluctuations, AC( t ) , from the measured time recordings
of Mp(t ), a transfer function, H ( f ) , between AC( t ) and Al p(t ) is needed. The theoretical
calculation, given in the Appendix, leads to
FSD
A / . ( ~ )
H(f)=AC(t~ sin h [ ~ : ~ ] d (6)
where Alp(to) and AC(to) are the Fourier transforms (FF) of Alp(t) and AC(t), respectively,
and to = 2"rrf (where f = frequency).
The time recording of AC(t) can be determined from Alp(t) in three successive steps: ( l )
taking the fast Fourier transform (FFF), Alp(to), of Alp(t); (2) dividing Alp(to) by H ( f ) which
gives AC(to); and (3) taking the inverse FFF (IFFT) of AC(to)
[ F F r [ A l p ( t ) ] ]
AC(t) = IFFT [_. ~ J
( 7 )
Two problems of digital signal processing arise when using this procedure:
1.
2.
The first concerns the first points and the last points of the AC(t) time recordings which
are not correctly calculated by this procedure; these points will be cancelled in the
AC(t) plots.
The second is introduced by Step 2; as H ( f ) tends towards zero for high frequencies,
the division in Eq 7 introduces high-frequency components with large amplitudes into
the AC(t) recordings; these parasitic component s can be avoided by considering H ( f )
as a constant for frequencies higher than fo, where fo is taken such as: ]H(fo)l = 2%
H(0). This 2% value was chosen to obtain a reasonable level of spurious noise on
AC(t) recordings. It was checked and found that the fluctuations of AC(t) induced by
bubble evolution were not affected by the choice of f o.
Concerning the electrochemical noise measurement, it was first necessary to separate the
ohmic drop fluctuations from the overall EPN AV(t) according to Eq 1. The measurement
of the electrolyte resistance fluctuations, which uses a 100-kHz excitation signal of small
amplitude, has already been reported [2] and is summarized in Fig. I. The calibration factor,
a, between the R e channel output, VRe, and the electrolyte resistance, R e, was a = 36 mV
1) -1. The experimental arrangement described in Fig. 1 allows the simultaneous measurement
of two other quantities: the EPN, AV(t), of the iron surface, and, by means of the electro-
chemical permeation technique the ECN, Alp(t), of hydrogen permeation through the iron
sample.
Procedure
Our purpose was to use the permeation method to investigate surface phenomena related
to hydrogen evolution on an iron electrode, especially hydrogen concentration j ust inside the
entrance side. Therefore, the sample was a flat sheet of Ar mco iron, sufficiently thin to
minimize the diffusion time (thickness d = 0.02 cm). Samples were cut from an annealed
(920~ for 1 h, slow cool i ng in the furnace) bar of 2-cm diameter; both sides were polished
(emery paper grade 1200), then the exit side was immediately electroplated in a palladium
chloride (PdC12) solution to obtain a thin film of palladium (less than 0.1 ixm thick). The
complete plating procedure is described elsewhere [7]. The role of this palladium coating is
to ensure complete oxidation of hydrogen atoms [8,9]. The iron membrane was placed ver-
tically between the t wo cells; the useful surface on the entrance side was a narrow, horizontal
strip (0.07 by 0.06 cm), to limit draggi ng by bubbles detached from the surface. The strip
was delimited by a 15-1~m-thick electrophoretic coating (epoxy t ype used in the automotive
industries). The useful surface of detection side (exit side) was larger (disk of 1-cm 2 area),
because reproducing such a narrow strip facing the other one was difficult. The hydrogen
diffusion was though to be practically unidirectional from the entrance side to the exit side.
HUET ET AL. ON INFLUENCE OF HYDROGEN ABSORPTION 379
Hydrogen evolution on the entrance side was achieved galvanostatically, in 0. 5M sulfuric
acid (H2SO4) solution. The exit side solution (0.1N NaOH) was deaerated by argon bubbling
before the experiment in the oxygen-free detection cell.
After mount i ng the sample, a potential on the exit side was imposed at - 4 5 0 mV with
respect to the saturated sulfate electrode. When the corresponding anodic current was very
small and constant (less than 100 nA), the entrance cell was filled with the acid solution and
polarized at once to a 80-mA cm -2 constant cathodic current density. The permeation current
transient was traced with an analog recorder. After a fast transient of a few seconds, the
evolution of surface condition induced a slow decay in the flux for a period of a few minutes.
After this time, the mean concentration of absorbed hydrogen at the entrance side had be-
come quite constant and a steady current lp = 8/ xA was reached. The analog recorder was
then disconnected to minimize the 50-Hz noise caused by the power supply, and deaeration
was stopped in the detection cell to obtain a noise-free permeation current. This did not
affect the permeation current. Then the voltage fluctuations, AV(t), the permeation current
fluctuations, Alp(t), and the electrolyte resistance fluctuations, z~ge(t), we r e simultaneously
recorded with an audio tape (TEAC RD-180T) for more convenient signal processing. After
these recordings, the analog recorder was connect ed again and the charging current was cut
off. A new permeation transient was then recorded, leading to a new steady state. The analog
recorder was once again disconnected to allow new recordings of AV(t), AE(t), and IAee(t
) under free corrosion conditions. Later on, the recorded signals were digitized with a real-
time comput er (Concurrent Comput er Corporation RTU 5450).
Resul t s
Figure 2 shows time recordings of Alp and AC(t) induced by hydrogen bubbles evolving
at the entrance side of the iron membrane at a 80- mA cm -2 cathodic current density. As
onl y fluctuations were investigated, both time and ordinate origins are arbitrary. The AC(t)
recordings were calculated as explained above for a diffusion coefficient D = l 0 -4 cm 2 s -t
obtained in Ref 4. As this value was slightly higher than the one given by Devanathan [10]
for Ar mco iron membranes (8 10 -5 cm 2 s-l ), a lower value of D was tried; in that case,
a pronounced oscillation of AC(t) at each bubble departure was obtained, which had no
physical meaning. The transfer function used for calculating AC(t) was plotted in the Nyquist
plane in Fig. 3. The 200-s duration recordings (Fig. 24) show that AC(t) and Alp(t) fluctu-
ations were very similar; in the 20-s duration recordings (Fig. 2B), the concentration increase
of hydrogen absorbed in the first layers of metal induced by a bubble departure was found
to occur, as expected, before the permeation current increase, because of the diffusion time
of hydrogen in the membrane. In Fig. 2B, the parasitic high frequency noise was limited by
choosi ng the value fo = 3.7 Hz.
Owi ng to this method for calculating AC(t), the Ale(t) recordings have been replaced by
AC(t) plots in the following figures. The surface phenomena at the entrance side can be
investigated in the cathodic domain and at the corrosion potential by analyzing the fluctua-
tions IARe(t ), AV(t), AE(t), and AC(t), all related to the entrance side.
Cathodic Polarization
Figure 4 presents: the IARe(t ) and AV(t) fluctuations, measured in the entrance cell; the
AE(t) fluctuations calculated from AV(t) and IARe(t); and the AC(t) fluctuations, calculated
by the method described above, corresponding to the same experiment as Fig. 2.
Previous works [1,2] have shown that bubble departures induce sudden decreases in R e
(ARe < 0) as a result of the release of the surface screened by the bubbles. In Figs. 4A and
=- 2
: - , , , i
9 < 0
,9.
E
-<:]
-2
A
0
-1
0
, i , l , l , l , l , i , l , l , I
20 40 g0 80
AC
i , i , l , i , F , i , t , r , l , i ,
100 120 140 180 180 200
t i me / s
.5
< 0.0
=k
o
~ -
r..)
<] -S
, i , i , I , I , r , i , I , I I T ' ] ' 1 ' [ ' 1 ' l ' l ' J ' l ' ( ' l '
2 4 g 8 tO 12 I4 i8 I8 20
t i me / s
FIG. 2- - Ti me recordings of the fluctuations of the permeation current Alp(t) and o f the absorbed
hydrogen concentration AC(t ) in the f i rst layers of an iron membrane pol ari zed at a 80 mA cm -2 cathodic
current density. Arbitrary origins. ( A) Recording duration 200 s; sampling f requency 10 Hz. ( B) Re-
cording duration 20 s; sampling f requency 100 Hz.
HUET El" AL. ON INFLUENCE OF HYDROGEN ABSORPTION 381
2, 5
'7,
" 15
"~ - , 5
10 Hz
- i , 5 - . 5
R E AL P AR T /
1 Hz
0.01 Hz
' l ' , ' l ' , ' l ' l ' l ' l ' ,
.5 1.5 2.5 3.5 4,5
10 -23 A ( at . H) "1 c m 3
FI G. 3--Nyquist plot of the transfer function between AC( t ) and Alp(t).
4B, lfiaYe(t) recording presents positive j umps (as 1 < 0 in the cathodic domain); these j umps
can be attributed to " bi g" bubble departures (bubbles of several hundred micrometres in
diameter), while the small fluctuations are due to departures of numerous small bubbles. In
Fig. 4A, the comparison between ~e(t ), AE(t), and AC(t) fluctuations indicates that AE(t)
and AC(t) fluctuations are highly correlated with big bubble evolution. When such a bubble
leaves the surface, a AE(t) j ump is observed in the anodic direction, followed, after a short
delay of a few tenths of a second, by a fast increase of C(t) (Fig. 4B). This indicates that
the concentration of absorbed hydrogen under a bubble is lower than under a free area.
Not e that the recordings of AE(t) and AC(t) are very smooth, which shows that small
bubbles do not induce E or C fluctuations. Therefore, under cathodic polarization, AC(t)
fluctuations are onl y due to big bubble departures.
Corrosion Potential
The evolution of the permeation current Ip(t) after cutting off the current applied to the
entrance side of the cell is represented in Fig. 5. A two-step evolution is observed: the first
step is a sudden drop of Ip, leading to a mi ni mum in about 10 s. The second one is a slow
increase of Ip(t). The Ip(t) value reached after a few minutes corresponds to a permeability
about three times the value obtained under cathodic polarization.
Figure 6 gives the AC(t) fluctuations, together with the corrosion potential AE(t) ( =
AV(t), since 1 = 0) and electrolyte resistance ARe(t ) fluctuations. Because of the parasitic
high frequency noise of AC(t), Alp(t) fluctuations have also been plotted for a more con-
venient reading of Fig. 6. A very good temporal correlation between AE(t) and - AC( t ) is
shown in Fig. 6. Not e that, contrary to what was observed under cathodic polarization, an
increase of C is linked to a decrease of E, and the compari son of AE(t) or AC(t) with
fiaYe(t) does not show any obvious influence of bubble evolution on E and C.
Di s c us s i on
At the corrosion potential, in spite of a lower hydrogen reduction current, the hydrogen
permeability is higher than under cathodic polarization. This could be explained only by
considering that under cathodic polarization, an important portion of the surface is blocked,
382 E L E C T R O C H E M I C A L NOI S E M E A S U R E M E N T
I00
=
50
<~ 0
- 5 0
,?
E 1
0
.~. -~.
0 20 40 60 80 100 I20 I40 180 180 200
time / s
40
20
- 20
<
~, AE
E 5
0
- 5
0 2 4 6 8 i0 12 14 18 18 20
<
time / s .~
FIG. 4--Time recordings of the fluctuations of the ohmic drop IAR~(t), the voltage AV(t), the electrode
potential AE(t), and the absorbed hydrogen concentration AC(t) at the entrance side of an iron electrode
polarized at an 80 mAcm 2 cathodic current density. Arbitrary origins. (A) Recording duration 200 s;
sampling frequency 10 Hz. (B) Recording duration 20 s/ sampling frequency 100 Hz.
HUET ET AL. ON INFLUENCE OF HYDROGEN ABSORPTION 3 8 3
<
=:L
e~
~4
13
12
lo
9
8
7
8
5
4 ' [ ' ~ ' ~ ' ~ ' [ ' ~ ' ~ I ' ~ ' ~ ' I ' ~ ' ) ' ~ ' ) ' ~ ' } ' ' ' ~ ' } ' ' ] '
0 40 80 120 i80 200 240 280 320 380 400
time / s
FIG. 5- - Evol ut i on of the permeation current when the charging current at entrance side is cut off.
2
<
<
i
" 7 ,
<
.5
0.0
- , 5
1
-1
0
-1
0.0
- - Al p
0 20 40 60 80 100 f20 140 160 180 200
time / s
FI G. 6 - - ~ me recordings of the f l uct uat i ons of the electrolyte resistance/~R~(t), the electrode pot ent i al
AE(t ), the absorbed hydrogen concentration AC(t ) and the permeation current /kip(t) f or an iron
membrane at the corrosion potential. Arbitrary origins. Recording duration 200 s; sampling f requency
lO Hz.
leaving only a small active surface for the hydrogen absorption. After cutting off the cathodic
current, the sudden drop of lp would indicate a sharp decrease of the Volmer reaction rate.
The subsequent slow increase of hydrogen permeability could be explained by the freeing
of the blocked surface by the anodic dissolution reaction. The resulting increase of the active
surface would be high enough to induce the increase of the absorbed hydrogen amount, in
spite of the low rate of the Volmer reaction. The nature of the blocking species in the cathodic
domain has not been identified, but some authors [11,12] have assumed the existence of a
strongly adsorbed hydrogen, Had~*, involved as a blocking species in the hydrogen reduction
mechanism. I f hydrogen absorption through Had~* is impossible or very slow with respect to
the absorption through H,d ~, Had,* is acting as a blocking species for hydrogen penetration.
Under cathodic polarization, a bubble departure induces a positive AE j ump, in spite of
the local increase of the current density (which leads to a local negative AE j ump) which
increases the adsorption rate, and then the absorption rate: a positive AC j ump is effectively
observed. The positive AE j ump can be first explained by an increase of the useful surface
which induces a lower mean current density. On the other hand, the existence of a blocking
species in the cathodic domain leads to an increase of the mean overvoltage [3,12]. Then a
positive AE j ump at a bubble departure means that the blocking species has partly disap-
peared under the detached bubble, perhaps because of a very low current density under the
bubbles or a slow molecular recombination. Then the release of an active area without
blocking species induces a lower overvoltage (AE > 0), and a sudden increase of adsorbed
hydrogen, which leads to a subsequent positive AC(t) jump. The absence of AE and AC
j umps at small bubble departures shows that the elimination of the bl ocki ng species requires
enough time to occur.
The existence of blocking species allows one to understand why big bubbles induce
AE( t ) fluctuations at a cathodic polarization rather than at the corrosion potential. At this
potential, because of the absence of bl ocki ng species [11,12], such AE and AC j umps are
not observed at bubble departures, which means that there is no sudden variation of adsorbed
hydrogen concentration. The origin of the observed AE( t ) fluctuations is unknown, but it
can be noticed that there is a correlation between AE(t) and - AC( t ) : a slow variation of E
towards cathodic potentials (AE < 0) corresponds to an increase of the adsorption rate, and
therefore to an increase of C(t ) (AC(t) > 0).
Concl usi ons
In this study, a significant difference has been observed in the mechani sm of hydrogen
absorption in iron when cathodically polarized versus when at the corrosion potential. At
the corrosion potential, hydrogen absorption is more important than at a high cathodic po-
larization, in spite of the lower rate of the Volmer reaction. Under cathodic polarization, big
bubble evolution rules the potential and absorbed hydrogen concentration fluctuations, which
is not true under corrosion conditions. This result can be explained by the hypothesis that a
blocking species is formed under cathodic polarization, which limits the hydrogen absorption.
This blocking species is eliminated under a growing attached bubble; its elimination needs
a somewhat long time, and does not occur under small bubbles.
Under corrosion conditions, when the blocking species do not exist, a correlation between
potential and concentration fluctuations has also been observed, but its origin could not be
identified. At the present stage of this research, additional work is necessary to identify
precisely the nature of the blocking species and to understand the origin of fluctuations at
the corrosion potential.
HUET ET AL, ON INFLUENCE OF HYDROGEN ABSORPTION 385
APPENDIX
Theoretical Calculations
I f hydrogen atoms are supposed to diffuse only in the x direction, the fluctuations, AC(x, t),
of the concentration of absorbed hydrogen at position x and time t around the steady value,
C(x), obey Eqs 2 and 3:
02
O_ [AC(x, t)] = D - - [AC(x, t)] (8)
Ot Ox 2
aC(d, t) = 0 (9)
The fluctuations, Al,(t), of the permeation current are given by Eq 5:
[ 0 ]
Alp(t) = - F S D ~xx [AC(x, t)] (10)
x=d
The FI" of Eqs 8 through 10 are:
a 2
j to AC(x, to) = D Ox--- S [AC(x, to)] (11)
aC(d, to) = 0 ( 12)
[ 0 ]
Alp(.,) = - F S O ~ [AC(x, ~) ] ( 13)
x=d
where AC(x, to) and Alp(to) are the FT of AC(x, t) and AIp(t), respectively. Equation 11 gives
AC(x, t o ) = A e x p ( ~ x ) + B e x p ( - l/-J@~DX ) (14)
Accordi ng to Eq 12, the constants A and B are related by:
B = - A exp ( 2 ~ d ) (15)
The transfer function H( f ) between AC(0, to) = A + B and Alp(to) is derived from Eqs
13 through 15 and is given by Eq 6 in the main body of the paper.
References
[1] Gabriclli, C., Huet, F., Keddam, M., and Sahar, A., Journal of Applied Electrochemistry, Vol. 19,
1989, p. 683.
[2] Gabrielli, C., Huet, E, and Keddam, M., Journal of the Electrochemical Society, Vol. 138, 1991,
p. L82.
[3] Benzaid, A., "Etude du D6gagement d' Hydrog~ne sur Electrode Verticale en Acier 42CD4, par la
M6thode du Bruit Electrochimique. Application h la Fragilisation par l' Hydrog~ne," Thesis, Ecole
Centrale Pads, Chatenay-Malabry, France, 1992.
[4] Amrani, Z., Huet, E, JEr6me, M., Manolatos, E, and Wenger, E, Journal of the Electrochemical
Society, Vol. 141, 1994, p. 2059.
[5] Devanathan, M. A. V. and Stachurski, Z., "The Adsorption and Diffusion of Electrolytic Hydrogen
in Palladium," Proceedings of the Royal Society of London, London, Vol. A270, 1962, p. 90.
[6] Nanis, L. and Govindan Namboodhiri, T. K., Journal of the Electrochemical Society, Vol. 119,
1972, p. 691.
[7] Manolatos, P. and J6r6me, M., Electrochimica Acta, Vol. 41, 1996, p. 359.
[8] Manolatos, E, J6r6me, M., and Galland, J., Electrochimica Acta, Vol. 40, 1995, p. 867.
[9] Manolatos, E, J6r6me, M., and Galland, J., "Palladium as a Catalyst of Hydrogen Oxidation,"
International Conference on Hydrogen Transport and Cracking in Metals, A. Turnbull, Ed., The
Institute of Materials (U.K.), 1995, p. 155.
[10] Devanathan, M. A. V. and Stachurski, Z., Journal of the Electrochemical Society, Vol. 111, 1964,
p. 619.
[11] Caprani, A. and Morel, E, Journal of Applied Electrochemistry, Vol. 7, 1977, p. 65.
[12] Epelboin, I., Morel, E, and Takenouti, H., Journal of the Electrochemical Society, Vol. 118, 1971,
p. 1282.
Jos~ M. Ma l o 1 a n d Oc t av i o Vel azco ~
Electrochemical Noise Response of Steel
Under Hydrodynamic Conditions
REFERENCE: Malo, J. M., and Velazco, O., "Electrochemical Noise Response of Steel
Under Hydrodynamic Conditions," Electrochemical Noise Measurement for Corrosion Ap-
plications, ASTM STP 1277, Jeffery R. Keams, John R. Scully, Pierre R. Roberge, David L.
Reichert, and John L. Dawson, Eds., American Society for Testing and Materials, 1996, pp.
387-397.
ABSTRACT: Electrochemical potential and current noise (EPN, ECN) signals for a rotating
disk electrode (RDE) were measured with regard to the electrochemical and electrical contri-
butions. Particular attention was given to the resistance of the electrical connection to the disk
because this is considered a source of electrical noise. Electrical noise measurements were
obtained in the absence of an electrolyte using a passive load. The noise levels under static
and dynamic conditions did not exceed l0 I~V for potential and 0.1 p~A for current readings.
Electrochemical tests for mild steel in 0.1M sodium sulfate" (Na2SO4) show distinct noise
patterns for static and hydrodynamic regimes. It is shown that electrical noise contribution is
often negligible when compared to electrochemical noise signals obtained for a corrosion
process under uniform attack and laminar flow.
KEYWORDS: corrosion, rotating disk electrode, electrochemical noise, forced convection,
diffusion
Relative motion between a metal surface and a solution is a condition often found in
corrosion processes. In some cases, there is forced solution flow past a stationary electrode,
and, in others, the metal surface is in motion with respect to the bulk solution. In the case
of the rotating disk electrode (RDE) motion, surface drag causes swirling of the fluid, which
is forced radially over its surface, and axial flow brings fresh solution to the disk. With this
centrifugal force, the surface is uniformly accessible to species in solution. The advantages
of the RDE are that mathematical models for current and potential distribution have been
developed for well-defined hydrodynamic flow; the RDE system is easy to use and fabricate;
and, even at high rotation speeds, the disk operates under laminar flow conditions. However,
the current and potential distributions may not be uniform on the electrode surface [1], and
there are some difficulties in maintaining an efficient electrical connection to the rotating
electrode [2]. The latter effect has probably a greater influence on the limited use of rotating
disk or cylinder electrodes in the study of electrochemical noise measurements (ENM). The
majority of tests involving ENM are described under static flow or they address forms of
localized corrosion [3-5] in which the problem of interference by electrical noise is reduced
as a result of the high level of electrochemical transients. The results included here focus
on the feasibility of obtaining reliable ENM using an RDE for a system in a laminar flow
regime in which uniform corrosion is taking place. In this case, ENM can be considerably
Research engineers, Instituto de Investigaciones EtEctricas, Interior Internado Palmira s/n, Apartado
Postal 475, 62000 Cuernavaca, Morelos, Mrxico.
387
Www.astIII.0F~
influenced by the electrical noise that originates in instruments and accessories used in ex-
perimental work.
Experimental Method
Test Mat eri al s
The test material was mild steel with the following chemical composition: 0.28% carbon,
0.059% sulfur, 0.25% silicon, and 0.87% manganese. Solutions were prepared from analyt-
ical grade (p.a. Merck) reagents.
R DE Speci f i cat i on
Mild steel-working electrodes in the form of a 1-cm 2 disk were axially embedded on a
nylamid cylinder, which was filled with epoxy resin to reduce crevice formation on the edges.
The RDE was built using a bearing-guided shaft to minimize wobble. The rotation speed of
the RDE was varied in the 0 to 1500-rpm range. The electrical connection of the rotating to
the fixed elements of the RDE was made by using three carbon/ si l ver (graphalloy) brushes,
120 ~ axially spaced, in contact with a silver ring to ensure electrical continuity and a low
electrical noise level.
El ect ri cal Noi se Tests
Electrical measurements were made of the noise level produced by the RDE' s brush con-
tact by replacing the aqueous medi um with 30 mL of mercury in which the rotating electrode
was fully immersed (Fig. 1). The circuit was closed by adding a passive load in series and
by immersion of copper leads into the mercury pool. Electrical potential and current noise
readings were carried out under static conditions and three rotation speeds, 500, 1000, and
1500 rpm, using a two-electrode configuration.
0
I B I
o
F
FIG. 1--Schematic diagram showing the experimental setup f or measuring electrical potential or
current noise: (a) potentiostat, (b) passive load, (c) brush contact, (d) RDE, (e) mercury pool, and (f)
copper lead immersed in the mercury pool.
MALO AND VELAZCO ON ELECTROCHEMICAL NOISE RESPONSE OF STEEL 3 8 9
Electrochemical Tests
Tests were carri ed out for mi l d steel in 0. 1M sodi um sulfate (Na2SO4) (pH = 6) in an
aerat ed 200- mL sol ut i on at r oom t emperat ure. The di sk speci mens exhi bi t ed a 0. 78-cm 2 area
(0. 5-cm radi us) and were pol i shed to a 1200-grit finish and degr eased wi t h acetone. The
count er el ect rode was a 4- cm 2 area pl at i num sheet. Pot ent i al s were measured agai nst a stan-
dar d cal omel el ect rode (SCE). Cat hodi c pot ent i ost at i c pol ari zat i on t est s were car r i ed out
starting at t he corrosi on pot ent i al and sweepi ng down to - 1.8 V at a scan rat e of 60 mV/
min.
El ect r ochemi cal tests were carri ed out usi ng a Sol ar t on/ Scl umber ger 1286 el ect r ochemi cal
i nt erfact cont rol l ed by a personal comput er. El ect r ochemi cal pot ent i al and current noi se mea-
surement s ( EPNM and ECNM: maxi mum resol ut i on 1 txV and 100 pA, respect i vel y) were
obt ai ned at a sampl e rat e of 1 r eadi ng/ s to pr oduce records of 1024 or 2048 points. A 1-
k l l current sensor st andard resi st or was sel ect ed for current measurement s (whi ch corre-
sponds to a 200- ~A ful l -scal e current value). Fast Four i er t ransform ( FFI ' ) anal ysi s was
appl i ed to t he experi ment al t i me series usi ng a di gi t al al gori t hm [6]. EPNM and ECNM wer e
obt ai ned from i ndependent tests usi ng soft ware devel oped by the authors.
Results and Discussion
Background Noise
Noi se from the i nst rument s and accessori es (see Fi g. 1) used was first eval uat ed, al l owi ng
a 50-1xA current flow t hrough a 150-12 resistor. The choi ce of t he current val ue cor r esponds
to si mi l ar currents found in an el ect r ochemi cal syst em descr i bed in the fol l owi ng section.
Fi gur e 2 shows pot ent i al and current fluctuations (upper and l ower pl ot , respect i vel y)
obt ai ned for the exper i ment al set up descr i bed in Fi g. 1. For bot h t i me series, t he first half-
per i od readi ngs, 1024 s, were t aken under static condi t i on. The r emai ni ng per i od corresponds
to pot ent i al and current fluctuations under dynami c condi t i ons for t hree speeds of rot at i on:
500, 1000, and 1500 rpm.
Not e that the maxi mum l evel of pot ent i al fl uct uat i ons is appr oxi mat el y 0.01 mV and the
same i nt ensi t y of fluctuations, wi t h a sl i ght decrease in t he t rend of t he signal, is mai nt ai ned
regardl ess of the static or rot at i ng condi t i on. For t he current fluctuations, the maxi mum l evel
is 0.1 ~A and remai ns const ant for t he per i od studied. A sl i ght i mpr ovement in t he br ash-
cont act effi ci ency was obser ved for the rot at i ng condi t i on because some of t he current spi kes
obt ai ned in static condi t i on were not present for the rot at i ng condi t i ons.
Fi gur e 3 shows the pot ent i al and current power spect ral densi t y (PSD) pl ot (upper and
l ower pl ot , respect i vel y) for the first 1024 dat a poi nt s (rpm = 0) of the t i me series of Fi g.
2. The si gnal s cl osel y r esembl e a whi t e noi se source. The ampl i t ude is i ndependent of
frequency for the range of frequenci es studied, whi ch is the expect ed response for t he passi ve
el ement s in the el ect ri cal syst em studied. The PSD pl ot s are further anal yzed by compar i son
wi t h t hose obt ai ned f r om an el ect rochemi cal syst em in the fol l owi ng section.
The above results can be used to define t he i nt ri nsi c el ect ri cal noi se of the syst em to
est abl i sh a basel i ne for maki ng ENM wi t h t he syst em. For t he sampl i ng rat e studied, an
i nherent level of noi se is associ at ed wi t h t he i nst rument s and accessori es. Thi s noi se cont ri -
bution must be t aken i nt o account in any test at or bel ow a si mi l ar current level. The concern
for t he brush-cont act of the RDE as a source of noi se is j ust i fi ed, but i mpr ovement s in t he
noi se l evel of current noi se signal can be expect ed for dynami c condi t i ons. Thi s behavi or is
val i d for the part i cul ar brush-cont act eval uat ed, and di fferences can be expect ed dependi ng
on t he nature of the mat eri al s used for this pur pose [7]. The l evel s of pot ent i al and current
Pot ent i al mV
0. 1
0 . 0 5
-0.05
500 1 o00 1500
rpm=0 i
- 0. 1 i i i
0 500 1000 1500 2000
Time s
Current density pA
r pm = 0 5 0 0 1 0 0 0 1 5 0 0
9 i - h L t L ~ . u . , i . , , , l a ~ - . a .
50.0
4 9 . 8
0 500 1000 1500 2000
Time s
FIG. 2--Electrical potential and current noise time series obtained f or (a) static and (b) dynamic
condition shown in Fig. 1.
noi se fluctuations can be regarded as a basel i ne for compar i ng ENM. The noi se levels of
the i nst rument s should be consi der abl y l ower than t hose of the el ect rochemi cal syst em.
El ect r ochemi cal Noi se Tests
To est abl i sh a basi s of compar i son bet ween the backgr ound noi se and a t ypi cal el ect ro-
chemi cal corrosi on syst em, mi l d steel in a neutral aerat ed sol ut i on was sel ect ed (0. 1M
Na2SO4). Here, oxygen reduct i on is t he mai n cat hodi c reaction, and its di f f usi on- cont r ol l ed
ki net i cs depend on the flow rate. Therefore, the flow rate wi l l det er mi ne corrosi on rat e of
the sampl e studied.
Fi gur e 4 shows the cat hodi c pol ari zat i on curves for mi l d steel in 0. 1M Na2SO 4 under static
and t wo hydr odynami c condi t i ons. A di f f usi on- cont r ol l ed pot ent i al range can be identified,
al t hough for the static r egi me a compet i t i ve hydr ogen reduct i on react i on is al so present but
is not domi nant . For an i ncreasi ng rat e of stirring, the oxygen- l i mi t i ng current values are
i ncreased as wel l as its pot ent i al range. At mor e cat hodi c pot ent i al s, t he act i vat i on-cont rol l ed
MALO AND VELAZCO ON ELECTROCHEMICAL NOISE RESPONSE OF STEEL 391
Amplitude dB/ Hz^l l 2
0 . . . . . . ' . . . . . . . ' . . . . . .
-2O
a
-60
b
-120 . . . . . . . . . . . . . . . . . . . . . .
0.001 0.01 0.1 1
Frequency Hz
FIG. 3 - - P S D pl ots for the ( a ) potential and ( b ) current t i me seri es shown in Fig. 2.
E
m
=
- 5 0 0
-IOO0
' 9 ' , , t , t l . . . . . . . . t t , r t . . . . . i i , x * i . . . . . . . . . . . .
I E - 8 1E-5 1s I E - 3
Current de ns i t y A / n m 2
FI G. 4--Cathodi c polarization curves obtained for a mild steel RDE in O. 1M NazSO 4 under ( a ) static
conditions and two hydrodynamic conditions, ( b ) 500, and ( c ) 1200 rpm.
hydrogen reduction reaction occurs at a higher rate than that of the oxygen. It is accepted
that the corrosion rate depends on the oxygen reduction rate for this type of diffusion-
controlled system [2].
Figure 5 shows the EPN response of the corrosion potential under hydrodynami c (500
rpm) and static conditions. Bot h signals are displayed in comparable scales, 4 mV, so their
differences can be readily observed. The signal for the static condition (rpm = 0) has t wo
components. One component corresponds t o relatively slow variations in the potential level,
fluctuations of about 1-mV amplitude, whereas the other contribution is made of smaller
potential fluctuations, of about 0.1 mV. The signal fluctuations differ between the potential
fluctuations measured for the background noise mentioned above and the one described here,
suggesting its electrochemical origin. In the forced convection case, it can be observed that
the noise signal shows an entirely different pattern. The corrosion potential under a hydro-
dynami c regime (500 rpm) showed a drastic removal of the slow-frequency fluctuations and
a uniform amplitude band of potential fluctuations. Here, the low-frequency components
virtually disappear, whereas the higher frequency components increase their amplitude.
Potential
-641
-641.5
-642
-642.5
-643
-643.5
-644
-644.5
-645
mV vs SCE
a
0 200 400 600 800 1000
Time s
Potenti al mV vs SCE
-600
-600.5
-601
-601.5
-602
-602.5
-603
-603.5
-604
0
b
200 400 600 800 1000
Time s
FIG. 5 - - EPNM f or mi l d steel in 0. 1M Na2SO 4 under (a) static and (b) hydrodynamic conditions.
Figure 6 shows the potential PSD plots for the time series of Fig. 5. The amplitude
obtained from the electrochemical systems and the one produced by the background noise
are well differentiated. For the static condition, a 1/ f behavior is found with a slope in the
spectrum. For the hydrodynamic condition, a similarity is found between the background
and the electrochemical signal, showing a random appearance. However, the main difference
lies in the amplitude of the signal, which, in the electrochemical system, is considerably
bigger. These results emphasize the insignificant influence of the background noise in EPNM
Amplitude dB/ Hz^l / 2
4 0
20
0
-20
-40
-60
0.001
. . . = . . . . . . !
0.01 0.1
Frequency Hz
1
Amplitude dBIHz^ll2
40
2O
0
-2O
-4O
-60
0.001
0.01 0.1 1
Frequency Hz
FIG. 6--Potential PSD plots f or (a) background noise and the time series in Fig. 5 under (b) static
and hydrodynamic conditions.
for the two flow conditions using the RDE in which the contact noise appears not to affect
the electrochemical readings.
Figure 7 shows the ECN fluctuations under static and hydrodynami c (rpm = 500) con-
ditions in comparable scales, 0.05 mA/ c m 2. For the static condition signal and in similar
manner to the potential noise described above, slow current variations were obtained in which
the smaller fluctuations that are superimposed on the slower current fluctuations are close to
the level of the background electrical noise. For the hydrodynami c condition, intense current
fluctuations, confined to a 40-1xA peak-to-peak amplitude, were obtained.
Figure 8 shows the current PSD plots for the time series in Fig. 7. In contrast with the
potential PSD plot for the static condition, the spectrum intersects at high frequencies with
the background spectrum in agreement with current fluctuation similarities observed above
between the background noise and the ECN time series. Therefore, for the static conditions
and the particular experimental setup of this work, the background noise is significant at low
frequencies. In the case of the hydrodynami c condition, although the background and the
Current density mA/cm2
0.05
0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0005
0
0
f
i i i
200 400 600 800 1000
Time s
Current density mA/cm2
-0.15
-0,16
-0.17
-0,18
-0.19
0 200 400 600 800 1000
Time s
FIG. 7 - - ECNM f or mi l d steel in 0. 1M Na2S04 under (a) static and (b) hydrodynamic conditions,
pol ari zed at corrosion potentials of - 6 4 2 and - 6 0 2 mV versus SCE, respectively.
0
-20
-40
-60
-80
-100
-120
0.001
. . . . . . . , . . . . . . . , , f . . . . . . .
0.01 0.1 1
Frequency Hz
-60
-60
-100
-120
0 . . . . . . . ' . . . . . ' . . . . .
C
-20
-40
0.001 0.01 0.1 1
Frequency Hz
FIG. 8--Current PSD plots f or (a) background noise and the time series in Fig. 7 under (b) static
and hydrodynamic conditions.
electrochemical spectra bel ong to different amplitude ranges, both spectrum amplitudes are
virtually independent of the frequency. This ECN behavior is also found in the EPN results
in which the rotation of the RDE effect is reflected in a white noise signal.
The hydrodynami c effect appears even at a very slow rotation speed, as shown in Fig. 9,
in which the EPN and ECN time signals are presented for 30 rpm (t wo full rotations/s),
w
o
E
i -
o
Q.
-622
-622.5
-623
-623.5
- 624
-624.5
-625
-625.5
-626
0. 05
0. 045
0. 04
0.035
0 . 0 3
"~ 0.025
r
r 0.02
"E 0.015
~. 0.01
0 0.005
0
a
D i i
200 400 600 800 1000
Time s
b
. j .
0 200 400 600 800 1000
Time s
FIG. 9- - ENM f or mild steel in O.1M Na2SO4 for an RDE rotation rate of 30 rpm (a) EPN and (b)
ECN time series.
Here, bot h the EPN and the ECN al r eady exhi bi t a r emoval of t he l ow-frequency cont ri bu-
tion, i ndi cat i ng that even a smal l flow i ncrease can affect ENM.
Therefore, EPNM and ECNM are suscept i bl e to flow condi t i ons of the cor r osi ve medi a
exhi bi t i ng evi dent modi fi cat i ons in the t i me series patterns. Compar i son bet ween dynami c
and static t est s reveal that the ECN is mor e sensi t i ve to the stirring effect of the RDE because
fluctuations of this t ype of noi se undergo a st ronger modi fi cat i on (40 versus less than 5 txA)
than in EPN tests (1 versus 0.3 mV). In addi t i on, EPN and ECN undergo a si mi l ar modi fi -
cat i on in t hei r signal as f or ced convect i on is i nt roduced showi ng an i ncrease in ampl i t ude,
pr edomi nance of l ow-frequency component s, and an associ at ed whi t e noi se-l i ke spectrum.
Thus, t he charact eri st i c l ow-frequency si gnal , frequent l y found in el ect r ochemi cal passi ve
syst ems or syst ems undergoi ng uni form surface at t ack [8], is r epl aced by a hi gher frequency
signal.
Table 1 shows ENM st andard devi at i ons for vari ous flow test condi t i ons al ong wi t h the
cal cul at i on of el ect rochemi cal resi st ance noi se (ERN) usi ng
ERN- O'EPN
O' EC N
where O'Ep N is t he st andard devi at i on of the EPN and (lrEC N is the st andard devi at i on of the
ECN [8]. An i ncrease in convect i ve transport, obt ai ned by an i ncrease in RDE rot at i on speed,
reduces t he ERN value. Because resi st ance values are i nversel y proport i onal to corrosi on
MALO AND VELAZCO ON ELECTROCHEMICAL NOISE RESPONSE OF STEEL
TABLE l--Standard deviation and electrochemical resistance
noise values f or various f l ow conditions.
rpm aEv N, mV aecN, mA ERN, 1)
0 0.709 0.00 161 440
30 0.181 0.00067 262
60 0.859 0.01 68 51
500 0.237 0.01 302 18
1000 0.086 0.00243 35
397
rate, values calculated are in agreement with the trend expected for a corrosion system in
which the corrosion rate increases with increasing flow. This behavior is also predicted by
polarization curves for a diffusion-controlled system [9] in which displacement of the ca-
thodic branch to higher current values is indicative of an increase in the rate of oxygen
reduction and, therefore, of an increasingly aggressive condition. Therefore, the equation
above proposed for the calculation of ERN corresponds well to the system studied in which
lower resistance values correspond to higher flow and more aggressive conditions.
Conclusions
The level of electrical current and potential noise of the instrumental setup used in this
study was lower than that obtained from mild steel in Na2SO4 under various RDE flow rates.
Therefore, ENM can be carried out with little interference from the background noise in the
study of general corrosion.
The effect of flow is apparent at relatively low RDE rotation speeds from 30 up to 500
rpm. The ENM undergo modifications as flow is introduced, in which the low-frequency
electrochemical noise components are replaced by higher frequency and amplitude noise
signals.
References
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No. 4, 1983, p. 391.
[2] Bard, A. J. and Faulkner, Electrochemical Methods, John Wiley & Sons, New York, 1980, p. 280.
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[4] Hladky, K. and Dawson, J. L., "The Measurement of Corrosion Using Electrochemical 1 I f Noise,"
Corrosion Science, Vol. 32, 1982, p. 231.
[5] Bataillon, C. and Fiaud, C., "Spectral Analysis of Noise Potential During Pitting," in Electrochemical
Methods in Corrosion Research, M. Duprat, Ed., Transactions Technical Publications, Switzerland,
Vol. 8, 1986, p. 141.
[6] Press, W. H., Flannery, B. P., Teukolvsky, S. A., and Vetteding, W. T., Numerical Recipes, Cambridge
University Press, New York, 1986, p. 381.
[71 Fei, Z., Hudson, J. L., and Kelly, R. G., "A Low-noise Contact for Rotating Electrodes," Journal of
the Electrochemical Society, Vol. 141, No. 9, 1994, p. 123.
[8] Eden, D. A., Hladky, K., John, D. G., and Dawson, J. L., "Electrochemical Noise," Paper 274,
Corrosion 86, NACE, Houston, TX, 17-21 March 1986.
[9] Cash, G. A., Schweinsberg, D. P., and Hope, G A., "The Corrosion Rate of Low Carbon Steel in
Stationary and Stirred Sugar Juice: A Mathematical Analysis of Polarization Curves," Corrosion
Science, Vol. 30, No. 6/7, 1990, p. 543.
J uan de Dambor enea ~ and Bernardo F erndndez I
Electrochemical Noise Measurements
During Exfoliation of Aluminum Alloys
RE F E RE NCE : de Damborenea, J. and Femfindez, B., " El e c t r o c h e mi c a l No i s e Measure-
ments During Exfoliation of Aluminum Alloys," Electrochemical Noise Measurement f or
Corrosion Applications, ASTM STP 1277, Jeffery R. Keams, John R. Scully, Pierre R. Roberge,
1996, pp. 398-410.
ABS TRACT: Electrochemical noise measurements (ENMs) have been carded out during ex-
foliation corrosion of an aluminum-lithium alloy (8090) in the EXCO (ASTM Test Method
for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX Series Aluminum Alloys [EXCO
Test] [G 34]) test solution. By means of the maximum entropy method (MEM), the potential
and current fluctuations were converted into power spectral density (PSD) plots to study the
specific variables related to electrochemical noise (low frequency amplitude, slopes). Noise
resistance obtained from the standard deviation of potential and current was compared with
the charge transference resistance (R~) from electrochemical impedance spectroscopy (EIS)
measurements. The results show that ENM can be used to detect early stages in localized
corrosion. However, when the solution is very aggressive, indications of localized corrosion
can be masked by uniform corrosion.
K E Y WO R D S : electrochemical noise measurement, intergranular corrosion, exfoliation cor-
rosion, EXCO test, aluminum-lithium alloy, electrochemical impedance spectroscopy
Al umi num al l oys are one of t he most wi del y used mat eri al s in t he aerospace i ndust ry
because of t hei r i nt ri nsi c low density, hi gh mechani cal strength, and cor r osi on resi st ance.
The per f or mance of ai rcraft is i mpr oved by the use of l i ght er mat eri al s. The al umi num-
l i t hi um (A1-Li) al l oys are among t he most recent to be devel oped for ai rcraft industry. Li t h-
i um is the l i ght est al l oyi ng el ement and di ssol ves wel l in Al (4.2 wt % at 600~ in a bi nar y
A1-Li al l oy), pr ovi di ng the al l oy wi t h a l ower densi t y t han it woul d have wi t h ot her al l oyi ng
el ement s such as copper or zinc, and a hi gher el ast i c l i mi t as a resul t of the f or mat i on of
i nt ermet al l i cs (21% hi gher than al umi num al l oy 2024-T351 and 26% hi gher t han al umi num
al l oy 7075-T651) [1 ].
Li t hi um is, however, a hi ghl y react i ve el ement . Thus, corrosi on resi st ance is an i mport ant
fact or in t he ser vi ce l i fet i me of t hese al l oys. Cor r osi on behavi or of A1-Li al l oys has been
st udi ed [2]. General l y, i ncreasi ng t he degr ee of overagi ng, the number of nucl eat i on si t es
for g phase ( AI - Li ) preci pi t at i on, and the amount of Li avai l abl e to f or m the ~ phase i ncr eased
cor r osi on suscept i bi l i t y. Ot her pri mary phases as 5' (A13Li), 0' (AI2Cu), T~ (A12LiCu), or T 2
(Al t CuLi 3) t end to segregat e al ong the grai n boundar i es and i ncrease in size accor di ng t o
the t hermal t reat ment appl i ed to the pi ece. When t he al l oy is subj ect ed to an aggressi ve
medi um, t he anodi c di ssol ut i on t ends t o occur preferent i al l y at grai n boundar i es resul t i ng
Senior Research, Centro Nacional de Investigaciones Metaltirgicas (CENIM-CSIC), Avenida de Gre-
gorio dei Amo, 8, E-28040-Madrid, Spain.
398
www.astm.org
DE DAMBORENEA AND FERNANDEZ ON NOISE MEASUREMENTS 399
from the electrochemical action between the precipitates and the adjacent solute denuded
zones. The end result is pronounced intergranular attack. Because of their large volume, the
ensuing corrosion products tend to separate the metallic grains, producing the phenomenon
known as exfoliation, which is well reported in literature [3].
The ASTM Test Met hod for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX
Series Al umi num Alloys (EXCO Test) (G 34) is used to detect susceptibility to exfoliation.
It consists of submerging the samples in an acid solution and waiting a given time, between
48 and 96 h, for the attack to occur. After the immersion period, the specimens are cut and
prepared for metallographic observation to determine whether or not they have undergone
attack and in what form.
The introduction of electrochemical techniques, especially electrochemical noise, has
opened new horizons for the study and analysis of corrosion kinetics. This means that lo-
calized corrosion can be detected in its early stages [4-6]. In contrast to the other techniques,
electrochemical noise has the advantage of not imposing an external signal, thus avoiding
disturbance to the working electrode.
The present study focuses on the use of an electrochemical noise measurement technique
to establish a correlation between electrochemical current and potential noise measurements
and the existence of exfoliation in an 8090 aluminum-lithium alloy.
The specimens used in this study were an 8090 alloy in the form of an extruded plate of
cross section 100 by 25 mm in the T8 condition (solution heat-treated, cold-worked, and
artificially aged 12 h to 150~ Chemical composition was (wt%): copper 1.15, iron 0.05,
magnesi um 0.67, silicon 0.02, zirconium 0.11, lithium 2.4, and aluminum balance.
The samples were polished to a 600-grit finish and degreased in an acetone bath.
The solution proposed in the ASTM Practice for Laboratory Immersi on Corrosion Testing
of Metals (G 34) for exfoliation corrosion susceptibility test consisted of a mixture of nitric
acid ( HNO3) , potassium nitrate (KNO3), and sodium chloride (NaC1), with an initial pH of
0.5. This pH evolves with time to a value of 4. 0 in 96 h.
The experimental arrangement for the measurement of electrochemical potential and cur-
rent noise consisted of t wo similar 0. 5-cm 2 samples of 8090-T8 aluminum alloy placed
parallel to each other in a specially designed test cell, as shown in Fig. 1. Bot h samples
were connect ed to an Schlumberger Solartron 1286 Electrochemical Interface used here as
a zero-resistance ammeter. The data were gathered by a personal comput er connect ed to the
electrochemical interface through an RS232 port. Electrochemical potential noise (EPN) was
measured between a saturated calomel electrode and one of the samples. EPN was recorded
by a Schlumberger Digital Multimeter 7061 connected to a comput er via a GPIB (IEEE 488)
interface. For both the potential and current measurements, a 0.7-s sampling rate was used
to collect 1024 data per record.
The data were stored on a disk and analyzed using the maxi mum entropy met hod (MEM)
as suggested by Press et al. [7]. It was used to change data in the time domain to the
frequency domain, giving us a power spectral density (PSD) value. MEM was used instead
of the fast Fourier transform (FFF) algorithm because it produced a smoot her plot [8]. The
mean values of electrochemical potential and current were removed before calculating the
standard deviation to remove DC linear trends.
Electrochemical impedance spectroscopy (EIS) tests were performed using a three-
electrode arrangement, with a graphite counter electrode and a saturated calomel electrode
as the reference. A system based on the same electrochemical interface as before j oi ned to
t COMPUTER
[
I
DVM I ZRA
I
r i c
FIG. 1--Scheme of instrumentation for electrochemical noise measurements.
a Schl umberger/ Sol art ron 1250 frequency response analyser (FRA) was used. The frequency
range was between 3 kHz and 10 mHz, collecting ten points per decade. Measurements were
made initially at set intervals (4, 24, 48, 72, and 96 h).
In the first stage, the test duration was 96 h until the corrosive phenomenon was typified.
Parallel to these electrochemical measurements, specimens were withdrawn at the same time
intervals and were analyzed by optical mi croscope to compare results. After 24 h, the first
evidence on localized attack had already appeared as pictured in Fig. 2 and continued to
spread t hrough the rest of the experiment till exfoliation had completely developed.
R e s u l t s a n d D i s c u s s i o n
The objective of the research was to predict the appearance of exfoliation by means of
electrochemical noise measurements in the EXCO test solution. Other electrochemical tech-
niques as Rp or EIS were also used to help in the interpretation of the results.
It is well known that aluminum alloys undergo heavy attack at pH values below four and
above eight. Because of the high corrosion rate, electrochemical techniques should be used
with precaution to avoid polarization of the working electrode. As shown in Fig. 3, the
values of the polarization resistance detected by applying a 10-mV signal to the specimens
are small, indicating a high corrosion speed as a result of the highly aggressive medium.
The potentiodynamic polarization curve for the 8090-T8 alloy is shown in Fig. 4. As small
steps of potential are applied, the current reaches extremely high current densities ( >100
txA/cm2). Therefore, not onl y do the polarization curves provide no information about the
mechani sm of the attack, but also produce deleterious effects on the samples as a result of
their polarization.
From the above, we can expect that corrosion begins immediately after the immersion of
the samples in the test solution. The measurements of potential fluctuations and current are
DE DAMBORENEA AND FERNANDEZ ON NOISE MEASUREMENTS 401
FIG. 2IEXf ol i at i on attack on 8090-T8 alloy surface after 24 h in the EXCO test solution (xlO0).
thus particularly useful during this time. Figure 5 shows variations in potential after removing
the DC linear trend, 30 min (Fig. 5a) and 3 h (Fig. 5b), after the start of the test. In Fig.
6, the variations in current for the same times (Fig. 6a for 30 rain and Fig. 6b for 3 h) are
presented.
The activation process of the aluminum in a given medium involves the rupture of the
passive film. If the material were in a passive state, initial response observed during this
time of exposure could be explained in terms of a crack-heal model for localized passive
film breakdown values. However, in the experimental medium, breakdown of passive film is
facilitated by the extremely acid pH and the high concentration of aggressive ions. Solution
1200
E
r,3
t -
O
o.
CE
1000
800
600
400
200
0
j ~
I I I I
0 20 40 60 80 1 O0
Ti me (hours)
FIG. 3--Polarization resistance values of the alloy during 96 h of immersion in the acid solution.
LLI
o
>
E
, . i -
r a
no
-700
-720
/
/
/
/
/ "
/
/
/
/
/
-740 / /
/
/ /
-760
. 7 ~ ( ~ 9 , i , . . i i I f , , I . . . . . . . . I . . . . . . . . . , . . . . . I .
1 E-07 1E--06 1E-05 1 E-04 1E-03
Cur r ent densi t y, Nc m 2
FIG. 4--Potemiodynamic polarization curve of 8098-T8 alloy. Sweep rate of 12 mV/min.
pH change the stability of the oxide film of aluminum oxide (A1203) formed on surface of
al umi num and aluminum alloys. In acid solutions (pH < 4), the oxide film is highly soluble
and this lead to higher rates, as deduced from polarization data. Moreover, corrosion is
enhanced by the acceleration of the cathodic reaction because of the high concentration of
H + ions [9].
A correlation of these results with those obtained from electrochemical impedance tech-
nique can be done. At the start of the experiment, the impedance diagrams had similar Re,
levels to those found using the polarization resistance method. At lower frequencies, a dis-
torted capacitive loop was formed (Fig. 7). EIS also has application problems because of
large scattering in low-frequency range. Some authors suggest that the presence of a resistive-
capacitive semicircle at high frequencies and an inductive loop or semicircle at low fre-
quencies could be related t o the activation process [10,11 ]. Here, aggressive ions compete
in the surface adsorption process preventing quick repassivation of cracked flaws and re-
sulting in a higher anodic flow. This is the process of pit incubation [12]. As pointed out
by Bessone and coworkers [13 ], a model interpretation of the Faradaic process of the system
is relatively difficult because of the cathodic hydrogen evolution reaction superimposed on
the anodic dissolution of aluminum. In the same sense, Frers et al. [14], ascribed this ca-
pacitive loop to uniform dissolution of the oxide film before the onset of pitting corrosion,
probably through the formation of chloride-containing aluminum complexes that readily go
into solution.
This behavior was maintained 50 h into the test, when the Nyquist diagram evolved into
other forms, such as the one shown in Fig. 8. In a previous paper [15], we mentioned that
these deviations could be due t o exfoliation, which produces multiple electrical paths along
which the signal can be distributed. For that, an uneven current distribution on the electrode
DE DAMBORENEA AND FERNANDEZ ON NOISE MEASUREMENTS 4 0 3
1, 5
9
(.u
o
,v-o
x
Ld
0
D..
ILl
a
0, 5
-0,5
- 1 ~
0 250 500 750
Ti me, s e c o n d s
4
31-
o 2
LU
v 1
LU
D..
LU
-2
b . 3
0
250 500 750
Ti me, s e c o n d s
FIG. 5- - El ect rochemi cal noise on AI-Li alloy in the EXCO test solution. Voltage fluctuations: (a) 30
rain before immersion and (b) 3 h later.
can be expected to produce a similar effect t o a porous electrode [16, 17]. What ever the case,
this behavi or only appears to be detected clearly when the process is quite advanced and
not in the initial stages.
Transitory variations also appear, however, that could well be due to the initial stages of
localized corrosion and propagation of these events. The PSD plots for potential fluctuations
and amplitude under the conditions given above are shown in Figs. 9 and 10, respectively.
Above 10 -I Hz, the noise is masked by parasitic noise in the equipment. The low-frequency
amplitude was similar at the beginning of the test and after 3 h. It decreased from - 5 5 to
- 6 5 dBV/ Hz I/2 for potential noise and from - 1 3 5 t o - 1 4 0 dBA/ Hz t~2 for current noise.
The rol l -off frequency was also similar at 30 min and 3 h. The figures also show that, at
lower frequencies ( <10 -3 Hz), the electrochemical noise can be considered to be white or
independent of the frequency. In Fig. 11, noise variation at low frequencies (1 mHz) during
the first 6 h of testing is presented. As shown, it indicates high levels for potential noise and
low levels for current noise. Accordi ng to the literature, the difference between potential and
10
6
4
x
W
O
-2
a
- 4
0 2 5 0 500 7 5 0
Ti me, seconds
1
9
UJ
x~
<
z"
0
W
b
-0,5
0,5
L . . . . _ I I I
0 250 500 750
Time, seconds
FIG. 6--Current norse recorded f or 8090-T8 alloy in exfoliation solution: (a) after 30 min and (b)
after 3 h of running the test.
current noi se PSD is rel at ed to the di fference bet ween uni form and l ocal i zed corrosi on: the
begi nni ng of l ocal i zed corrosi on generat es hi gh vol t age noise, whi l e current noi se is l ow
[18]. However, note that r andom vol t age and current fluctuations of hi gh frequenci es coul d
al so be i nt erpret ed in t erms of strong uni f or m corrosi on.
The di fferences bet ween the PSD l i nes appear cl ear l y in rel at i on to the slope. In bot h
cases, the sl opes of the el ect r ochemi cal pot ent i al and current noi se power spect rum densi t y
has been cal cul at ed in t he range f r om 10 -3 and 10 -2 Hz. Represent i ng t he vari at i on of t hese
sl opes over t i me (Fig. 12), we find that t hose cor r espondi ng to the pot ent i al noi se r emai n
const ant at around - 18 dB/ de c a de t hroughout t he experi ment , whi ch woul d be in the bound-
500
._c
O )
N
" ' T"
4O0
3OO
2 0 0
100
0
-100
- 200
- 300
0
I I I i I i
150 300 4 5 0 6 0 0 750 9 0 0
Z real
FIG. 7--1mpedance measurement o f aluminum alloy 8090-T8 corroding electrode in EXCO test so-
lution 30 rain af t er immersion.
3 0 0
0 3
E
N
" ' T"
2 0 0
100
O - I I I
0 200 400 600
Z real
FIG. 8- - I mpedance pl ot s at corrosion pot ent i al f or 8090-T8 alloy in the aci d solution 3 h before
starting the test.
-40
~ -60
N
n-
I I 1
a
Go
i:1. -80
~ " ~ , 3 0 min
- 100 . . . . . . ' ' ' '
1 E - 0 3 1 E - 0 2 1 E - 0 1 1 E + 0 0
Log Frequency (Hz)
FIG. 9 - - Po we r spectral density ( PSD) o f the pot ent i al f l uct uat i ons o f the electrode af t er 30 rain and
3 h o f immersion.
ary values between uniform and localized corrosion. In contrast, the slopes of intensity PSD
increase to higher levels (from - 3 0 to - 1 0 dB/decade). This type of noise output with
shallow slope is associated in literature [19] with pitting corrosion processes. This results
are in accordance with the previous comments.
From these results, a mixing of localized and uniform attack can be expected on the
samples. After 6 h of testing, samples were removed and optically analyzed. The A1-Li 8090-
-130
N
<
r.n
C)
0-
-140
-150
-160
-170
~ ~ 3 0 rain
-180 . . . . . . . . . . . . . . . . . . . . . . . . .
1.0E-03 1.0E-02 1.0E-01 1. 0E+00
Log Frequency (Hz)
FIG. l O- - Po we r spectral densi t y ( PSD) o f the current f l uct uat i ons using the dat a shown in Fig. 6.
0
- 50 n
N
,1-
, . Q
" O
" O
CL
E
,<
>. ,
t ~
t -
|
-,n
O "
m
L L
o,
- I O0
-15o
i
0
J I I i ~ I
1 2 3 4 5 6
Ti me, hour s
I "=- Pot ent i al -~- Cur r ent I
FIG. 1 l - - Low frequency amplitude noise f or potential and current.
T8 alloy samples showed uniform corrosion together with some points of localized attack,
as pictured in Fig. 13.
Anot her interesting aspect in relation to electrochemical noise measurements is the pos-
sibility of monitoring corrosion rates. The corrosion process is regarded as a stochastic
process coupled to the electrochemical kinetics (deterministic process). As indicated by Eden
et al. [20], the correlation of potential and current noise signals is typically >90%, hence
the standard deviation of the potential (cry) and the current (cry) (calculated using all points
from t = 0) may be used to obtain a value of corrosion resistance that is similar to the one
provided by polarization resistance or that derived from the impedance diagrams:
0
-5
-10
t~ - 15
0 _
o ,
o~ - 20
- 25
- 3 0
- 35
. . . . . I J I
0 1 2 3
Ti me ( hour s)
4 5 6
Pot. + S l o p e Int.
FIG. 12--Variation of electrochemical potential and current noise PSD slopes during the first 6 h of
testing.
FIG. 13- - Local i zed attack of 8098-T8 alloy i mmersed in aci d solution after 6 h, x200.
R n = trv / cr l
The values found for R, are represented along with those obtained by the EIS in Fig. 14.
The R, and Re, have similar tendencies, although the values differences exceed by an order
of magnitude. These differences could be explained according to the corrosion mechanism
described before; these are two different processes (uniform and localized) at same time. As
it was mentioned, the anodic dissolution of the aluminum occurs along with the cathodic
production of hydrogen. The hydrogen first nucleates over the surface as an H ion, then
recombines with another identical ion, and finally is released in the form of molecular
hydrogen. This recombination and release cause fluctuations in the potential because of
a screening effect by the hydrogen bubble that grows on the surface [21 ]. For this rea-
son, electrochemical noise measurements could be masked as a result of the different ef-
fects (uniform corrosion, hydrogen evolution, and localized attack) that can take place
simultaneously.
Conclusion
Electrochemical noise measurement can be used as an important tool to study the corrosion
mechanism of aluminum-lithium alloys in strong acid solutions (pH < 1). Noise analysis
seem to be related to initial stage of corrosion. According to the results found in this work,
uniform and localized attack (exfoliation process) are developed at same time. This situation,
combined with the highly aggressive action of the solution on aluminum, can make inter-
pretation of the data difficult. However, these results are consistent with those obtained from
the EIS technique and metallographic analysis. Corrosion rates deduced from R, and Re, have
similar values, although differences of one order of magnitude can be found. This could be
due to the different reactions that occur on the metal surface (uniform corrosion, hydrogen
evolution, and localized attack) simultaneously.
DE DAMBORENEA AND FERNANDEZ ON NOI SE MEASUREMENTS 4 0 9
r.}
x
E
t -
O
ro-
D
t -
n--
1 0 . 0 0 0
1. 000
100
10
Rn
Rct
I I I I I I
1 2 3 4 5 6 7
FIG. 14--Noise resistance
measurements.
Time, h o u r s
(Rn) determined from current and potential noise and from EIS
Acknowledgments
The aut hor s wi sh t o t hank t he E. C. f or f undi ng this st udy as part o f t he BRI TE BE- 3355
Pr oj ect " Ne w Ac c e l e r a t e d Cor r os i on Test Me t hods . "
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Elisabete Almeida, 1 Liboria Mariaca, 2 Abelardo Rodriguez, 2
Jorge Uruchurtu Chavadn, 2 and Marfa A. Veloz 2
Characterization of Prerusted Steels in
Some Ibero-American Atmospheres by
Electrochemical Potential
Noise Measurement
REFERENCE: Almeida, E., Mariaca, L., Rodriguez, A., Uruchurtu Chavarin, J . , and Veloz,
M. A., "Char act er i zat i on of Pr er ust ed Steels in Some I ber o- Amer i eau At mospheres by
El ect rochemi cal Potential Noise Measur ement , " Electrochemical Noise Measurement f or
Corrosion Applications, ASTM STP 1277, Jeffery R. Kearus, John R. Scully, Pierre R. Roberge,
1996, pp. 411-424.
ABSTRACT: The purpose of the MICAT project (Ibero-American Map of Atmospheric Cor-
rosiveness) was to foster collaborative ventures between groups conducting research on at-
mospheric corrosion. Overall, 14 Ibero-American countries, including Spain and Portugal, are
involved with a network of 71 test stations distributed throughout the region and on 4 conti-
nents. These test stations represent a broad spectrum of climatological and atmospheric pol-
lution conditions. The objective of the MICAT electrochemical studies was to characterize the
protective properties of the corrosion products formed during atmospheric exposure at the
different test sites. Prerusted carbon steel specimens at different locations were immersed in a
sodium sulfate solution. Some specimens were rust pretreated in phosphoric acid solution with
additions of aluminum hydroxide (rust converters) electrochemically evaluated. Electrochemi-
cal noise measurements (ENM) and linear polarization resistance (LPR) measurements were
performed for different times of immersion. Corrosion rates were related to the presence of
the oxides that were initially formed. For specimens rusted in marine atmospheres, the presence
of chlorides in the corrosion products promotes localized attack. As to the different rust-
converted specimens, ENM revealed the pretreatment evolution and corrosion performance over
time. ENM was able to characterize and evaluate the protective properties of oxides and pre-
treatments according to the nature and environmental conditions to which specimens were
exposed.
KEYWORDS: MICAT, rust converters, electrochemical potential noise measurement, oxides,
atmospheric corrosion
At mos phe r i c cor r os i on is r es pons i bl e f or mor e t han 50% of t he e c onomi c l osses caus ed
by cor r os i on accor di ng t o Toma s hov [1]. The at mos pher i c cor r os i on of met al s is di r ect l y
r el at ed t o t he envi r onment al and pol l ut i on condi t i ons t o whi ch t hey ar e expos ed and can be
hundr eds o f t i mes hi gher in s ome pl aces t han in ot hers. Thi s account s f or t he i ncr eas i ng
i nt er est in det er mi ni ng whi ch var i abl es are i nvol ved i n t he pr oces s [2]. The char act er i st i c
pr oper t i es o f oxi des depend on t he pol l ut ant s pr esent , t he envi r onment al and cl i mat i c con-
Researcher, I NETI / I MP Laboratorio de Tintas e Revestimentos, 1699 Lisboa Codex, Portugal.
2 Researchers, IIE Depto. de Fisicoquimica Aplicada, A. E 475 Cueruavaca, Morelos, M6xico.
411
Www.astIII.Org
ditions, and the time of exposure of the metals to the atmosphere. In Ibero-Ameri can coun-
tries, atmospheric corrosion data are scarce and little is known about the protective properties
of oxides developed during variable atmospheric corrosion conditions.
On the other hand, the study of rust pretreatment layers based on phosphoric acid (H3PO4)
already had a long story being among the oldest rust converters [3-6]. Recently, it was
verified that this process depends strongly on the interfacial conditions, and that acid solution
concentration or steel-weathering conditions play a significant role in the rust conversion
mechani sm [7,8].
MI CAT Project
The MICAT project (Ibero-American Map of Atmospheric Corrosiveness) was set up in
1988, within the CYTED- D Programme of Science and Technol ogy for Development as part
of the Spanish festivities of the 5th Centennial "Encount er of Two Worlds." The aim of the
project was to foster collaborative ventures between groups that have been conducting re-
search on atmospheric corrosion in their respective countries and to train others on this topic
[9,10]. Overall, 14 Ibero-Ameri can countries, including Spain and Portugal, are involved.
Research is conduct ed both at laboratories and in a network of 71 atmospheric exposure test
sites distributed throughout the region and on 4 continents. The participants are considering
a broad spectrum of climatological and atmospheric pollution data. The objectives to be
fulfilled in the first phase of the project are:
(1) to increase the present knowledge on the mechani sm of atmospheric corrosion,
(2) to develop mathematical relations t o predict atmospheric corrosion from climatological
and contamination parameters, and
(3) to draw up the Ibero-Ameri can Map of Atmospheric Corrosiveness (MICAT).
Meeting the above objectives will allow optimal selection of materials and coatings under
specific conditions of atmospheric aggressiveness. In the second phase of the project, the
performance of a variety of protective coatings against atmospheric corrosion will be as-
sessed. The project followed some aspects outlined by the I SOCORRAG [11] and I CP/
UNECE [12] projects, and whenever possible, ISO standards have been followed for field
studies. Four groups were established to study different aspects of the exposed specimens.
These include: corrosion product morphology, chemical analysis of corrosion products and
water-soluble contaminants, and statistical analysis of environmental data and electrochem-
ical testing. The objective of the MI CAT electrochemical studies was to characterize the
protective properties of the corrosion products formed on different materials during atmos-
pheric exposure in the different test sites.
This work presents preliminary results obtained using linear polarization resistance (LPR)
and electrochemical potential noise (EPN) on steels prerusted in different Ibero-Ameri can
atmospheres to characterize the protective properties of the oxides that developed. The cor-
rosion behavior of pretreatments or different rust conversion layers (RCL) formed in phos-
phoric acid (H3PO4) and solutions containing aluminum hydroxide (AI(OH)3) were also
evaluated.
The materials, used in the form of fiat plate specimens, were low carbon steel and were
exposed to the atmosphere in conventional racks at the test sites accordi ng to the I SO "Metals
and Al l oys- - At mospher i c Corrosion Test i ng- - Gener al Requirements for Field Tests" draft
ALMEIDA ET AL. ON PRERUSTED STEELS 413
standard (ISO/DIS 8565). Pollution deposition rates were calculated according to the ISO
"Corrosion of Metals and Alloys. Classification of Corrosivity Atmospheres" draft standard
(ISO/DIS 9223). Meteorological data were provided by the meteorological service of each
country and calculated according to ISO "Corrosion of Metals and Alloys--Aggressivity of
Atmospheres--Methods of Measurement of Pollution Data" draft standard (ISO/DIS 9225).
The exposures sequence includes: three 1 year, one 2 year, one 3 year, and one 4 year. Four
specimens were exposed in each sequence, of which three are used for mass loss calculations
according to the ISO "Corrosion of Metals and Alloys--Corrosivity of At mospheres--
Methods of Determination of Corrosion Rate of Standard Specimens for the Evaluation of
Corrosivity" draft standard (ISO/DIS 9226) and the fourth for electrochemical studies. The
detailed experimental procedure, test site, locations, and preliminary field results have been
reported in the literature [2,9,10].
Table 1 presents the names and environmental features of the test sites of the materials
being considered here. The test sites provide a variety of climatological and pollution
conditions.
Mat eri al s
Pr e r us t e d- - Af t e r the exposure period, the 150-cm 2 prerusted steel specimens were kept in
a plastic bag and removed from the test stations ready for electrochemical testing. No further
treatment of the surface was carried out.
Pr et r eat ed- - I n the case of pretreated specimens, the experimental work was carded out
using the mild steel panels prepared according to ISO Structural Steels (ISO 630), allowed
to rust for 10 or 24 months at a Portuguese field station with a low level of atmospheric
contamination (see Table 1), and brushed using an automatic and reproducible technique
TABLE l - - Tes t sites and environmental characteristics.
Koppen [131 ISO Real
Climatic Apparent Atmosphere
Country Test Station Classification Atmosphere SO2-C1
Argentina V. Martelli Cf ~ Urban P0-S1 b
San Juan Cf Rural P0-S0
Brazil Caratinga Cw Rural P0-S1
Ipatinga Cw Ind. P1-S0
Colombia Isla Naval Aw Marine P0-S 1
San Pedro Cw Rural P0-S0
Cotov6 Aw Rural P0-S0
Costa Rica Arena] Af Marine P0-S 1
San Jos6 Aw Rural P0-S1
Chile Cerrillos Cs Urban P1-S 1
Ecuador Guayaquil Aw Rural P0-S0
Mexico Mexico Cw Urban P1-S0
Cuernavaca Aw Rural P0-S0
S. L. Potosf Bs Urban P1-S0
Acapulco Aw Marine P1-S1
Peru Arequipa Bw Rural P0-S0
Portugal Lumiar Cs Rural P0-S0
Koppen climatic nomenclature, that is, capital letter indicates climatic group and small letter indicates
climatic type.
b ISO 9223 nomenclature based on deposition rate R for SO 2, S for chlorides, and numbers for degree
of pollution level.
[14] to a preparat i on degr ee desi gnat ed CSt 2 as descr i bed in accor dance to the Sweden
Inst i t ut e St andard SIS "Pi ct or i al Surface Preparat i on St andard for Pai nt i ng St eel Ar t i cl es"
( SI S 055900).
As pret reat ment s, a H3PO 4 sol ut i on at 33.2 and 38. 6% ( w/ w) sat urat ed wi t h AI ( OH) 3 wer e
used because t he rust conversi on l ayer s obt ai ned wi t h i nt ermedi at e concent rat i ons seem to
show t he best results for pai nt i ng under t he actual steel surface weat heri ng condi t i ons [8].
The sampl es prepared were desi gnat ed P30P10, P30P24, P35AI 0, and P35A24, respect i vel y.
For each sampl e wi t h a 150-cm 2 ar ea of corroded and subsequent l y wel l - br ushed steel
surface, 0.7 mL of pret reat ment sol ut i on was spread as a pai nt on t he surface in a cross
mot i on wi t h the ai d of a cl ean and dr y brush. Then the pret reat ed surfaces were dr i ed in
l aborat ory duri ng 24 h at 25~ bef or e eval uat i on tests were performed.
Instrumentation
A Sol art ron model 1286 el ect rochemi cal i nt erface coupl ed to a personal comput er, whi ch
act ed as dat a l ogger / anal yzer , was used for al l el ect rochemi cal measurement s. A sat urat ed
cal omel el ect r ode (SCE) and a wor ki ng el ect r ode (met al sampl es) were used for EPN, and
a graphi t e auxi l i ar y el ect r ode was used in a t hree-el ect rode setup for LPR measurement s.
Working Conditions
The el ect r ochemi cal cel l was bui l t by at t achi ng a 3. 1-cm di amet er and 1-cm-hi gh gl ass
t ube to the speci men wi t h a cl i p holder. A Neoprene ri ng was pl aced bet ween the gl ass t ube
and the met al sampl e to prevent the el ect r ol yt e from l eaki ng out of the cel l .
A sol ut i on cont ai ni ng 0. 1M sodi um sulfate (Na2SO4) was used as the el ect rol yt e, pr ovi di ng
a nonaggr essi ve conduct i ng medi a. Af t er about hal f an hour, the corrosi on pot ent i al r eached
a st eady state. El ect r ochemi cal pot ent i al noi se (EPN) measurement s and l i near pol ar i zat i on
resi st ance (LPR) measurement s were obt ai ned on each sampl e.
For t he pret reat ment sampl es, this pr ocedur e was per f or med on a mont hl y basi s on di f-
ferent areas of t he speci men t o f ol l ow t he t i me evol ut i on of the conversi on l ayers as wel l as
its ant i corrosi on propert i es. The speci mens were kept in a desi ccat or bet ween per i ods of
i mmersi on.
Electrochemical Tests
EPN--The pr ocedur e adopt ed for this wor k consi st ed of measuri ng the corrosi on pot ent i al
osci l l at i ons as a function of t i me bet ween t he wor ki ng el ect r ode and the SCE. Thi s was
achi eved usi ng the el ect rochemi cal i nt erface in the vol t met er mode at a sampl i ng rat e of one
readi ng every 0.7 s cont rol l ed by a personal comput er. Af t er gat heri ng the dat a as a pot ent i al -
t i me r ecor d of 2048 sampl es, the DC dri ft was removed, fitting a st rai ght l i ne to t he ori gi nal
data. The devi at i ons of i ndi vi dual poi nt s wi t h respect to that line pr oduce a new set of dat a
that compr i ses negat i ve and posi t i ve values around the base line. The power spect ral densi t y
pl ot s were obt ai ned usi ng an al gor i t hm based on the fast Four i er t ransform ( FFI ' ) of spect ral
anal ysi s. The r esol ved frequency bandwi dt h of interest l i es bet ween 0.69 and 700 mHz.
An EPN t i me r ecor d and cor r espondi ng power spect ral densi t y pl ot s were obt ai ned. The
soft ware was devel oped l ocal l y based on the ENM procedure of the UMI ST group [14].
Al so, the st andard devi at i on of the EPN as an i ndi cat i on of i ncreasi ng l ocal i zed corrosi on
act i vi t y was cal cul at ed [15,16]. The det ai l ed pr ocedur e adopt ed for t he present wor k is de-
scri bed el sewher e [13,15].
L PR- - A 20-mV anodic pulse was applied around the corrosion potential, and the current
decay response was registered until it became asymptotically stable. At this point, the current
response was obtained, and the polarization resistance and corrosion current density were
calculated. A B = 26-mV value suggested in the literature [1 7] as representative of most
corrosion systems was assumed only for comparative purposes.
Prerust ed
Table 2 presents the electrochemical parameters obtained for the specimens exposed for
one year to different atmospheric and climatic conditions. Most of the samples present active
corrosion potentials except Arenal, San Jos4, Mrxico, Cuernavaca, San Luis Potosf, and
Arequipa where more noble corrosion potentials are observed.
The corrosion current density values varied from as low as 0.01 ixA/cm 2 for Guayaquil
up to 71.3 ixA/cm 2 for Acapulco. Values above 1 ixA/cm 2 were obtained for Caratinga, Isla
Naval, Cerrillos, San Pedro, Ipatinga, Mrxico, San Luis Potosf, and Acapulco. The highest
EPN standard deviations (above 2 mV) were obtained for Guayaquil, Acapulco, San Josr,
Caratinga, and Mrxico.
Under the electrochemical test conditions considered, potentials above - 0. 250 V are in-
dicative of passivation and below that of active conditions [18]. The noblest potentials were
associated with the formation of more stable and protective oxide films, which were obtained
in similar climatic or environmental conditions [19] or both.
The higher LPR corrosion rates for the test samples were associated with general corrosion
and ascribed to the increasing amounts of chlorides or sulphur dioxide or both in the at-
mosphere. Caratinga and Isla Naval contain relatively high amounts of chlorides (15 mg/
m 2 9 d); Ipatinga, Mexico and San Luis Potosf contain some sulphur dioxide (25 mg/ m 2 9
d) and Cerrillos and Acapulco contain both pollutants (15 mg/ m 2 9 d for SO 2 and 25 mg/
TABLE 2--Electrochemical parameters f or mild steel specimens exposed f or one year.
Test Station
Current
Corrosion Density, EPR Standard
Potential, V i~A/cm 2 Deviation, V
V. Martelli -0.695 0.789 0.000 40
San Juan -0.698 0.789 0.000 26
Caratinga -0.473 1.700 0.002 98
Ipatinga -0,746 7.890 0,000 36
Isla Naval -0.385 3.940 0,001 09
San Pedro -0.597 6.310 0.000 67
Cotov6 -0.605 0.947 0.000 53
Arenal 0.220 0.958 0.000 12
San Jos6 0.237 0.031 0.002 97
Cerrillos -0.749 4.730 0.000 62
Guayaquil -0.552 0.010 0.009 82
Mexico -0.140 12.400 0.002 87
Cuernavaca 0.130 0.196 0,001 89
S. L. Potosf -0.210 40.900 0.001 99
Acapulco -0.492 71.300 0.008 26
Arequipa -0,136 0.789 0.000 48
Blank -0.452 0.710 0.001 82
m 2 9 d for C1) [2]. The exception is San Pedro where very little pollution is present (less
than 10 mg / m 2 9 d for both pollutants).
The presence of sulfur dioxide in the atmosphere of M6xico and San Luis Potosf appears
to affect the protective properties of the oxides. Al t hough in both cases noble corrosion
potentials were obtained, higher corrosion current density values were registered (see Table
2). This behavior was associated with a porous, less protective oxide formed on the surface.
For localized corrosion to occur, a stable homogeneous and protective oxide is needed.
The oxide can be damaged by cracking and spalling, exposing bare metal transiently, and
corrosion can take place as "hot spots" in local areas. I f aggressive ions such as chlorides
are present, then this localized corrosion will take place in the form of pitting. Hi gh EPN
standard deviations are indicative of the degree of localized attack [16]. The highest values
obtained were Guayaquil, Acapul co, Caratinga, San Jos6, and M6xico, in that order. Of these,
Guayaquil registered a very low corrosion current density and M6xico registered a noble
potential. Neither has significant chloride content in its atmosphere. The other three sites
have variable chloride contents and pollution conditions [19].
Figure 1 illustrates the differences in the noise response and contains the EPN time record
and corresponding spectral density analysis obtained for samples exposed to different
atmospheres.
Figure l a corresponds to a steel plate exposed for three years to a rural atmosphere
(Cuernavaca). The EPN response obtained is a high-amplitude, low-frequency noise signal
with little or no high-frequency components superimposed, as can be seen in the EPN time
record, and the PSD for these data has a steep slope.
The low-frequency component s are associated with the presence of oxides or corrosion
products over the surface, and the high-frequency components are related to the stability of
the oxide film in the passive state [20]. As the oxide film becomes more porous, the spectra
are less smooth and more high-frequency component s of variable intensity (spikes) appear
in the spectrum. The standard deviation was 1.89 mV.
Figure l b presents the EPN time series and corresponding spectra for a steel sample
exposed for three years to an urban atmosphere (Mexico). The EPN response is similar to
the previous case, presenting an increase in the high-frequency component s as the corrosion
products or oxide film becomes more porous or heterogeneous when formed in a polluted
atmosphere. More active sites will be present for cracks to occur, whi ch are responsible for
the observed increase [ 21] . The standard deviation was 2.87 mV.
Figure l c presents the EPN time record and associated spectra for a three-year marine
(Acapulco) exposure steel plate sample. The noise characteristics are of a high amplitude
and low frequency, and an increase in the high-frequency components related to film rupture
or localized attack is observed as compared to the previous cases [16,20]. As the attack
becomes more intense, the spectra thus obtained resemble a white noise spectra (that is,
independent of frequency). The standard deviation also increases compared to the previous
ones and, in this case, was 8.26 mV.
P r e t r e a t e d
Figure 2 presents the corrosion potential as a function of RCL time evolution, obtained
for the pretreated steel plates. Figure 2a presents the corrosion potential versus time. Nobl e
corrosion potentials were observed, except for the P30P10 pretreated sample where an active
potential was registered. The potential evolution of all four samples was in the anodic di-
rection reaching a steady state after the third month.
Figure 2b presents the polarization resistance (Rp) versus time registering a sudden drop
of four orders of magnitude after the first month of the experiment for all four samples
ALMEI DA ET AL. ON PRERUSTED STEELS 417
x 10 "3
4
~" 2
-2
/
Z
400 800 1200
time s
-20 \
-60
-100
1600
10 .4
10 -2 100
f requency Hz
a) C u e r n a v a c a
x 10-3
~ - 2 /
4
0 ' 400 800 1200 1600
time s
-2E
t~
m
~ ' - 1 0 0
10 -4
10 -2 100
f r e que nc y Hz
b) M e x i c o
x 10 "3
0 400 800 1200 1600
t i me s
-20
N
~' -1oo
10-4
10 -2 10 0
f r e que nc y Hz
c) A c a p u l c o
FIG. 1--EPN time record and PSD plot for samples exposed for three years in different atmospheres:
(a) rural, (b) urban, and (c) marine.
es peci al l y t he P30P10. A s t eady- s t at e val ue wa s obt ai ned t he t hi rd mont h, coi nci di ng wi t h
t he cor r os i on pot ent i al behavi or .
Never t hel es s , t he Rp val ues obs e r ve d f or t he P30P10 ar e t wo or der s o f ma gni t ude l owe r
wi t h r es pect t o t he ones obt ai ned f or t he ot her t hr ee t est s ampl es . Thi s i ndi cat es t hat t he
4 1 8 E L E C T R O C H E M I C A L N O I S E M E A S U R E M E N T
r -
0
( 3 .
E
c-
O
V
n~
t -
O
i1)
r
0,4 I
0,2
- 0 , 2
- 0 , 4
- 0 , 6
I
- 0 , 8
0 2 4 6 8 10
t m o n t h s
r
I
7 [
5
3
[
J
1 [
0 2 4 6 8
0,1
0,01
0,001
0,0001
0,00001
t m o n t h s
a)
b )
l O
, , , i , , , L , , , i , , . = . , ,
2 4 6 8 10
t m o n t h s
-=- P3OPI O - +- P 3 0 P 2 4 - ~ P 3 5 A 1 0 ~ P 3 5 A 2 4
FIG. 2--Electrochemical parameters as a function of time for the pretreated steel plates: ( a ) corrosion
potential, ( b ) polarization resistance, and ( c ) EPN standard deviation.
protecti ve properties o f the P30P10 sampl e are poorer than for the others, whi ch is consi st ent
wi th the observed corrosi on potential behavior.
Figure 2c presents the EPN standard devi ati on versus ti me obtained for the four sampl es.
A decrease in t wo orders o f magni tude was registered the second month, i ncreasi ng again
and reachi ng a steady state the third month, except, once again, for the P30P10. Thi s sampl e
s hows great variability in its standard devi ati ons, never reaching a steady-state val ue. Thi s
can be related to the pretreatment characteristics, whi ch presents a higher corrosi on rate than
the other three, as observed bef ore by one o f the authors wi th analytical techni ques [8,19].
For the purpose o f clarity, the Y axis in Figs. 2b and 2c is in a logarithmic scale.
ALMEIDA ET AL. ON PRERUSTED STEELS 4 1 9
It is useful to recall that measurements were made monthly in different parts of the sample,
and that between measurements the samples were dried and kept until the next measurement.
These permitted the evolution of pretreatments and the changes in its characteristics and
corrosion properties to be followed.
Changes in time in all the electrochemical parameters measured coincide. The Rp and
standard deviations present similar trends, suggesting that the corrosion properties of the
different pretreatments can be characterized by these parameters. Although this appears to
be true, an interesting observation can be made analyzing the EPN time series and associated
spectra obtained for all the samples during the time of the experiment.
Figures 3, 4, and 5 present a few examples of EPN time record and PSD of the four
sample pretreatments and different periods of immersion. The EPN at the start of the ex-
periment (Fig. 3) presents similar features in all four samples. The noise signal presents
high-frequency components with sudden potential drops and exponential recoveries, asso-
ciated to film rupture-repassivation events [ 1 6 ] . The corresponding spectra show the
amplitude almost independent of the frequency (soft slopes) with variable intensity in the
high-frequency components.
Figure 4 presents ENM after five months of exposure. The EPN time record for the four
samples is essentially a high-amplitude, low-frequency signal with some superimposed high-
frequency components in P30P10 and P30P24. In P35A10 and P35A24, the high-frequency
components are almost nonexistent. PSD plots all have steep slopes but are very smooth for
the samples treated with aluminum hydroxide.
Figure 5 presents the ENM at the end of the experiment, nine months after exposure. The
EPN time record and PSD are similar to the previous example, except that in this case only
P35A24 presents no high-frequency components with very smooth spectra. With these re-
suits, the optimal protective characteristic of the RCL can be established when this had been
reached. This is because subsequent ENM and PSD (not shown) increased slightly their
high-frequency components up to the end of the experiment, as in Fig. 5. This was observed
by one of the authors using analytical techniques [2,8,22].
In a recent study [23], it was established that the sample P30P24 reached this condition
after six months of exposure and P30P10 never did. Of the two, P30P10 presents the poorest
corrosion performance because of its porous RCL structure [ 2 1 ] . In fact, P30P10 had the
worst performance of all according to the electrochemical results.
The results confirm reports that the time of exposure influences the behavior of the RCL
[8,24]. For surfaces enriched in goethite by natural aging in the atmosphere, the application
of H3PO 4 appears to enhance such enrichment in the film of corrosion products, thus in-
creasing its stability and improving its anticorrosion properties [8]. The greater the atmos-
pheric exposure time, the less effective the converting action of H3PO 4 as a result of the
growth of goethite grain size with increasing exposure time [21].
Not only the time of exposure, but also the treatment is of importance when considering
these pretreatment rust converters. The best anticorrosive properties were the samples satu-
rated with AI(OH)3 (P35AI0, P35A24), probably as a result of the low solubility of the
newly formed layers [ 2 2 ] . It reached optimum condition five months after exposure.
It is proposed that not only their protective characteristics could be established with ENM,
but also the RCL morphological features, which provide such properties according to the
literature [8,22]. The RCL obtained with H3PO 4 solution at 38.6% and saturated with
AI(OH) 3 change more or less continuously as observed with the scanning electron micro-
scope [ 2 2 ] . The change observed leads to the growth of spirals and a final complex structure,
which correlates with the PSD changes registered [23].
In summary, the results demonstrate the utility of ENM for the study of prerusted and
pretreated steel. This technique was able to characterize the protective properties of iron
0.02
9 -0.02
-0.06
0 400 800 1200 1600
t ~e s
xl 0- 3
-15
0 400 800 1200 1600
t l m e s
t~ -20
-.>
~ -60
~-100
10-4
a) P 3 O P I O
-2G
N
m
-60
~ - 1 ~
10-4
b) P 3 0 P 2 4
10- 2 10 0
f r e que nc y Hz
~, " . . . . . . ]
10-2 100
f r e que nc y Hz
o . o j
~. 0
' -0.02
-0.04~
0 400 800 1200 1600
t i me s
c )
x l ~ 2
1.5
0.5
-0.5
-1,5
-2{
P 3 5 A I 0
10-4 10-2 100
f r e que nc y Hz
- 2 O
-60
m - 1 ~
0 400 800 1200 1600 10 ~ 10-2 100
t i me s f r e q u e n c y Hz
d) P 3 5 A 2 4
FIG. 3 - - EPN time record and PSD plot f or the pretreated steel plates obtained at the start of the
experiment.
ALMEIDA ET At . ON PRERUSTED STEELS 421
x 10 -4
1
~" 0
-2
xlO-3
400 800 1200 1600
t i m e s
1.5
~' 0.5
~-0.5
-1.5
xlO-5
400 800 1200 1600
t i m e s
xlO -3
400 800
t i m e s
1200 1600
6 q
-2O
m
-60
~'-100
10-4 10-2 10 0
f r equency Sz
a) P 3 O P I O
-2O
-6t]
- t ~
10-4
10 -2 I00
f r equency Hz
b ) P 3 0 P 2 4
- 2 O
-60
-1oo
l O - 4
c) P 3 5 A I 0
lO-2 1oO
f r equency Hz
-2O
-60
- 1 ~
1o-4
d ) P 3 5 A 2 4
o 4o0 s00 12oo 16oo 1o-2 1o 0
Clme s f r equency Hz
FIG. 4- - EPN time record and the PSD plot obtained five months after surface preparation f or the
pretreated steel plates,
1
0
- 2
x l O - 4
2, /
0 4 0 0 800 1 2 0 0 1 6 0 0
t i m e s
x l O- 4
6
2
- 6
1
- 3
0 4 0 0 800 1 2 0 0 1 6 0 0
t ~e s
x l 0 - 4 b )
3
%
0 4 0 0 8 0 0 1 2 0 0 1 6 0 0
t i me s
x l 0 - 3
-20
- 6 0
- 1 0 0
1 0 - 4
a) P 3 0 P I 0
' \
\v/' ~
10 - 2 100
f r e q u e n c y Hz
-20
- 6 0
m - 100
10 - 4
P 3 0 P 2 4
- 2 0
- 6 0
- 1 0 0
1 0 - 4
10- 2 100
c ) P 3 5 A I 0
10 - 2 1 0 0
1
0
- 1
0 4 0 0 8 0 0 1 2 0 0 1 6 0 0
- 2 o !
- 6 0
v
- 100
t i m e s
d) P 3 5 A 2 4
0- 4 1 0 - 2 100
FIG. 5- - EPN time record and PSD plot f or the pretreated steel plates obtained nine months after
surface preparation.
oxides developed under different environmental conditions. It was also possible to establish
the corrosion behavior of RCL and its time evolution for the surface pretreatment samples
considered.
Conclusions
The noise response obtained shows a distinctive behavior for different surface conditions
and correlates well with its protective characteristics obtained by LPR. In general, for sam-
ples exposed to rural atmospheres without chlorides (P0-S0), low current densities and a
smooth PSD suggest compact and protective oxides over the surface. For samples exposed
to polluted atmospheres (PI, SI), high current densities and a variable increase in the PSD
high-frequency components reflect the poor protective characteristics of oxides formed or
localized attack as a result of the presence of chlorides.
For pretreated samples, the electrochemical parameters describe the RCL corrosion be-
havior. P30AI0 shows the worst performance with an active potential, a higher corrosion
rate, and a variable ENM standard deviation as compared to the other, three. The PSD
obtained for the four samples reflect the RCL changes over time and allow the establishment
of the most protective pretreatment when this condition was reached.
Acknowledgments
The authors wish to express their gratitude to the Programa Iberoamericano de Ciencia y
Tecnologfa (CYTED) and Instituto de Investigaciones El6ctricas (liE) for the support given
in this project.
References
[1] Tomashov, N. D., Ed, Theory of Corrosion and Protection of Metals, MacMillan, New York, 1966.
[2] Morcillo, M., "Atmospheric Corrosion in Iberoamerica," in Atmospheric Corrosion, ASTM STP
1239, W. W. Kirk and H. H. Lawson, Eds., American Society of Testing and Materials, West
Conshohocken, PA, 1994.
[3] Bums, R. and Bradly, W. W., Eds., Protective Coatings for Metals, Reinhold, New York, 1959.
[4] Hendry, M., "Reader Response on Rust Converter," Journal of Protective Coatings and Linings,
Vol. 2, No. 8, 1985, p. 18.
[5] Frondistou Yannas, S., "Evaluation of Rust Tolerant Coatings for Severe Environments," Journal
of Protective Coatings and Linings, Vol. 3, No. 8, 1986, pp. 26-35.
[6] Alvarez, Z. E., Callozo, I., and Valdrz, D., "Convertidores de Herrumbre," Revista Iberoamericana
de Corrosion y Proteccion, Vol. XVII, No. 1, 1987, pp. 35-38.
[7] Nigam, A. N., Tripathi, R. R, and Dhoot, K., "The Effect of Phosphoric Acid on Rust Studied by
Mossbauer Spectroscopy," Corrosion Science, Vol. 30, No. 819, pp. 799-803.
[8] Almeida, E., Pereira, D., Waerenborgh, J., Cabral, J. M., Figueiredo, V. M., et al., "Surface Treat-
ment of Rusted Steel with Phosphoric Acid Solutions," Progress in Organic Coatings, Vol. 21, No.
4, 1993, pp. 327-338.
[9] Uller, L. and Morcillo, M., "Mapa Iberoamericano de Corrosividad Atmosferica MICAT," in Pro-
ceedings of the 3rd lberoamerican Congress on Corrosion and Protection, Vol. 1, ABRACO, Rio
de Janeiro, 1989, p. 462.
[10] Uller, L. and Morcillo, M., "The Setting Up of an Iberoamerican Map of Atmospheric Corrosion,"
in Proceedings of the 11th International Corrosion Congress, Vol. 5, AIM, Florence, 1990, p. 2.35.
[l l] Knotkova, D. and Vrobel, L., "ISOCORRAG: The International Testing Program Within ISO/TC
156/WG4," in Proceedings of the l l th International Corrosion Congress, Vol. 5, AIM, Florence,
1990, p. 5.581.
[12] Kucera, V., Coote, A. T., Kenriksen, J., Knotkova, D., Leygraf, C., and Reinhardt, U., "Effects of
Acidifying Pollutants on Materials Including Historic and Cultural Monuments," in Proceedings of
the llth International Corrosion Congress, Vol. 2, AIM, Florence, 1990, p. 2.433.
[13] Trewartha, G. T., Ed., An Introduction to Climate, 4th ed., McGraw-Hill, New York, 1968.
[14] Hladky, K. and Dawson, J. L., "The Measurement of Corrosion Using Electrochemical 1 I f Noise,"
Corrosion Science, Vol. 22, 1982, p. 231.
[15] Hashimoto, M., Miyajima, S., and Murata, T., "A Stochastic Analysis of Potential Fluctuation
during Passive Film Breakdown and Repair on Iron," Corrosion Science, Vol. 33, No. 6, 1992, p.
885.
[16] Uruchurtu, J., "Electrochemical Investigations of the Activation Mechanism of Aluminum," Cor-
rosion, Vol. 47, No. 6, 1991, p. 472.
[17] Fontana, M. and Greene, N. D., Eds., Corrosion Engineering, McGraw-Hill, New York, 1978.
[18] Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous Solutions, NACE, 1974.
[19] Morcillo, M., "Mapa Iberoamericano de Corrosion Atmosferica Resultados Preliminares," in Pro-
ceedings of the 1st Pan American Congress on Corrosion and Protection, Mar del Plata, 1992.
[20] Uruchurtu, J., "Transient Behavior of Pure Aluminum During Noise Analysis," presented at the
NACE Conference in Advances in Localized Corrosion, NACE9, Orlando, 1987, p. 141.
[21] Granese, S. L., Rosales, B. M., Ayllon, E. S., Varela, E E., Gervasi, C. A., and Vilche, J. R.,
"Characterization of the Atmospheric Corrosion Products," in Proceedings of the 1st Pan American
Congress on Corrosion and Protection, Mar del Plata, 1992.
[22] Almeida, E., Pereira, D., Figueiredo, V. M., Lobo, V. M. M., and Morcillo, M., "Why the Improved
Performance of Phosphoric Acid Pretreatments under Aluminum Hydroxide Addition," presented
at the 12th International Corrosion Congress, Houston, 1993.
[23] Veloz, M. A., BCh. Engineering Dissertation, Instituto Tecnolrgico de Pachuca, Hidalgo, Mexico,
1994.
[24] Stratmann, M. and Hoffmann, K., "In Situ Mossbauer Spectroscopic Study of Reaction Within
Rust Layers," Corrosion Science, Vol. 29, No. 1329, 1989.
Standardization
Go r d o n P. Bi e r wa g e n , t Do u g l a s J. Mi l l s , ~ De n n i s E. Tal l man, 2 a n d
Br i a n S. S k e r r y 3
Reproducibility of Electrochemical Noise
Data from Coated Metal Systems
REFERENCE: Bierwagen, G. P., Mills, D. J . , Tallman, D. E., and Skerry, B. S., " Repr o-
ducibility of Electrochemical Noise Data from Coated Metal Systems," Electrochemical
Noise Measurement f or Corrosion Applications, ASTM STP 1277, Jeffery R. Kearns, John R.
Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds., American Society
ABSTRACT: The use of electrochemical noise (ECN) as a method to characterize the cor-
rosion-protection properties of organic coatings on metal substrates was pioneered by Skerry
and Eden, and since then has been used by others as a probe for coating metal corrosion
studies. However, no statistical examination of the reproducibility of the data from such mea-
surements has been published. In the data we present, we have done a systematic analysis of
important experimental variables in such systems. We have examined the method for accuracy
and reproducibility with respect to sample preparation, sample immersion, and metal substrate
preparation. We have taken several marine coatings systems typical of U.S. Navy use, prepared
duplicate samples of coating metal systems, and examined them under the same immersion
exposure. The variables we considered for reproducibility are paint application (in three-coat
systems), metal panel preparation (grit-blasted steel), and immersion conditions. We present
ECN data with respect to immersion time on the values of noise voltage standard deviation
tr v, noise current standard deviation cr t, and the noise resistance R, as given by crvl~r I. The
variation among supposedly identical sample pairs in identical immersion monitored under
identical conditions is presented. The statistics of the time records of the data are considered,
and the variations with respect to specific coatings classes are also considered within the limits
of the data. Based on these data, comments concerning ECN on coated metal systems as a
predictive test method are presented along with special considerations that must be made to
properly use the method for coating ranking and lifetime prediction.
KEYWORDS: electrochemical noise, marine coatings, reproducibility, coating testing,
corrosion
The use o f el ect r ochemi cal noi se met hods ( ENM) to e xa mi ne cor r os i on pr oces s es is cer-
t ai nl y a gr owi ng ar ea o f i nt er est f or cor r os i on sci ent i st s [1-6] i ncl udi ng t hose st udyi ng cor-
r odi bl e met al subst rat es " p r o t e c t e d " by or gani c coat i ngs [7-11]. Thi s i mpor t ant met hod has
muc h t o of f er t hose s t udyi ng cor r os i on becaus e it is a noni nt r usi ve t echni que, has a fai rl y
we l l - de ve l ope d t heor et i cal basi s [1,2,4,12-16], al l ows cont i nuous moni t or i ng o f cor r odi ng
s ys t ems [7], and enabl es ki net i c and mechani s t i c i nf or mat i on t o be obt ai ned [5,171. Ot her
i mpor t ant f eat ur es of ENM ar e t he wi de r ange of its appl i cabi l i t y, t he r el at i ve si mpl i ci t y of
t he e qui pme nt necessar y, and t he way in whi ch dat a can be used f or pr edi ct i ve pur poses.
Department of Polymers & Coatings, North Dakota State University, 54 Dunbar Hall, Fargo, ND
58105.
2 Department of Chemistry, North Dakota State University, Fargo, ND 58105.
3 Sherwin-Williams Co., Cleveland Technical Center, 601 Canal Rd., Cleveland, OH 44113.
427
www.astm.org
Also, because the measurement is electrochemical in nature, it provides objective numerical
data. By way of comparison, in most conventionally used methods of characterization of
corrosion protection by coatings, assessment is qualitative and subjective.
One of the goals of our work at North Dakot a State University (NDSU) was to take the
ENM developed by Skerry and coworkers [7-9,11,17-21] to characterize mainly industrial
maintenance coatings, and extend them to high-performance marine coatings. Preliminary
parts of this work have already been reported [22-25]. In this work, we used a DENIS ENM
system from Capcis March, Ltd. of Manchester, UK (Capcis March Limited, Corrosion and
Protection Centre, UMIST, Manchester, UK). This is fairly straightforward and easy to use.
In addition to driving the hardware and gathering and storing the raw data, the DENIS system
also has software for the reduction and analysis of the acquired data.
Anot her goal of this work, and the one we report in this paper, is to develop a validation
of the reproducibility of the method for use as a laboratory t ool in the study, of corrosion
protection by coatings. The studies to date present data for single samples run in compari son
to other single samples. There has been no well-documented study of the reproducibility,
accuracy and precision of ENM for the study of organic coatings. This is also true of other
electrochemical methods used to investigate corrosion with the exception of two recent pa-
pers [26,27] on the reproducibility of electrochemical impedance spectroscopy (EIS) data
for coated metal systems. Regarding data gathered from noise experiments, there is a need
for work that looks at the variation from one incremental time period to the next and the
variation between sets of different but nominally idehtical specimens whether coated or
uncoated. Such work is essential to validate the conclusions obtained from noise experiments
and particularly the level of significance to give to changes in values. In this paper, we
present the first data examining the reproducibility of ENM for characterizing the corrosion-
protection properties of coatings. These data were obtained on two complete marine coatings
systems, typical in substrate and coating to U.S. Navy u s e . 4
Our ENM studies are described in the context of using them as a test met hod to study
the corrosion-protection performance properties of coatings. There will be some focus on
the barrier properties of anticorrosive coatings [28]. ENM test results can be compared to
other corrosion test methods, ASTM or otherwise [29]. We use standard statistical methods
for considering experimental data [30,31]. The data presentation used is specific to our data,
as shown below.
Experimental Program
Materials
The metal panels before coating were supplied by Cust om Lab (Route 20, EO. Box 85,
Sheridan, NY 14135), grit blasted to an SSPC 5-10 surface (equivalent to about Sa 2.5), and
then stored in a desiccator until coatings application. For these specific studies, two complete
three-coat marine coatings systems were used. The first was a brown epoxy primer top-
coated by two coats of an epoxy haze-gray (referred to below as BHH), and the other was
two coats of a standard naval red alkyd primer top-coated by a single coat of a gray silicon
alkyd (AAS below). The brown epoxy primer was supplied by Southern Coatings, Inc. (EO.
Box 160, Sumpter, SC 29151), and the other naval coatings were supplied by International
Coatings Ltd. (Courtaulds Coatings Ltd., 6001 Antoine Dr., Houston, TX 77210). We ex-
4 Coating selection advice provided by Naval Surface Warfare Command, Coatings Group, Carderock,
MD.
BIERWAGEN ET AL. ON REPRODUCIBILITY OF ELECTROCHEMICAL NOISE DATA 429
ami ned six nomi nal l y i dent i cal sampl es of each coat i ng. Each sampl e is spl i t into t wo spec-
imens. The t hi ckness of t he pai nt was measured in t en pl aces on each speci men usi ng an
El comet er TM 345 gauge ( El comet er Inst rument s Lt d. , Manchest er M35 6BU, Engl and). Pai nt
t hi ckness values on all speci mens used for the ENM experi ment s wer e hi ghl y reproduci bl e.
Ther e was mor e scat t er for the speci mens used for the accel er at ed exposure tests. Because
it is a cri t i cal fact or in det er mi ni ng t he l evel of prot ect i on afforded, al l pai nt t hi cknesses of
ENM speci mens are gi ven in Table 1.
E N M Me t h o d
The ENM equi pment used was made by Capci s Mar ch Li mi t ed (CML). It is a comput er-
cont rol l ed, aut omat ed di gi t al syst em for t he si mul t aneous measur ement of el ect r ochemi cal
vol t age and current noise. In mul t i pl ex mode, it can cont rol dat a acqui si t i on from t wel ve
cells. A bl ock di agr am showi ng t he set - up i s i l l ust rat ed in Fi g. 1.
Two nomi nal l y i dent i cal el ect rodes (j oi ned t oget her duri ng measur ement vi a a zero resi s-
t ance ammet er) and a reference el ect rode compr i se one probe. Wi t h our present confi gurat i on,
as many as t wel ve pr obes can be moni t ored. The machi ne i nt errogat es each probe for a fi xed
t i me per i od (8.5 mi n in our experi ment s), and then moves on to the next. Moni t or i ng is
cont i nuous, and dat a can be gat hered over a per i od of days, weeks, mont hs, or even years.
The actual exper i ment al cel l ar r angement was di fferent f r om that used pr evi ousl y [7]. Inst ead
of cont rol l i ng the area of cont act of the el ect r ol yt e wi t h t he panel s by a cyl i ndr i cal seal, t he
backs and sides of t he speci mens wer e coat ed wi t h a Col ophony Ros i n/ Bees wax mi xt ure
( 3/ 1) . Thi s is appl i ed mol t en (m. p. 60~ and is a hi ghl y effective, inert, hi gh-resi st ance
( > 1012 ohms- cm 2) prot ect i ve coat i ng. Each i mmer sed panel in the ENM exper i ment s had 50
cm 2 of pai nt l eft exposed. Thi s panel confi gurat i on makes it easi er t o assess t he effect of
t emperat ure and agi t at i on, because the t hree el ect rodes that compr i se each pr obe wer e in t he
same cont ai ner rat her t han in t wo di fferent cel l s j oi ned by a sal t bri dge. The set up is i l l us-
t rat ed in Fi g. 2. The sol ut i on used was 3% sodi um chl ori de (NaC1) except for t wo l ong- t er m
BHH probes (10a and 1 l a) when for the second hal f of the exposur e per i od t he sol ut i on
TABLE 1- - Thi ckness o f AAS and BHH ENM specimens. Al l data in Izm.
Specimen 1 Specimen 2
Probe Specimens First Second Third Total First Second Third Total
l a AAS la-5d 16 129.3 52 197.3 18 125.6 33 176.6
5a AAS lb-7a 19 125.6 48 192.6 23 120 47 190
9a AAS 15c-17d 22 121 29 172 27 119 48 194
10a AAS 12c-13d 28 111 23 165 29 118 24 166
l l a AAS 8b- l l d 24 120 34 178 19 122.3 26 167.3
12a AAS 12b-16a 32 110 23 165 17 125.9 25 167.9
average 23. 5 1 1 9 . 4 8 34.83 1 7 8 . 3 22.17 1 2 1 . 8 33.83 177
standard devi~ion 5.86 7.72 12.51 13.85 5.0 3. 38 11.05 12.3
4b BHH21d-23a 44 153 45 242 41 148 14 203
8b BHH36b-39c 52 146 53 251 40 154 29 223
9b BHH35d-37c 39 152 24 215 45 152 25 222
10b BHH33a-38c 48 149 40 237 42 153 61 256
l l b BHH34a-37d 42 145 20 207 46 153 33 232
12b BHH 32b-34d 40 155 41 236 38 155 28 221
average 44.17 150 37.17 231.3 42 152. 5 31.67 226.2
standard devi~ion 5.0 4 12.67 16.81 3.03 2.43 15. 74 17.41
FIG. 1--Block diagram of the electrochemical noise-monitoring instrumentation.
FIG. 2--Cell arrangement for measuring electrochemical noise.
was swi t ched to sea water. (We not ed no changes in the ENM dat a wi t h this change in
i mmer si on fluid.)
Experi ment al dat a were acqui red at 2-s i nt erval s up to a t ot al of 256 dat a poi nt s in one
set. Fr om each dat a set, the st at i st i cal paramet ers di scussed bel ow are cal cul at ed. The as-
sumpt i on is made that over this acqui si t i on t i me the noi se dat a set is l ocal l y st at i onary [32]
(that is, the averages t aken in the i ndi vi dual dat a sets are t i me i ndependent ).
In this work, six sampl es from t wo pai nt syst ems ( AAS and BHH) were exami ned. The
t i me on test varied. AAS sampl es were moni t ored for up to 118 days (four sampl es) or 125
days (two sampl es); BHH sampl es were moni t or ed for up to 94 days (four sampl es) or 194
days (t wo sampl es). Al l sampl es were cont i nuousl y moni t or ed over t he first 20 days of
exposure. However, because ot her pai nt syst ems had al so to be investigated, it was not
possi bl e to moni t or all t wel ve sampl es cont i nuousl y wi t hout a break in the dat a acqui si t i on
over t he full per i od of t he test. At t i mes when t hey were not bei ng moni t or ed (i ndi cat ed as
st rai ght -l i ne sect i ons on the graphs), sampl es were l eft in the same vessel s cont ai ni ng 3%
NaC1.
ENM Data Analysis
Fr om each 256-poi nt current and 256-poi nt vol t age raw dat a file, t wo ENM paramet ers
and one deri ved val ue were obt ai ned. These are tr I (st andard devi at i on of the noi se current),
Gr v (st andard devi at i on of the noi se pot ent i al ), and the noi se resi st ance R, . The cal cul at i on
of ~r I and ~v from the raw noi se dat a is the first st ep in reduci ng the dat a to a t echni cal l y
usabl e form. The average current and pot ent i al values, (/),(V), used to cal cul at e the st andard
devi at i on values const i t ut e the l ocal l y st at i onary values of current and pot ent i al that bol d for
the syst em over t he measur ement peri od, whereas the crl and ,rv values const i t ut e measures
of t he fluctuations in current and pot ent i al duri ng this peri od. Fr om Bi er wagen [32] we can
cal cul at e a noi se resi st ance for the syst em that is gi ven by R, = ~v/~rl. R, val ues have proven
to be the si ngl e most useful val ue that we can deduce from ENM data. Thi s par amet er
charact eri zes the resi st ance of the whol e syst em to the movement of charge. Thi s val ue may
be domi nat ed by processes at t he met al coat i ng i nt erface (pol ari zat i on or charge t ransfer
resi st ance) or by movement of i ons through the coat i ng (ionic resi st ance). As shown by the
wor k of Sker r y [7-9,11,17,19-21], the l arger t he val ue of R, , the great er the prot ect i on
afforded to the met al subst rat e by the pai nt syst em. We have shown that R, t racks very
cl osel y the measured DC resi st ance values for several pai nt syst ems i ncl udi ng t hese mari ne
pai nt s [33]. Si mi l ar concl usi ons have been drawn on the use of di rect l y measured DC resi s-
t ance dat a [34]. (Not e t hat the values of (I> and (V> are not true " noi s e" measurement s.
They are average, or DC, values of t he noi se current or voltage, respect i vel y, obt ai ned over
a st andard t i me i nt erval [normal l y 10 min], whereas ~r~, tr~ and R, are true noi se paramet ers,
charact eri zi ng the spont aneous fluctuations in current and vol t age that we are measuri ng. )
Some exper i ment s ran for up to 6 months. Thi s semi cont i nuous dat a acqui si t i on met hod
provi des a mor e compl et e t i me record than any ot her avai l abl e cor r osi on- moni t or i ng met hod
for coat ed syst ems. However, it i nevi t abl y means accumul at i ng l arge amount s of data, per-
haps as many as 2000, 10-min raw dat a files from t he moni t ori ng of a part i cul ar speci men
pair. I f unedi t ed, this woul d pr oduce a graph wi t h 2000 poi nt s on it. To cl ari fy the presen-
tation of the results in this work, deri ved noi se paramet ers from every sixth dat a set are used.
Thus, values of the t hree paramet ers as cal cul at ed at 12-h i nt erval s (from the l arger dat a sets
where we have dat a sets every 2 h) have been exami ned versus the t i me of i mmer si on values.
Accelerated Test Methods
A separat e but nomi nal l y i dent i cal (except that t hey were scri bed) set of panel s were
subj ect ed to accel erat ed tests. Two tests were used. One was a cycl i c test, whi ch was con-
duct ed in t wo di fferent cabi net s. For the first 500 h, t ri pl i cat e panel s of AAS and BHH were
in a Q- f og sal t spray cabi net with t emperat ure cycl i ng every 2 h bet ween 20~ (fog, sal t
spray on) and 40~ (dry, sal t spray off). The sol ut i on was 3% NaCI, and the ai r pressure
was 24.5 psi (168.9 kPa). The panel s were then t ransferred to a QUV cabi net where t hey
were subj ect ed to a UV (2-h, 55~ humi di t y (2-h, 60~ cycl e for a total of 250 h.
They were then ret urned to the sal t spray cabi net for 300 h. The total test t i me was 1050 h.
Thi s cycl e has been used by Skerry and ot hers [17,19-21].
The second test was the hot salt bat h test [35]. In this cont i nuous test, panel s are t ot al l y
i mmer sed in a 5% NaCI sol ut i on hel d at 55~ for 240 h. Set s of scri bed AAS and BHH
sampl es were exami ned in quadrupl i cat e. Panel s were assessed usi ng the visual scal e shown
in Table 2. The scribe and the face were assessed separately.
R e s u l t s
ENM
Values of R, obt ai ned duri ng the first 20 days are pl ot t ed versus t i me of sampl e i mmer si on
in Fi gs. 3 and 4 (BHH) and Fi gs. 5 and 6 ( AAS) . Fi gures 3 and 5 are t i me- l i ne graphs for
si x-sampl e dat a sets for the t wo coat i ng syst ems pl us t he averages and st andard devi at i on of
the i ndi vi dual dat a sets, BHH and AAS, respect i vel y. These graphs, as wel l as t he l i ne pl ot
of the par amet er for each of the sampl es, gi ve the curve for the average of the par amet er in
quest i on al ong wi t h the st andard devi at i on of t hese dat a as a function of t i me. Fi gur es 4 and
6 show a t hr ee- di mensi onal (3D) proj ect i onal represent at i on of the same dat a t hat vi sual l y
i l l ust rat es the sampl e spread somewhat mor e effect i vel y than Figs. 3 and 5. Fi gur e 7 gi ves
the pl ot of the sampl e average R, val ues for t he BHH and AAS sampl e sets for 20 days '
TABLE 2--Qualitative assessment data for cyclic spray and hot salt bath exposure
of BHH and AAS specimens.
Accelerated Test Results--Visual Assessment
Cyclic Salt Spray (1050 h) ~ Hot Salt Bath (240 h)
Protection Rating Protection Rating
Paint Specimen Face Scratch Specimen Face Scratch
AAS b
BHH c
6a 7
6d 7
7d 6
lO
27c 9
29c 7
3 5a 6 7
3 13a 8 6
3 14a 6 6
16b 7 6
- 6" 29b 8 6
6 30a 8 6
6 30d 8 6
9 . 33b 9 6
9 . 35c 9 6
The specimens were exposed to UV/humidity cycle at Coffeyville for 250 h.
b AAS: alkyd primer, alkyd middle coat, silicone alkyd top coat.
c BHH: brown epoxy primer, haze gray epoxy middle coat, haze gray epoxy top coat.
BI ERWAGEN ET AL ON REPRODUCI BI LI TY OF ELECTROCHEMI CAL NOI SE DATA 433
1.00E+10
BHH Statistical Analysis
1.00E+09
1.00E+08
A
E
?
1.00E+07
1. 00E
1' . ~E~5
1.00E+04
x
x +
. 4,
" . & ; ~, . , x
V
A X " "" * X X " A 9 ' X~ " ,
o + + + .
. X - + )~ + A A
D
~ +
CI +
O ~O O O
O
9 O o
a ~ g o * * * - * go
o r o o o o o o
~176176 o o ~ * o r . 8 o O
0 O O 0
0 0 0 0 0 0 0
i
2
FIG. 3- - ~
. 4 R Noise 1
O 8 R Noise /
A 9 R Noise /
x 10 R Noise /
+ 11 R Noise J
. 12 R Noise J
Sampl eAvg
. . . . . . SamStdev
I I I . . . . .
4 6 8 110 112 14 116 18
I mmersi on Ti me (days)
versus immersion time for BHH samples (20-day continuous data).
FIG. 4--R. versus immersion time for BHH samples (20-day continuous data) 3D projection of
Fig. 3.
1E+09
AAS Statistical Analysis
1E+08
E
?
1E+07
o
1E+06
1E+05
o
o
o
o * o o o
o: ',, .". o ~"
x , o = " ~ " " ,~
n 0 + " . ,
, ' "o ". ~..t" ~ . . . . "-:-'o "'+%~ | ':,-"" ~
. & " " + * . " - - o
+ . - - "
5 10 15 20
I mmeml on Ti me ( da ys )
o 1 R N~se
13 5 R N~se
a, 9 R No4se
x 10 R Nol N
+ 11 R Noi se
12 R Noi se
, Sampl eAvg
. . . . . . SamSt dev
FIG. 5--R. versus immersion time for AAS coating samples (20-day continuous data).
FIG. 6--Immersion time for AAS samples (20-day continuous data) 3D projecton of Fig. 5.
BI ERWAGEN ET AL. ON REPRODUCI BI LI TY OF ELECTROCHEMI CAL NOI SE DATA 435
1.00E+O{
1.00E+08
1.00E+07
Noise Resist
1.00E+OE
1,00E+05
Rn vs Time
2 4 6 8 10 12 14 16 18
Immemlon Time
FIG. 7--R. (sample average) versus time for BHH and AAS.
{
+AA8 <Rn 1
- l - - BHH <Rn j
immersion. The longer-term data, obtained over 200 days for BHH and 125 days for AAS,
are plotted as 3D graphs (Figs. 8 and 9). The latter method of plotting shows more clearly
the separation of the different samples. Figure 10 gives the plot of the sample average R,
values for the BHH and AAS sample sets for 120 to 200 days of immersion. For the 120-
to 200-day period for BHH samples, only two panels of the original six were examined.
FIG. 8--R, versus immersion time for BHH coating samples, 3D projection of 200-day data.
FIG. 9--R. versus immersion time for AAS coating samples, 3D projection of 120-day data.
IE+11
Rn vs Ti me
1E+10
1E+09
A
E
u
1E+08
o
i
~ E+07
~ 1E*06
1E+05
F - ~_ AAS <Rn> (6 Panels)-
i <. . . ( . Pane,.)
! --e- BHH <Rn> 12 Panels)
I E+04 ~ i , I
0 20 40 60 80 100 120 140 160 180 200
I mmeml on Ti me (days)
FIG. lO--Sample average R~ values versus immersion time for BHH and AAS coatings (indicating
removal of four BHH panels from test).
Accel er at ed Tests
Thes e resul t s ar e pr esent ed in Tabl es 2 and 3. It can be seen f r om Tabl e 2 t hat t he BHH
panel s have cons i der abl y hi gher obj ect i ve pe r f or ma nc e r at i ngs at bot h t he scri be and t he f ace
in t he cycl i c cabi net t est t han AAS. In t he hot salt bat h test, t he vi sual r at i ngs at t he f ace of
BHH sampl es ar e hi gher, al t hough vi sual rat i ngs at t he scr i be ar e s i mi l ar f or bot h coat i ngs.
The DC r esi st ance dat a o f Tabl e 3 s how si mi l ar resul t s.
Di s c us s i o n o f Ex p e r i me n t a l Re s ul t s
General Comment s
Sever al t hi ngs ar e appar ent f r om t he dat a shown in t hese fi gures and t abl es. The first is
that a mong t he six i ndi vi dual panel sets, t her e is qui t e a var i at i on in resul t s. Concent r at i ng
on t he R, gr aphs up t o 20 days f or t he BHH s ampl es f or t hi s s ame 20- day expos ur e per i od
as s hown in Fi gs. 3 and 4, t wo sampl es have r el at i vel y l ow val ues ( si mi l ar t o AAS ) wher eas
t he ot her f our ar e muc h hi gher ( ar ound 1 x 108 f l 9 cm2). Thes e dat a s ugges t that t hi s
di st r i but i on is not nor mal but bi modal , al t hough mor e sampl es ar e needed t o val i dat e t hi s
obser vat i on. The scat t er is cer t ai nl y hi gh (st andard devi at i on _+ 108 I I 9 c m 2) at mos t t i mes.
I n t he case o f t he AAS sampl es (Fi gs. 5 and 6), all si x s ampl es var y consi der abl y, but a
vi sual i ns pect i on suggest s t hat t he R, dat a are c o mi n g f r om one popul at i on. Be yond 5 days,
t he dat a are gr ouped ar ound 8 x 105 I I 9 c m 2. The hi gh er r or (st andard devi at i on about _+ 105
9 c m 2) r ef l ect s t he r ange in val ues ( f r om 1 105 ~q 9 c m 2 t o 5 x 106). However , t he dat a
cer t ai nl y gi ve suf f i ci ent r epr oduci bi l i t y t o pr ovi de a val i d and r api d di f f er ent i at i on of t he
AAS coat i ng s ys t em f r om t he BHH coat i ng syst em.
Furt her, based on t he wor k o f Sker r y [ 7- 9, 11, 17- 19] , and al so our par al l el but separ at e
exposur es o f coat i ng s ampl es [22- 24], we have a ver y fi rm ar gument f or usi ng t he R, val ues
f or r anki ng o f coat i ngs. Wi t hi n a week, we can t el l f r om t he R, dat a t hat t he BHH s ys t em
wi l l out per f or m t he AAS syst em. The l onger - t er m dat a bear t hi s out, as wel l as pr ovi de an
TABLE 3 - - DC resistance data taken after cyclic salt spray and hot salt bath exposure
of AAS and BHH specimens.
Accelerated Test Resul t s- - DC Resistance
Cyclic Salt Spray (1050 h)" Hot Salt Bath (240 h)
DC Resistance, f l 9 cm 2 DC Resistance, f l 9 cm 2
Paint Specimen Face Scratch Specimen Face Scratch
AAS h 6a 1.0E + 9, 1.5E + 9 3.5E + 03 5a 9.0E + 07 3.50E + 03
6d 5.0E + 8, 4. 0E + 8 6.0E + 03 13a 1.0E + 09 2.50E + 03
7d 1.0E + 9, 1.0E + 9 4.5E + 03 14a 1.0E + 07 3.00E + 03
16b 1.0E + 09 3. 00E+ 03
BHH c 26c 5.0E + 9, >2. 0E + 10 6.0E + 03 29b 7.0E + 09 3.00E + 03
27c >2. 0E + 10, >2. 0E + 10 7.0E + 03 30a >2. 0E + 09 3.00E + 03
29c 3.0E + 9, 3.0E + 10 6.0E + 03 30d 2.0E + 09 3.00E + 03
33b 1.5E + 10 3.50E + 03
35c 1.0E + 10 1.10E + 04
a The specimens were exposed to UV/ humi di t y cycle at Coffeyville for 250 h.
b AAS: Alkyd primer, alkyd middle coat, silicone alkyd top coat.
" BHH: brown epoxy primer, haze gray epoxy middle coat, haze gray epoxy top coat.
est i mat e of t he degradat i on t i me of the coat i ngs. We show exponent i al fits to t he dat a to
si mpl i f y exami nat i on of the dat a sets and to cl ari fy the di fferent i at i on bet ween sampl e sets
that the dat a indicate.
The rel at i ve errors (st andard devi at i on/ aver age) for the all paramet ers for the sampl es all
range from 20 to 200%. Yet, as the pl ot in Fig. 7 shows, we are st i l l abl e to di st i ngui sh
bet ween t wo rel at i vel y hi gh- per f or mance coat i ng syst ems by average R, values aft er a rel -
at i vel y short time, in this case wi t hi n the 20- day per i od of this ori gi nal work. Further, the
degradat i on of the coat i ngs by sal t wat er i mmer si on is i l l ust rat ed by the gradual decrease in
R, values wi t h t i me for AAS and up to 150 days for BHH. These dat a are shown in Fi gs.
8 t hrough 10. The t wo l ong- t er m BHH sampl es do appear to show a sl i ght ri se in R, val ue
duri ng the l ast mont h on test. The expl anat i on for this is not known.
The hi gh val ue of st andard error for the BHH sampl es means that, i f the resul t s were
pl ot t ed on a l i near scale wi t h error bars, t here woul d be overl ap wi t h the error bars of AAS.
Thi s reduces the si gni fi cance that coul d be at t ached to the di fference. A st at i st i cal t echni que
appr opr i at e for si t uat i ons where values come from mor e than one popul at i on (that is, where
t here are out l i ers) woul d be appr opr i at e for t he dat a sets we have generat ed in t hese exper-
iments. One such is the l og normal di st ri but i on [36]. Anot her is the use of robust statistics
[37]. A br i ef di scussi on of the use of this t echni que and its appl i cat i on to our resul t s are
gi ven in the Appendi x and Fi gs. 11 and 12. We are exami ni ng t he anal ysi s of our l ong- t er m
dat a (that is, >30 days of i mmersi on) to at t empt to per f or m l i fet i me pr edi ct i on based on
such st at i st i cal t echni ques for t hese coat i ng sampl es. Thi s anal ysi s wi l l be pr esent ed in a
l at er publ i cat i on.
Specific Comments on ENM Results: AAS Panels
For the AAS sampl es, al l the ENM pl ot s are similar. The R, values start around 108 I I 9
cm 2 and sharpl y decrease in a day or so to 1061"~. cm 2 ( o r sl i ght l y l ower) r emai ni ng rel at i vel y
100E+08
A A S S t a t i s t i c a l A n a l y s i s
E
o
100E+ 06
>
100E+05
. W
5:
ip i
J
20
- - - o - - St d D e v
, . . m - . R o b u s t SD
' l m J ~ . g
"'.. t, ,raP:: ,..
4 1 0 J I +
6 0 8 0 1 0 0
Immlrlton IIn,,4, ( d l y l )
FIG. 1 l - - Compar i s on of robust versus Gaussian standard deviation trR. f or AAS coating.
BI ERWAGEN ET AL. ON REPRODUCI BI LI TY OF ELECTROCHEMI CAL NOI SE DATA 439
1E+11
IE+I0
IE+09
5
1E+08
a 1E+07
1E+06
1E+05
i: i ~ i
B H H S t a t i s t i c a l A n a l y s i s
, , : ~ .
$ *
i :, , ?
e !
I I
20 40 60 80 100 120 140 160 180
Immersion Time, days
FIG. 12--Comparison of robust versus Gauss9 standard deviation (rR, f or BHH coating.
200
constant up to 20 days. Our current interpretation of this rapid drop in R, is that we are
observi ng the initial electrolyte penetration into the pol ymer film, and the system is probabl y
not in local steady state during the measurements. We believe this early time period of
immersion needs to be reexamined by ENM, but using a higher rate of data acquisition. This
is necessary to obtain locally "st at i onary" measurements that are required t o meet the criteria
shown by Bierwagen [32] to be required for the use of R, calculations to be valid. This will
be addressed in further work from our laboratory. Most specimen pairs then exhibit a sig-
nificant drop to 3 to 5 x 105 (five probes) and 105 (one probe) in the next data-gathering
period (namely, around 50 days). This value remains fairly steady through the final data-
gathering period (around 110 days). Correcting for area (50 cm2), most values appear to
come to a "st eady state" at 5 x 10 6 to 2 107 ohms-cm 2, which previous Rn data indicate
is in the "borderl i ne" range with respect to a system that will provide adequate corrosion
protection [7-9, 11, 17-19, 21, 22, 24].
Visual observation showed that after 118 (125) days' immersion in 3% NaCl at room
temperature, there was no corrosion. However, all twelve panels exhibited significant blis-
tering (0.5 to 3 mm) with typically between 6 and 20 blisters on each panel. All of the AAS
data show reproducible behavior in the ENM test. Not e that the AAS system is not a hull
paint system, but more of a system for above-waterline use, that is, it is not really intended
for continuous immersion. It takes up considerable quantities of water, and this allows some
ionization of carboxyl groups on this type of polymer. The blistering is probably osmotic.
The relatively low resistance suggests that eventually sufficient chloride ions will reach the
pai nt -met al interface to cause acceleration of the very low rate of corrosion reaction contin-
ually in place under the coatings.
Specific Comment s on ENM Results: BHH Panels
For t he BHH panel s, the R, behavi or of the six probes shown in Fi gs. 7 and 8 is mor e
vari abl e wi t hi n t he si x- pr obe set than the AAS set. Two probes, 4b and 6b, exhi bi t an i ni t i al
r api d fal l t o around 2 to 5 105 1) 9 cm 2, whi ch then remai ns steady. The four others, aft er
the t ypi cal sharp initial drop of R, from the hi gh initial value, mai nt ai n a hi gh val ue above
l07 to 1 0 8 ~' ) 9 c m 2 for 45 days. At around 80 to 90 days, t wo of t hese dr op to bet ween 105
and 106 l'~ 9 c m 2, but then r ecover to l 0 7 to 108 ~-~ " cm 2 to gi ve four panel s agai n at the
hi gher f l 9 cm 2 value. The final pai r (10b and 1 l b) mai nt ai n a val ue of R, > 107 ~ 9 cm 2
t hroughout the test. There is some evi dence for a fall bet ween 100 and 140 days and then
a rise agai n up to 194 days. However, the val ue is al ways above 108 f~ 9 cm 2.
At the end of the ENM test, t here was no apparent corrosi on vi si bl e on any panel s coat ed
with the BHH system. However, a DC resi st ance scan run at the end of t he exposure of the
t wo probes that had gi ven the initial low val ues of R, showed one panel of each pai r maki ng
up the pr obe had a l ow-resi st ance area in a comer. Cl ose i nspect i on showed a t i ny amount
of rusting. We bel i eve this smal l weak poi nt in each probe was enough of a l ow-resi st ance
area to gi ve t he smal l R,, values obser ved for t hese probes, because it is bel i eved that t he R,,
measur ement gi ves the paral l el resi st ance of the t wo panel s maki ng up t he probe. 5 The BHH
syst em is an epoxy r esi n- based syst em desi gned for cont i nuous i mmersi on, and no panel
fai l ed by visual i nspect i on within six mont hs. However, any l ow-resi st ance areas are pot ent i al
weak points, whi ch may in the l ong t erm fail to prevent corrosi on. Under stress condi t i ons
(for exampl e, flexing, t emperat ure cycl i ng or agi t at i on), at t ack at weak poi nt s is l i kel y ac-
cel erat ed. We bel i eve t hese dat a and the AAS dat a above show that t he R, measur ement is
excel l ent for di fferent i at i ng among the corrosi on prot ect i on the coat i ngs syst ems pr ovi de and
accurat e enough to di fferent i at e among the qual i t y of the i ndi vi dual panel sets t hat were
vi sual l y j udged to be equivalent. The dat a al so show that wi t h ENM, as wi t h ot her studies
of organi c coat i ngs, a mul t i pl e sampl e set (six to ten sampl es) is requi red because of the
vari at i on present in sampl e preparat i on. Thi s is di scussed below.
Comparison with Accel erat ed Test Results
The ENM resul t s agree very wel l wi t h the vi sual assessment of accel er at ed test results,
par t i cul ar l y the face (unscri bed area) results. These results are gi ven in Table 2. The obj ec-
t i vel y eval uat ed accel erat ed test showed average prot ect i on by AAS, whi ch was r epr oduci bl e
exact l y as was found in the ENM exper i ment s and as woul d be pr edi ct ed from the R, values.
The BHH sal t fog accel erat ed t est results were gener al l y bet t er than AAS but were vari abl e.
Thi s was agai n in good agreement with the ENM t est results.
Life Prediction Based on ENM Dat a
The t i me vari at i on of the noi se resi st ance, R,(t), const i t ut es a measure of the sl ow t i me
changes of prot ect i ve propert i es of the syst em that underl i e the l ocal l y t i me invariant "whi t e
noi se" propert i es of the (coat i ng + i nt erface + substrate) system. Thi s l ong-t erm t i me var-
i at i on of t he noi se resi st ance appears to be a par amet er that can be used for rel at i ve ranki ng
of (coat i ng + pret reat ment of the metal + substrate) syst ems, al l owi ng appr oxi mat e l i fet i me
predi ct i on of cor r osi on- pr ot ect i on l i fet i mes for such syst ems. It is a si ngl e paramet er, R,(t),
5 David Eden, statements made in the discussion of this paper at the Montreal Symposium, 17 May
1994.
that can be used to describe the present state of corrosion protection inherent in a system at
time t. From the data we have seen thus far [22-24], and also that seen be Skerry and
coworkers [7-9,11,17-19], R,,(t) values rapidly differentiate between coating samples on the
degree of corrosion-protection protection afforded by a given coating, and the length the R,
values maintain their relatively high values in immersion gives a relative estimate of the
lifetime of protection the coatings will provide. I f an absolute standard (that is, a coating
system for which a true lifetime is known from exposure) is included in the sample set, a
more accurate lifetime estimate may be given relative to this standard.
Spectral Analysis
Spectral analysis can also be performed on the raw ENM data, and results can be extracted
in the frequency domain relevant to the (coating + pretreatment of the metal + substrate)
system [38]. The application of spectral analysis to coatings is at a relatively early stage of
development, and we could find onl y one reference on the use of spectral data v i s a vis
coated metal substrates [39]. We intend to examine the raw time data using spectral tech-
niques available within DENIS or of our own development at a later date. But, at the present
time, we believe it woul d be premature for use to attempt to present any spectral analysis
results from our time-domain data.
Di s cus s i on of Reproduci bi l i t y o f Corros i on Test Resul t s f or Coat ed Met al Syst ems
General Issues o f Reproducibility in Coatings Testing
An ongoi ng issue with respect t o the testing of the corrosion-protection properties of
organic- coatings over metal substrates is the reproducibility of experimental test results.
Recent papers [26,27] show good examples of why this is so. Use of a single test method
like continuous salt fog testing for corrosion-protection lifetimes for coatings is no longer
considered acceptable. Modern corrosion testing of coatings performance now emphasizes
multiple test methods, including cyclic salt fog testing, EIS measurements, subjective visual
analysis of exposed panels, (corrosion + UV exposure) testing, and direct exposure testing
of multiple panels in known corrosive environments [7-11, 19-21, 27]? Before making con-
clusions on the reproducibility of ENM results on coated metal systems, a few comment s
are in order with respect to the state of the art on the testing of corrosion protection afforded
by coating.
Among the coatings science community, reproducibility of test data of any sort is known
to be very difficult to achieve. Replicates of coatings sample preparation, coatings applica-
tion, substrate replication, and so forth are needed t o avoid production of coatings materials
not "r obust " enough to provide the performance the "one time good" testing had predicted.
Coatings Film Thickness
The single largest source of errors in coatings test samples that have all been prepared
from a single test batch of the original coating is the lack of control of film thickness in
coatings application. In high-speed, high-precision coatings application processes such as
reverse roll coating, the best control that can be achieved is _+5%. 6 For most common
laboratory coatings application methods such as spraying, brushing, draw-down bars or dip-
6 D. Coyle, private communication, General Electric Research Laboratories, April 1993.
pi ng, the expect ed vari at i ons can be larger and can al so occur from poi nt to poi nt on the
coat i ng as wel l as from sampl e to sampl e. Our film t hi ckness dat a from Table l for air-
assi st ed spray appl i cat i on of the t hree-coat syst ems under st udy show that our appl i cat i on
procedures were good but still have a rel at i ve st andard devi at i on based on the mean t hi ckness
of + 7%. Fi l m t hi ckness vari at i ons have oft en caused pr obl ems in the anal ysi s of coat i ngs
data, especi al l y for such fi l m-t hi ckness-dependent measurement s as col or [40], opa c i t y] and
permeabi l i t y. Thi s makes it especi al l y i mport ant for mul t i pl e sampl es to be run for coat i ngs
testing, as wel l as for measur ement of film t hi cknesses to be carri ed out in conj unct i on wi t h
coat i ngs testing. Thi s is oft en difficult, however, because of the l ack of rapid, accurat e t ech-
niques for measuri ng coat i ng film t hi ckness. In Table 1, we gi ve dat a on our sampl es as
measured by an El comet er ~, a fi l m-t hi ckness measur ement devi ce dependent on l ocal film
capaci t ance for its values. These measurement s, t oget her wi t h visual i nspect i on of all panel s,
i ndi cat ed that fi l m t hi ckness was rel at i vel y wel l cont rol l ed in our experi ment s. However, it
was observed that, although t he i ndi vi dual coat s all had si mi l ar actual t hi ckness, t here was
more scatter among the t wo pai rs of BHH sampl es, whi ch gave a R, l ow compar ed wi t h the
four that had a hi gher Rn. Thi s al so appl i ed to t he mor e severel y bl i st er ed AAS sampl es. A
l ocal fi l m-t hi ckness fluctuation can cause a si gni fi cant corrosi on fai l ure to occur in an oth-
er wi se uni f or ml y coat ed sampl e, because corrosi on failure l oci oft en begi n as l ocal site
failures. Corrosi on fai l ure in coat ed syst ems is al ways a l ocal fai l ure that grows enough to
cause a si gni fi cant loss of function in appear ance or coat ed obj ect performance.
Coating Sample Preparation
The ot her l arge source of error in the t est i ng of coat i ngs is the bat ch-t o-bat ch vari at i on in
coat i ng propert i es, such as opaci t y, that occurs in the preparat i on of coat i ngs sampl es, es-
peci al l y in the laboratory. In an exami nat i on of the sources of vari at i on in the measurement s
of the opaci t y of coat i ngs, it was found that the l ack of r epr oduci bi l i t y of pai nt sampl e
preparat i on under l aborat ory condi t i ons was the l argest single source of vari at i on in opt i cal
dat a measur ement [31]. One can expect si mi l ar issues to ari se in the t est i ng of the corrosi on
prot ect i ve propert i es of coat i ngs. In our case, al l test panel s were prepared si mul t aneousl y
from the same bat ches, so this vari abl e does not pert ai n to the dat a above.
Substrate Variation
To the best of our ability, we at t empt ed to excl ude this i ssue as a vari abl e for our exper-
iments. We pur chased all of our gri t -bl ast ed panel s from a single suppl i er and st ored t hem
careful l y until all were coat ed. We bel i eve we have uni form substrates. However, in the
t est i ng of the corrosi on-prot ect i on propert i es of coat i ngs, vari at i on in t he qual i t y of the met al
substrate, its surface preparat i on and pret reat ment , and its general cl eanl i ness are al l very
i mport ant [41]. St ri ngent precaut i ons must be t aken to ensure pr oper wet t i ng of the subst rat e
by the coat i ng duri ng sampl e preparat i on for corrosi on testing [42]. Al t hough most workers
in the field are aware of the need for pr oper subst rat e preparat i on, it can be an i mport ant
source of scat t er in corrosi on testing unless consi derabl e precaut i ons are taken.
Possible Film Spatial Variations in X-Linking, Composition, and So Forth
Anot her feat ure of coat i ngs t hat must be consi dered in corrosi on t est i ng is the possi bi l i t y
of poi nt -t o-poi nt i nhomogenei t i es in coat i ng film propert i es. This has been obser ved in the
7 R. L. Harper, unpublished results, Sherwin-Williams Research Center, 1975.
BIERWAGEN ET AL. ON REPRODUCIBILITY OF ELECTROCHEMICAL NOISE DATA 4 4 3
resistance and corrosion testing of coatings [43, 44] and has been observed using radiotracer
techniques [45]. Kumins has discussed some of these effects with respect to common coatings
polymers in terms of permselectivity of ions in pol ymer films [46]. These references and
others [44,47,48] discuss the further complications that occur in protective coatings films
with respect to local variations in transport properties, especially the conductivity of the
coating film, and how immersion in electrolyte affects this coating property.
Conclusions
We believe our data indicate that ENM is a valid and useful technique for evaluating the
corrosion protection afforded by organic coatings in coated metal systems. The reproduci-
bility of ENM results is as good as that expected for a typical coating property measurement.
ENM data using R, as the parameter for our sample evaluations show the same results as
traditional objective exposure evaluations, but much more rapidly. Variations inherent in
coatings systems manifest themselves as variations in electrochemical properties in nominally
identical samples. This becomes apparent also in ENM characterization. This seems to in-
dicate that the accuracy and reproducibility of the ENM data exceed the accuracy and re-
producibility of sample preparation for coated metal systems. The above implies a need for
large sample sizes in electrochemical testing of coat i ng/ met al systems. ENM on coated metal
systems are potentially a valuable tool for the study of coatings. Data scatter can be handled.
ENM offers promise as a rapid way of ranking coatings as well as being the onl y measure-
ment that gives a semicontinuous time record of the type we have presented. With the further
potential of providing kinetic information from spectral analysis of the time series data, ENM
may be one of the most valuable tools that the corrosi on/ coat i ngs scientist can use. Different
local variations in thickness leading to local structural variation are the most likely reason
for the variability observed in the ENM and corrosion results.
Ac k nowl e dgme nt s
This work was supported by the Office of Naval Research under Grant N00014-93-1-
0013. The experimental assistance of Seva Balbyshev, John Munkberg, Peter Elliott, and
Charles Schiltz is also gratefully acknowledged.
APPENDIX
Robust Versus Gaussian R.
Figures 11 and 12 compare the Gaussian standard deviation with the robust standard
deviation. The Gaussian value determines the standard deviation based on the mean of all
points in the sample, in this case six panels. The robust method bases the standard deviation
on the median of the sample. This eliminates possible outliers in the sample, hence the term
"robust . " Equation 1 is used for the robust standard deviation [37]:
SDRoBUST = 1.483 median{abs[Xi - median(X,)] } (1)
where the 1.483 is a mathematically derived constant of proportionality, median replaces the
average, and the absolute value resolves any sign problems.
Re f e r e nc e s
[1] Blanc, G., Epelboin, I., Gabrielli, C., and Keddam, M., "Electrochemical Noise Generated by
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[2] Bertocci, U. and Kruger, J., "Studies of Passive Film Breakdown by Detection and Analysis of
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[3] Bertocci, U., "Applications of a Low Noise Potentiostat in Electrochemical Measurements," Journal
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[5] Searson, P. C. and Dawson, J. L., "Analysis of Electrochemical Noise Generated by Corroding
Electrodes under Open-Circuit Conditions," Journal of the Electrochemical Society, Vol. 135, 1988,
pp. 1908-1915.
[6] Williams, D. E., Westcott, C., and Fleischmann, M., "Stochastic Models of Pitting Corrosion of
Stainless Steels," Journal of the Electrochemical Society, Vol. 132, No. 8, 1985, pp. 1796--1804.
[7] Eden, D. A., Hoffman, M., and Skerry, B. S., "Application of Electrochemical Noise Measurements
to Coated Systems," in ACS Symposium Series, Vol. 322, Polymeric Materials f or Corrosion
Control, R. A. Dicke and E L. Floyd, Eds., ACS, 1986.
[8] Skerry, B. S. and Eden, D. A., "Characterisation of Coatings Performance Using Electrochemical
Noise Analysis," Progress in Organic Coatings, Vol. 19, 1991, pp. 379-396.
[9] Chen, C. T. and Skerry, B. S., "Assessing the Corrosion Resistance of Painted Steel by AC Im-
pedance and Electrochemical Noise Techniques," Corrosion, Vol. 47, 1991, pp. 598-611.
[10] Bastidas, J. M., Feliu, S., Jr., Morcillo, M., and Feliu, S., "Study of the Electrochemical Noise
Generated by the Mild Steel/Zinc-Rich Paint/NaCl Solution System," Progress in Organic Coat-
ings, Vol. 18, 1990, pp. 265-273.
[11] Skerry, B. S. and Eden, D. A., "Electrochemical Testing to Assess Corrosion Protective Coatings,"
Progress in Organic Coatings, Vol. 15, 1987, pp. 269-285.
[12] Gabrielli, C., Huet, E, and Keddam, M., "Investigation of Electrochemical Processes by Electro-
chemical Noise Analysis. Theoretical and Experimental Aspects in Potentiostatic Regime," Elec-
trochimica Acta, Vol. 31, 1990, pp. 1025-1039.
[13] Seralathan, M. and Rangarajan, S. K., "Fluctuation Phenomena in Electrochemistry, Part 1: The
Formalism," Journal of Electroanalytical Chemistry, Vol. 208, 1986, pp. 13-28.
[14] Seralathan, M. and Rangarajan, S. K., "Fluctuation Phenomena in Electrochemistry, Part II: Mod-
elling the Noise Sources," Journal of Electroanalytical Chemistry, Vol. 208, 1986, pp. 29-56.
[15] Okada, T., "A Theoretical Analysis of the Electrochemical Noise During the Induction Period of
Pitting Corrosion in Passive Metals: Part 1. The Current Noise Associated with the Adsorption/
Desorption Processes of Halide Ions on the Passive Film Surface," Journal of Electroanalytical
Chemistry, Vol. 297, 1991, pp. 349-359.
[16] Okada, T., "A Theoretical Analysis of the Electrochemical Noise During the Induction Period of
Pitting Corrosion in Passive Metals: Part 2. The Current Noise Associated with Halide Nucleus
Formation in the Passive Film, " Journal of Electroanalytical Chemistry, Vol. 297, 1991, pp.
361-375.
[17] Moon, M. and Skerry, B. S., "Interpretation of Corrosion Resistance Properties of Organic Paint
Films from Fractal Analysis of Electrochemical Noise Data and Implications for Paint Performance
Predictions," Journal of Coatings Technology, 1994.
[18] Skerry, B. S., Alavi, A., and Lindgren, K. L., "Environmental and Electrochemical Test Methods
for the Evaluation of Protective Organic Coatings," Journal of Coatings Technology, Vol. 60, No.
765, 1988, pp. 97-106.
[19] Skerry, B. S. and Simpson, C. H., "Combined Corrosion/Weathering Accelerated Testing of Coat-
ings for Corrosion Control," NACE-Corrosion 91, Paper 412.
[20] Simpson, C. H., Ray, C. J., and Skerry, B. S., "Accelerated Corrosion Testing of Industrial Main-
tenance Paints Using a Cyclic Corrosion Weathering Method," Journal of Protective Coatings and
Linings, Vol. 8, No. 5, 1991, pp. 28-36.
[21] Skerry, B. S., Chen, C.-T., and Ray, C. J., "Pigment Volume Concentration and Its Effect on the
Corrosion Resistance Properties of Organic Paint Films," Journal of Coatings Technology, Vol. 64,
No. 806, 1992, pp. 77-86.
[22] Mills, D. J., Bierwagen, G. P., Tallman, D. E., and Skerry, B. S., "Characterization of Corrosion
Under Marine Coatings by Electrochemical Noise Methods," Proceedings of the 12 'h International
Corrosion Congress, Vol. 1, Paper 486, 1993, pp. 182-193.
[23] Bierwagen, G. E, Mills, D. J., and Tallman, D. E., "Electrochemical Noise Methods as a Possible
In Situ Corrosion Sensing Technique," Proceedings of the 12 'h International Corrosion Congress,
Vol. 6, Paper 576, 1993, pp. 4208-4218.
[24] Bierwagen, G. E, Mills, D. J., Tallman, D. E., and Skerry, B. S., "'Assessment of the Protective
Properties of Marine Coating by Electrochemical Noise Techniques," paper presented at Electro-
chemical Society 183 ~a Meeting, New Orleans, LA, Oct. 1993.
[25] Mills, D. J., Bierwagen, G. E, Tallman, D. E., and Skerry, B. S., presentation at Carderock, MD,
Nov. 1993.
[26] Tait, W. S., "A Discussion of the Reliability of Electrochemical Impedance Spectroscopy Data from
Coated Metals," Division of Polymeric Materials: Science & Engineering Preprints, American
Chemical Society National Meeting, Denver, April 1993, p. 101.
[27] Tait, W. S., "Coping with Errors in Electrochemical Impedance Spectroscopy Data from Coated
Metals," Journal of Coatings Technology, Vol. 66, No. 834, 1994, pp. 59-62.
[28] Pangerinan, A. B. and Rhodes, E, "Barrier Property Comparison of Traditional Solvent-Borne and
New Low VOC Water-Borne Coatings," to be published in Journal of Coatings Technology, 1994.
[29] Mills, D. J. and Boden, E J., "A Novel Method of Testing and Monitoring Anti-Corrosion Organic
Coatings," Corrosion Science, Vol. 35, 1993, pp. 1311-1318.
[30] Daniels, E, Williams, J. W., Bender, E, Alberty, R., and Cornwell, C. D., in Experimental Physical
Chemistry, 6th ed., McGraw-Hill, New York, 1962, pp. 393-414.
[31] Hamilton, W. C., Statistics in Physical Science, Ronald Press, New York, 1964.
[32] Bierwagen, G. P., "Calculation of Noise Resistance from Simultaneous Electrochemical Voltage
and Current Noise Data," Journal of Electrochemical Society, Vol. 141, 1994, pp. 155-157.
[33] Bierwagen, G. E, Balbyshev, V., Mills, D. J., and Tallman, D. E., "Fundamental Considerations on
Electrochemical Noise Methods to Examine Corrosion Under Organic Coatings," presented at Cor-
rosion Protection by Organic Coatings, Cambridge, UK, Sept. 1994 to be published as special
Electrochemical Society Proceedings.
[34] Bacon, R. C., Smith, J. J., and Rugg, E M., "Electrolytic Resistance in Evaluating Protective Merit
of Coatings on Metals," Industrial Engineering and Chemistry, Vol. 40, 1948, pp. 161-167.
[35] Mills, D. J. and Boden, E J., "A Novel Method of Testing and Monitoring Anti-Corrosion Organic
Coatings," Corrosion Science, Vol. 35, 1993, pp. 1311-1318.
[36] Aitchison, The Lognormal Distribution, Oxford Press, 1972.
[37] Rousseeuw, E J. and Leroy, A. M., Robust Regression and Outlier Detection, Wiley, New York,
1987, Chap. I.
[38] Searson, E C. and Dawson, J. L., "Analysis of Electrochemical Noise Generated by Corroding
Electrodes Under Open-Circuit Conditions," Journal of the Electrochemical Society, Vol. 135, 1988,
pp. 1908-1915.
[39] Moon, M. and Skerry, B. S., Journal of Coatings Technology, in press.
[40] Bierwagen, G. P., "The Effect of Film Thickness Fluctuations on the Optical Properties of Coat-
ings," Color Research and Application, Vol. 17, 1992, pp. 284-292.
[41] Fultz, B. S. and Peart, J. W., "Surface Tolerant Coatings for Marine Service," Journal of Protective
Coatings & Linings, Feb. 1994, pp. 29-37.
[42] Skerry, B. S., Culhane, W. J., Smith, D. T., and Alavi, A., "Prewashing Commercially Supplied
Cold-Rolled Steel Test Panels and Its Effect on Coating Adhesion," Journal of Coatings Technology,
Vol. 62, No. 788, 1990, pp. 55-58.
[43] Mills, D. J. and Mayne, I. E. O., "The Inhomogenous Nature of Polymer Films and Its Effect on
Resistance Inhibition," in Corrosion Protection by Organic Coatings, NACE, 1981, pp. 12-17.
[44] Kinsella, E. M. and Mayne, J. E. O., "Ionic Conduction in Polymer Films, I: Influence of Electrolyte
on Resistance," British Polymer Journal, Vol. I, July 1969, pp. 173-176.
[45] Kumins, C. A., "Fundamental Adhesive and Corrosion Control Studies," Journal of Coatings Tech-
nology, Vol. 62, No. 781, 1990, p. 63.
[46] Kumins, C. A., "Electrochemical Properties of Protective Coatings," Official Digest FSPT, Vol. 32,
1960, pp. 843-861.
[47] Kinsella, E. M., Mayne, J, E. O., and Scantlebury, J. D., "Ionic Conduction in Polymer Films, III:
Influence of Temperature on Water Absorption," British Polymer Journal, Vol. 3, Jan. 1971, pp.
41-43.
[48] Mayne, J. E. O. and Mills, D. J., "Electrical Resistance Measurements in Relation to Protection
by Organic Coatings," JOCCA, Vol. 58, 1975, p. 155.
Jef f ery R. Kearns, l Dav i d A. Eden, 2 Ma x R. Yaffe, 3
Jef f erson V. Fahey, 4 Dav i d L. Rei chert , 5 and Dav i d C. Si l ver man 6
ASTM Standardization of Electrochemical
Noise Measurement
RE F E RE NCE : Kearns, J. R., Eden, D. A., Yaffe, M. R., Fahey, J. V., Reichert, D. L., and
Silverman, D. C., " ASTM St andar di zat i on of El ect r ochemi cal Noise Me a s ur e me nt , " Elec-
trochemical Noise Measurement for Corrosion Applications, ASTM STP 1277, Jeffery R.
Kearns, John R. Scully, Pierre R. Roberge, David L. Reichert, and John L. Dawson, Eds.,
Ameri can Society for Testing and Materials, 1996, pp. 446--470.
ABSTRACT: The increased utilization of electrochemical noise measurement in corrosion
research and industrial process monitoring prompted the formation in 1991 of an ASTM Task
Group within the G1 Corrosion of Metals Committee. The scope of the task group was to
"devel op standards that describe instruments and methods for making and analyzing electro-
chemical noise measurements. " Task group activities are focused exclusively on measurements
to be made in the laboratory. The initial goal has been to develop consensus on: (a) terminology,
(b) specifications and configurations for laboratory instrumentation, (c) laboratory apparatus,
and (d) data analysis methods. A round robin was also organized to develop a body of data
on different mat eri al / envi ronment systems using a variety of instrument configurations and
data analysis techniques. A guide for making valid electrochemical noise results is bei ng pre-
pared based on the round robin results. The status of the effort to address these and ot her
standardization issues wi t hi n t he ASTM G1.11.04 Task Group on Electrochemical Noise Mea-
surement will be presented.
KE Y WOR D S : electrochemical noise measurement (ENM), laboratory testing, electrochemical
tests, corrosion, test standards
Th e AS T M GI . 1 1 . 0 4 Tas k Gr o u p on El e c t r o c h e mi c a l Noi s e Me a s u r e me n t ha s r e c e nt l y
pr oduc e d a dr af t o f a St a nda r d Gu i d e f or El e c t r oc he mi c a l Noi s e Me a s u r e me n t ( he r e a f t e r
r e f e r r e d t o as t he s t andar d gui de) . The s t a nda r d gui de out l i nes pr oc e dur e s t o c h e c k i ns t r u-
me nt a t i on, c o n d u c t t est s, and a na l yz e da t a f or e l e c t r oc he mi c a l noi s e me a s u r e me n t . Two ba s i c
E NM me t h o d s ar e de s c r i be d i n t he s t a nda r d gui de:
Method A: Electrochemical current noise measurement (ECNM)--Measurement o f ECN
ma d e on a s ys t e m at o p e n ci r cui t pot ent i al .
Staff engineer, Al umi num Company of America, Alcoa Technical Center, Alcoa Center, PA 15069;
formerly with Allegheny Ludlum Corporation.
2 Development manager, Real Time Corrosion Management Limited, Rutherford House, Manchest er
Science Park, Manchester, M15 6SZ, UK.
3 Vice president, GAMRY Instruments, Inc., 607-C1 Easton Rd., Willow Grove, PA 19090.
4 Research chemist, Teledyne Wah Chang Division of Teledyne Industries, Inc., 1600 N.E. Old Salem
Rd., P.O. Box 460, Albany, OR, 97321.
5 Senior research engineer, DuPont Central R&D-DuPont Experimental Station, Rt. 141, P.O. Box
80323, Rm. 213B, Wilmington, DE 19880-0323.
6 Fellow, Monsanto, 800 N. Lindbergh Blvd., St. Louis, MO 63167.
446
www.astm.org
KEARNS ET AL. ON ASTM STANDARDIZATION OF ENM 4 4 7
Method B: Electrochemical potential noise measurement (EPNM)--Measurement of EPN
made on a syst em at open ci rcui t pot ent i al .
It is r ecogni zed that ot her met hods are possi bl e usi ng ei t her or bot h of the t wo basi c
processes of el ect rochemi cal current noi se (ECN) measur ement and el ect r ochemi cal pot ent i al
noi se (EPN) measurement . One such met hod is pr oposed in the ENM st andard gui de:
Method C: Potentiostatic noise measurement (PSNM)--Measurement of el ect r ochemi cal
current noi se made on a syst em that is under an appl i ed pot ent i al .
Met hod C is deri vat i ve of Met hod A pl us t he addi t i on of pot ent i al control.
An i nt erl aborat ory t est pr ogr am is bei ng conduct ed to pr ovi de reference dat a on several
al l oy/ envi r onment combi nat i ons i l l ust rat i ng di fferent modes of corrosi on. The resul t s to dat e
are present ed in this paper.
ASTM began t he devel opment on t he st andardi zat i on of ENM in May of 1992 wi t h the
first meet i ng of G1. 11. 04 Task Gr oup on El ect r ochemi cal Noi se Measurement . At t hat t i me,
t here was a consensus among t he t ask group member s that the avai l abi l i t y of a st andard
pr ocedur e and round robi n dat a on a vari et y of syst ems woul d faci l i t at e t he qual i fi cat i on of
equi pment and exper i ment al t echni ques. It was hoped that an ASTM st andard woul d l ead
to t he appearance of ENM dat a in t he l i t erat ure t hat coul d be compar ed wi t h confi dence.
The scope of t he t ask group was l i mi t ed to the appl i cat i on of ENM for corrosi on research
and l abor at or y testing. Thi s l i mi t at i on was est abl i shed by the t ask group because t he appl i -
cat i on of ENM to i ndust ri al pl ant corrosi on moni t or i ng or pl ant process cont rol usual l y
requi red knowl edge of pr opr i et ar y i nformat i on and product s. The current effort consi ders
onl y t he corrosi on of cert ai n ferrous and nonferrous al l oys. The t est i ng of coat ed met al s is
beyond t he scope of the present act i vi t y wi t hi n t he G1 commi t t ee and, t herefore, is not
di scussed in this paper.
The ENM st andard gui de was not i nt ended to be a t ut ori al on t he t heoret i cal aspect s of
t he measur ement or anal ysi s of noi se phenomena. However, many t echni cal t erms rel at ed to
ENM and di gi t al si gnal processi ng are defi ned to ai d t he user. A few si gni fi cant references
are al so ci t ed to pr omot e mor e det ai l ed i nvest i gat i ons.
The intent of the st andard gui de is to pr ovi de i nformat i on to enabl e a user to make
measurement s wi t h confi dence. It is not meant to be excl usi ve regardi ng i nst rument speci -
fi cat i ons or exper i ment al procedures. The st andard gui de may not be appr opr i at e for al l
mat eri al s, product forms, or envi ronment s and does not address al l t he i ssues rel evant t o al l
t he el ect roni c i nst rument at i on and ot her apparat us that have been or can be successful l y used
for ENM.
Terminology
Terms are defi ned in Appendi x XI : Ter mi nol ogy for El ect r ochemi cal Noi se Measurement .
These t erms are uni que to t he ASTM Commi t t ee G1 in the cont ext used in t he ENM st andard
gui de and do not appear in ASTM Ter mi nol ogy Rel at i ng t o Cor r osi on and Cor r osi on Test i ng
(G15). The t wo basi c t erms are:
El ect r ochemi cal noi se
El ect rochemi cal noi se
measur ement (ENM)
Fl uct uat i ons of pot ent i al or current, t ypi cal l y of low frequency ( < 10
Hz) and low ampl i t ude. El ect rochemi cal noi se ori gi nat es, in part,
from natural vari at i ons in el ect rochemi cal rate ki net i cs duri ng a cor-
rosi on process. El ect rochemi cal noi se is often regarded as a r andom
(st ochast i c) phenomena coupl ed to det ermi ni st i c kinetics.
Techni que i nvol vi ng acqui si t i on and anal ysi s of el ect rochemi cal
noi se data. Dat a are t ypi cal l y acqui red by moni t ori ng the evol ut i on
of a corrosi on process wi t hout the appl i cat i on of an ext ernal signal.
Al t ernat i vel y, pot ent i ost at i c or gal vanost at i c met hods can be used to
measure el ect rochemi cal pot ent i al or current noise, respect i vel y.
Various met hods of anal ysi s of the el ect r ochemi cal noi se dat a can
provi de i nformat i on concerni ng the nature of the corrosi on processes
and the magni t ude of the corrosi on rate for a gi ven system.
Because the val i dat i on and i nt erpret at i on of dat a can depend on the det ai l s of the el ect roni c
si gnal processi ng t echnol ogy used, a suppl ement al list of defi ni t i ons regardi ng el ect roni c
i nst rument at i on are given in Appendi x X2: Ter mi nol ogy for El ect roni c Inst rument at i on. Thi s
appendi x was prepared for the conveni ence of the user who has a backgr ound ot her than
el ect roni cs or el ect ri cal engi neeri ng. Some defi ni t i ons are l i mi t ed in scope as appropri at e for
the cont ent of ENM. For more i nformat i on, the r eader may want to refer to the IEEE Stan-
dard Dictionary of Electrical and Electronics Terms [1].
The r eader is advi sed that none of t hese t erms, or any of the ot her part s of the st andard
gui de descr i bed in this paper, has been appr oved by ASTM Commi t t ee G1 as of the dat e of
this publ i cat i on. The first official G 1.11 subcommi t t ee bal l ot for the st andard gui de on ENM
was i ssued in March of 1994.
Summary of the Standard ENM Guide
The st andard gui de descri bes a pr ocedur e for i nst rument cal i brat i on and represent at i ve
l aborat ory appl i cat i ons. The appl i cat i on consi st s of a procedure and apparat us for tests of
the general and l ocal i zed modes of corrosi on for ferrous and nonferrous al l oys. In general
t erms, t he st andard gui de is al so appl i cabl e t o coat ed met al s, but cert ai n addi t i onal factors
must be consi dered. The met hod of dat a t reat ment wi l l vary dependi ng on the part i cul ar
met al / envi r onment combi nat i on under consi derat i on.
El ect rochemi cal current noi se (ECN) and el ect rochemi cal pot ent i al noi se (EPN), as defined
in Met hods A and B, respect i vel y, can be measured t oget her or separat el y usi ng vari ous
di gi t al or anal og i nst rument s and various el ect rode configurations.
It is r ecommended that Met hods A and B be combi ned so as to measure si mul t aneousl y
ECN and EPN from a t hree-el ect rode confi gurat i on in whi ch two or al l t hree are nomi nal l y
the same. Met hod C represent s a di st i nct l y di fferent t echni que i nvol vi ng the measur ement
of ECN under pot ent i al cont rol [2]. Met hod C woul d involve a pot ent i ost at and a conven-
tional t hree-el ect rode cel l (for exampl e, see t he ASTM Test Met hod for Maki ng Pot ent i ost at i c
and Pot ent i odynami c Anodi c Pol ar i zat i on Measurement s [G 5] wi t h di fferent worki ng,
counter, and reference el ect rodes). The gal vanost at i c mode of ENM (that is, t he measur ement
of EPN under current cont rol ) was not expl i ci t l y defi ned for two reasons: (1) the member s
of the t ask group deci ded that the resources avai l abl e to produce a st andard gui de were
sufficient to address onl y t hese two approaches and (2) most commer ci al pot ent i ost at / gal -
vanost at s measure current mor e accurat el y than pot ent i al , maki ng the pot ent i ost at i c ENM
t he more accurat e of the t wo opt i ons.
Electrode Configuration
Two t ypes of t hree-el ect rode confi gurat i ons are descr i bed in the st andard guide. In the first
case, as descr i bed by Met hods A and B, the confi gurat i on i nvol ves t wo of the three el ect rodes
as worki ng el ect rodes prepared from the same al l oy so as to be nomi nal l y i dent i cal ; t hese
two el ect rodes are referred to as the worki ng el ect r ode pair. The t hi rd el ect rode in Met hod
A may be either:
Option 1--a l ow- i mpedance, l ow- noi se reference el ect rode or
Option 2- - i de nt i c a l to the ot her t wo e l e c t r ode s - - a pseudoreference el ect rode.
Not e in regard to Opt i on 1 that a l ow- i mpedance reference el ect rode is r ecommended
because hi gh- i mpedance reference el ect rodes t end to be mor e suscept i bl e to el ect rost at i c
pi ckup. It is desi rabl e to mi ni mi ze the bi as caused by such envi ronment al noise. Inst rument
groundi ng and i sol at i on (for exampl e, ground l oops) may al so bi as measurement s in three-
el ect rode systems.
In the second case, as descr i bed by Met hod C, the confi gurat i on i nvol ves a convent i onal
t hree-el ect rode arrangement si mi l ar to that descr i bed in the ASTM Test Met hod G 5. In bot h
cases, all t hree shall be exposed to the same corrosi on condi t i ons.
The measur ement of current and pot ent i al is di fferent in the t wo cases of el ect r ode con-
figuration j ust descri bed. In Met hod A, t he current bet ween the t wo speci mens in the worki ng
el ect rode pai r is measured. In Met hod B, the el ect rochemi cal pot ent i al di fference is measured
bet ween a reference or pseudoreference el ect rode and one wor ki ng el ect rode or bot h of the
worki ng el ect rodes in a wor ki ng el ect r ode pair. In Met hod C, whi ch is anal ogous to a con-
vent i onal t hree-el ect rode arrangement si mi l ar to that descr i bed in ASTM Test Met hod G 5,
the current is measured bet ween the wor ki ng el ect rode and an i nert count er el ect rode,
whereas the pot ent i al of the worki ng el ect rode is measured agai nst a reference el ect rode.
When t he t wo speci mens in a wor ki ng el ect rode pai r are not i ndi vi dual l y pol ar i zed by an
ext ernal source and are coupl ed t hrough a zero resi st ance ammet er (ZRA), the response of
the worki ng el ect rode pai r is equi val ent to a si ngl e el ect rode rel at i ve to t he reference el ec-
trode. The ZRA offset and the el ect r ode si ze may bi as this measurement . Ideal l y, the el ec-
t rochemi cal current noi se from the worki ng el ect rode pai r and the associ at ed el ect rochemi cal
pot ent i al noi se are pr oduced by corrosi on processes. Unfortunately, t here are many ot her
sources of noi se in the envi ronment and measuri ng i nst rument s [2-4].
Instrument Calibration
Cal i brat i on for ENM is cri t i cal because the magni t udes of t he el ect ri cal si gnal s of i nt erest
can be qui t e low and masked by i nt ri nsi c i nst rument at i on noise. In addi t i on, the i nst rument
may di st ort the si gnal s bei ng measured. Therefore, before ENM it is essent i al to det er mi ne
and mi ni mi ze the i nt ri nsi c noi se and di st ort i on of the measuri ng i nst rument at i on and cal i br at e
accordi ng to this basel i ne. Known sources of el ect ri cal noi se are used in the cal i brat i on
procedure descr i bed in the Ex p e r i me n t a l Pr o c e d u r e sect i on of this paper.
Signal Magnitude
The magni t udes of the signals obser ved in ENM of passi ve al l oys and act i vel y corrodi ng
met al s can vary over a wi de dynami c range. The pot ent i al noi se t ypi cal l y varies in the range
10 6 tO 10 -~ V, and t he current noi se t ypi cal l y vari es in the range 10 ~t to 10 -3 A. Coat ed
speci mens may requi re great er sensi t i vi t y to el ect rochemi cal current noi se [5].
Frequency Spectrum
The measur ement of EPN signals generat ed by freel y corrodi ng el ect rodes at frequenci es
great er than about 10 Hz can be very difficult because t he levels of such si gnal s are t ypi cal l y
less than 10 6 V. Therefore, convent i onal i nst rument at i on can i mpose a pract i cal l i mi t at i on
on the frequency range for el ect rochemi cal noi se measurement s from 1 0 - 4 t o l 0 Hz.
Data Analysis
ECN and EPN dat a can be deri ved from the measured el ect ri cal current s and pot ent i al s
by vari ous met hods of signal processi ng and dat a anal ysi s. Some of t he mor e popul ar met h-
ods are consi der ed in the st andard guide. At a basi c level, useful i nformat i on can be obt ai ned
from anal yzi ng j ust the ECNM or j ust t he EPNM dat a as a funct i on of t i me. Compar i sons
and correl at i ons of the ECNM and EPNM dat a can l ead to vari ous "noi se par amet er s. "
These subj ect s wi l l be present ed in mor e det ai l in the Di scussi on section.
Experimental Pr o c e d u r e
Electronic Instrumentation
ENM Quality--To obt ai n t he best possi bl e qual i t y of results from di gi t al i nst rument at i on,
the f ol l owi ng i ssues rel at ed to el ect roni c measuri ng i nst rument s shoul d be addressed: accu-
racy, preci si on, i nput i mpedance, drift, nul l i ng, vol t age offset, i nt ri nsi c el ect roni c noise, and
resol ut i on. The degree to whi ch cri t eri a rel at ed to t hese i ssues are met is di rect l y rel at ed to
the qual i t y and rel i abi l i t y of t he ENM. However, the l evel of ENM qual i t y requi red in a
part i cul ar situation must be det er mi ned by the user based on consi der at i on of the cor r odi ng
syst em of i nt erest and the ki nds of quest i ons bei ng asked about it.
A schemat i c of a common ENM apparat us is i l l ust rat ed in Fig. 1. The el ect roni c com-
ponent s are gr ouped as vol t age- and cur r ent - measur i ng i nst rument s as descr i bed below.
Not e that the l i mi t s est abl i shed for frequency, current, and pot ent i al mandat e a l evel of
resol ut i on. The resol ut i on of an i nst rument is i nt ri nsi cal l y t i ed to the rat e of dat a conversi on.
Current- and vol t age- measur i ng i nst rument s wi t h conversi on rates equi val ent to 16 bi t s wi t h
a 90-dB dynami c range shoul d pr oduce excel l ent results for most syst ems. Low- l evel si gnal s
oft en associ at ed wi t h coat i ngs or passi ve fi l ms may requi re an effective 20-bi t conversi on
rat e wi t h a 120-dB dynami c range. (An "effect i ve 20-bi t conversi on r at e" does not neces-
sari l y requi re the use of a 20-bi t anal og- t o- di gi t al [ A/ D] converter, but one must consi der
the effect of convert er errors on resol ut i on. )
It is r ecogni zed that some of t he i nst rument speci fi cat i ons r ecommended bel ow may chal -
l enge the capabi l i t i es of current commer ci al i nst rument s market ed for corrosi on testing. The
r ecommended i nst rument speci fi cat i ons are not i nt ended to be excl usi ve, but rat her are in-
t ended to opt i mi ze the pr eci si on and bi as of a t est and to mi ni mi ze uncert ai nt i es in dat a
anal ysi s and i nt erpret at i on. The level of i nst rument resol ut i on requi red depends on the nature
of the corrosi on process of i nt erest and t he t ypes of i nformat i on that a wor ker want s to obt ai n
about it. Cert ai nl y, meani ngful dat a have been obt ai ned by usi ng ver y si mpl e i nst rument
confi gurat i ons [6,7]. The numbers r ecommended bel ow al so reflect r ecent t rends in pri ces
for el ect roni cs (specifically, 61/2 di gi t di gi t al vol t met ers are now avai l abl e from maj or man-
ufact ures for j ust under $1000).
KEARNS ET AL. ON ASTM STANDARDIZATION OF ENM 451
FIG. l--Schematic
~ , , ,,
u l
ENM apparatus.
Voltage-Measuring Instruments--The vol t age- measur i ng ci rcui t should have a hi gh-i nput
i mpedance at l east 100 t i mes the sum of charge t ransfer resi st ance and sol ut i on resi st ance
for a gi ven syst em. Input i mpedances on t he or der of 10 ]~ to 1014 IZ are desi r abl e but not
necessar i l y requi red to mi ni mi ze current drawn from the syst em duri ng el ect rochemi cal mea-
surement s. An i nst rument capabl e of accurat el y measuri ng a pot ent i al of 10 -6 in the presence
of a 1-V DC signal at the hi ghest frequency to be measured is r ecommended.
Current-Measuring Instruments--An i nst rument capabl e of accurat el y measuri ng a current
over a range bet ween 10 ]] and 10 -3 A at the hi ghest frequency to be measur ed is r ecom-
mended. Two opt i ons for a met hod to measure current are descr i bed below.
Option 1: Zero resistance ammeter (ZRA) opt i on- - A ZRA that i ncorporat es a l ow-offset
vol t age, l ow-noi se operat i onal ampl i fi er and several pr eci si on measuri ng resi st ors to
accommodat e a range of current si gnal s from nanoamps to mi l l i amps 0 0 -9 to 10 -3 A).
The ZRA shoul d be capabl e of mai nt ai ni ng a pot ent i al di fference bet ween the t wo
speci mens of a wor ki ng el ect r ode pai r at 1 t~V or l ess and shoul d have very low noi se
in t he frequency range 10 -4 t o l 0 Hz. The ZRA shoul d not i mpose a l oad on the
measur ement circuit. (See Appendi x X3 and Ref 8 for i nformat i on on the const ruct i on
and t est i ng of a ZRA. )
Option 2: Resistor opt i on--The current bet ween t wo wor ki ng el ect rodes is measured as
t he vol t age dr op across a resi st or pl aced bet ween the t wo speci mens of a wor ki ng
el ect r ode pair. The effect of the vol t age dr op in the syst em shoul d be consi der ed for
each syst em, and a maxi mum accept abl e val ue for t he vol t age dr op (for exampl e, 1
mV) shoul d be specified. For exampl e, a 1-ohm resi st or has been successful l y used for
carbon st eel in chl or i de sol ut i ons [7].
Not e that t he pr i mar y advant age of Opt i on 2 over Opt i on 1 is the avoi dance of ext raneous
f eedback bet ween the syst em bei ng moni t or ed and the measur i ng circuit. The di sadvant age
of Opt i on 2 is that t he vol t age drop across t he resi st or pol ar i zes one el ect rode rel at i ve to t he
ot her in t he pair. The si gni fi cance of the bi as resul t i ng from ei t her effect on the qual i t y of
t he ENM must be det er mi ned by the user.
Potentiostat/Galvanostat--A pot ent i ost at / gal vanost at can al so be used in Met hods A and
B pr ovi ded that current and pot ent i al can be measured si mul t aneousl y and i ndependent l y.
Ei t her the current or the pot ent i al can be measured alone, but the si mul t aneous measur ement
of bot h is r ecommended for opt i mum versat i l i t y in subsequent dat a anal ysi s. Speci fi cat i ons
for a pot ent i ost at / gal vanost at are gi ven in ASTM Test Met hod G 5. Dependi ng on t he desi gn
of the pot ent i ost at , the measur ement of current noi se from a worki ng el ect rode pai r may be
by means of ei t her a set of measuri ng resi st ors or a ZRA; the l at t er met hod is r ecommended
over the former method.
A pot ent i ost at is requi red to perform the pr oposed Met hod C, but, as previ ousl y stated,
the consi derat i on of pot ent i ost at i c el ect r ochemi cal noi se measurement s is beyond t he scope
of the ASTM t ask group and this paper. It must be poi nt ed out that much useful i nformat i on
has been obt ai ned by pot ent i ost at i c ENM t echni ques [2,9-12].
Recording Device--The pot ent i al and current signals are recorded cont i nuousl y usi ng a
personal comput er (PC) or a strip chart er recorder. In the former case, it is r ecommended
that ei t her a combi nat i on of a current and pot ent i al measuri ng i nst rument s or a scanni ng
pot ent i ost at be i nt erfaced with the PC. Numerous opt i ons for hardware and soft ware to
col l ect and anal yze dat a from the peri pheral i nst rument s are commer ci al l y avai l abl e. The
st orage requi rement s for some ENM may be subst ant i al and should be consi dered. St orage
requi rement s depend pr i mar i l y on the speci fi ed sampl i ng frequency (0.5 to 2 Hz are used
often for corrosi on studies) and the test period. The former factor is det er mi ned in part by
the t ype of dat a anal ysi s that is to be performed. Fi nal l y, the PC shoul d al so be i nt erfaced
wi t h an appropri at e output devi ce, such as a printer.
Electrochemical Cell--The test cel l shoul d be const ruct ed to al l ow the fol l owi ng i t ems to
be inserted i nt o t he sol ut i on chamber: t he wor ki ng el ect r ode pair, a reference or pseudo-
reference el ect rode, and a t hermomet er. Openi ngs in the cel l for gas i nl et and outlet shoul d
al so be provi ded. The test cel l shall be const ruct ed of mat eri al s that wi l l not corrode, det e-
ri orat e, or ot herwi se cont ami nat e the test solution. Bor osi l i cat e glass and TFE- f l uor ocar bon
have been found suitable.
The wor ki ng el ect rode pai r shall be prepared from the same pi ece of speci men mat eri al .
Each shall have a t ot al i mmer sed surface ar ea of at l east 1 cm 2.
A l ow- i mpedance, l ow-noi se reference el ect r ode is r ecommended. A sat urat ed si l ver / si l ver
chl ori de el ect r ode with a low rate of l eakage (about 3 ~L/ h ) has been found to be suit-
abl e [13]. The most appropri at e reference el ect r ode and bri dge for a gi ven envi ronment wi l l
vary [14].
A conduct i ve br i dge bet ween reference and worki ng el ect rodes may cont ri but e to the
i nt ri nsi c noi se of the measuri ng system. The use of a hi gh- i mpedance reference el ect r ode
j unct i on is not r ecommended because of noi se (60-Hz) pi ckup associ at ed wi t h such hi gh-
i mpedance apparat us. However, a conduct i ve br i dge bet ween the el ect rol yt e and reference
el ect r ode may not be needed because no current is bei ng ext ernal l y appl i ed in Met hods A
and B. I f one is to be used, a capi l l ar y- t ype Luggi n probe is r ecommended over one wi t h a
semi per meabl e membr ane or porous flit.
A pseudoreference el ect rode may be used i nst ead of a convent i onal reference el ect rode to
measure EPN. It is best to use a mat eri al i dent i cal to the el ect rode pai r that has ei t her the
same area of one worki ng el ect r ode or the sum of the t wo areas of the wor ki ng el ect rodes.
When an i dent i cal mat eri al is not used, it is r ecommended that the pseudoreference el ect r ode
have noi se charact eri st i cs that are not great er than the magni t ude of the pot ent i al noi se signal
to be measured. The charact eri st i c pot ent i al noi se of the pseudoel ect r ode in the el ect r ol yt e
should be measured and subt ract ed as backgr ound noi se f r om the noi se measur ed f r om t he
wor ki ng el ect rode pair.
Calibration of Instrumentation
Calibration for ENM is important because (1) the electrochemical cell is not being driven
by an external source (Methods A and B), (2) the levels of signals of interest can be quite
low and can be masked by intrinsic instrument noise, (3) the measuring instrument may
distort the measured signals, and (4) the worki ng environment often generates noise that is
not related to corrosion. Therefore, it is important to calibrate for intrinsic instrumentation
noise, distortion, and the response to DC and low-frequency signals. It is also important to
verify instrument characteristics. As with polarization and electrochemical impedance spec-
troscopy (EIS) tests, a dummy cell can be used instead of an electrochemical cell for cali-
bration and verification. One difference is that a known source of "noi se" must be used.
One possible test circuit is shown in Fig. 2.
In Fig. 2, the I - V peak-to-peak ( p- p) sine wave is used to generate a known "noi se"
signal. This signal is then translated to a 1-1~A p - p current signal to the ZRA and a 1-mV
voltage signal to the electrometer. Depending on the instruments, either the ZRA or the
signal generator may need to be electrically isolated. The resistor values, signal level and
the signal frequency may be adjusted to match the particular electrochemical system and
noise characteristics being investigated. For example, if the electrochemical system gives rise
to 10-mV voltage fluctuations, a 1 kO/ 99 kO voltage divider may be indicated.
Verification of Instrumentation Characteristics--Statistical analysis and frequency domai n
transforms [15-17], such as a fast fourier transform (FFI' ) or the smoother maxi mum entropy
met hod (MEM) [18], can be used to analyze results and thereby verify the instrumentation
characteristics. This calibration technique requires the use of known, low-frequency sine
wave sources, such as a signal generator or a frequency response analyzer. The statistical
analysis of such a low-frequency sine wave source should give a standard predictable re-
sponse. The FFI" or MEM should provide a precise indication of both the amplitude and
frequency of such a signal.
Method for Calibration with Respect to the Intrinsic Instrumentation Noise--In addition
to the normal calibration of an instrument, it is necessary to evaluate the noise characteristics
of the instrument and the ability of the instrument to reject environmental noise (for example,
interference from power lines or switching transients). To achieve this, the baseline current
and potential noise signals need to be measured. The following method is recommended.
U - -
W E I
G e ~ r
I M ~
2 ~ I signal
99.9 k~ y
E s ~nal
FIG. 2--Equivalent circuit test cell for calibrating ENM instrumentation.
Option / - - S h o r t ci rcui t the pot ent i al measurement t ermi nal s to ground. Thi s shoul d gi ve
a pot ent i al readi ng of 1 ixV or less of i nst rument noise. For the current noi se measure-
ment, the i nst rument l eads can be l eft as an open ci rcui t ( "dangl i ng l eads") . Inst rument
current noi se levels l ower t han 10 -~' A in the bandwi dt h from 0 to 10 Hz can be
obt ai ned wi t h the correct i nst rument at i on. Ti me records obt ai ned in this confi gurat i on
can then be used to charact eri ze the basel i ne noi se ari si ng from i nst rument at i on and
ext raneous effects.
Option 2 - - A I - V p- p, l - Hz si ne wave is appl i ed usi ng the signal generator. Current and
vol t age versus t i me records are obt ai ned by sampl i ng at 0.1 s ampl es / s . The si gnal s are
sampl ed for at l east 10.24 s to yi el d 1024 dat a points. Fi gur e 3 (top) is a sampl e of a
vol t age versus t i me trace. These dat a are then t r ansf or med to the frequency domai n
usi ng a Four i er transform. (Not e that ot her met hods of t ransformi ng the dat a are ac-
cept abl e). The resul t i ng pl ot of the nor mal i zed FFF is shown in Fi g. 3 (bot t om). Thi s
pl ot i ndi cat es that the i nst rument - and envi ronment -i nduced noi se vol t age is mor e than
t wo decades bel ow the 1-mV signal of interest.
Met hod o f Calibration in Terms o f Response to DC and Low-Frequency Si gnal s - - The
same dat a shown in Fig. 3 can be used to ext ract est i mat es of i nst rument al bi as bot h of DC
and AC signals. One caveat is that the cal i br at i on will onl y be as good as the signal gener at or
0. 8
0 . 8
0. 4
d
m 0. 2
o
>
0
- 0. 2
- 0 . 4
2 0 4 0 6 0 8 0 1 O0
time, s e c
1 2 0
t I i I u
G1
E o.m
0 O.O01
1 . 1 0 - 5 , J I ! l
1 2 3 4 5
Frequency, Hz
FIG. 3- - A voltage-time trace (top) and the Fourier transform of it (bottom) used to characterize the
intrinsic noise of ENM instrumentation.
and the resistors making up the dummy cell. These should be independently calibrated. These
errors, once known, can be mathematically removed in the data treatment.
The DC characteristic can be obtained by simply calculating the mean of the current and
voltage traces over an integral number of cycles. Alternatively, the FFT at 0 Hz may be used
to arrive at the DC offset mean (see Fig. 3).
The AC instrument characteristics may also be obtained from either the time domain or
frequency domain plots. It is useful to compare the acquired trace to the expected trace.
Figure 4 shows such a comparison. At this particular frequency, the instrument is attenuating
and phase shifting the AC signal as well as causing a DC offset. This same measurement
can be made in the frequency domain by compari ng the FFF of the measured trace to the
FFT of the expected trace. Several test curves at frequencies throughout the range of interest
should be run to characterize fully the instrument.
Procedure f or ENM
The use of the step-by-step procedures presented in the standard guide will enable the
user to obtain a result that can be compared with confidence to a set of reference data, such
as that contained in this section. The procedures presented in the standard guide are not to
be viewed as the only way for making ENM, but merely represent specific combinations of
the various options described in the previous sections. A round robin is currently being
conducted to provide information on a range of options for making ENM in terms of ma-
terials, environments, and laboratory apparatus.
Test Materials and Environments--The following combinations of working electrodes and
electrolytes are being evaluated in a round robin test program to develop reference data:
A- - Mi l d steel: AI SI 1018 rod in 0. 1M citric acid at 25~
B- - AS TM Electrochemical Test Standard: AI SI Type 430 stainless steel in 0. 495M
Na2SO4 + 0. 005M HzSO 4 at 30~ (specimen and solution per the ASTM Practice for
Verification of Al gori t hm and Equipment for Electrochemical Impedance Measure-
ments (G 106)
>
E
O
>
0.5
-0.5
- i . /
I I
i measured '
] ~ i l
l
\ / y
I
expected
I
2
/
V V 'V
i ~
! i
i
I
- 1 I 1. I
0 4 6 8 10
time, s e c
F I G . 4- - AC instrument characteristics determined by comparing a measured voltage-time curve ( s o l i d
l i n e s ) to that expected for the input ( d o t t e d l i n e s ) used to determine the bias of the ENM instrumentation.
REFERENCE I'HERMOIVETER PSEUDO-REFERENCE . "~ERE, IOME"~R
ELECI ~ODE ELECTRODE
WORKING WORKING WORKING WORKING
ELECTRODE ELECTRODE ELECTRODE ELECTRODE
1 2 Z 1
A B
FIG. 5--El ect rochemi cal cell f or ENM with three AI SI 1018 steel rod electrodes. Two options shown:
with a reference electrode (A) and with a pseudoreference electrode identical to those in the working
electrode pai r (B).
C- - Zi r c o n i u m alloy: Zircadyne| al l oy in 10% HC1 wi t h the t i med addi t i on of 500
M ppm ferric ion ( added as 2. 42- g/ L FeC13 9 H20) at 25~
D- - Al u mi n u m al l oy: AA 7075-T7 wi t h t he t i med addi t i on of 1000-ppm NaCI sol ut i ons
at 25~
Syst ems A and B wi l l corrode in a general mode, whereas the ot her t wo wi l l suffer l ocal i zed
corrosi on. The response of Syst ems A and B can be veri fi ed usi ng ot her el ect r ochemi cal
t echni ques (for exampl e, EIS or l i ner pol ari zat i on resi st ance) or mass-l oss measurement . The
results of the ot hers should be verified by vi sual and gravi met ri c observat i on of the speci mens
aft er the test. It is suspect ed that di fference in the behavi or of the syst ems l i st ed above wi l l
requi re separat e test procedures and anal ysi s t echni ques for each.
Test Sy s t e m A - - A I S I 1018 s t e e l i n ci t ri c aci d: The det ai l ed procedure for AI SI 1018 in
ci t ri c aci d that is bei ng used in round robi n testing pr ogr am is present ed in Appendi x X4.
The cel l confi gurat i on is shown in Fig. 5A. It is basi cal l y the same as t he round bot t om flask
wi t h various necks as descr i bed in ASTM Test Met hod G 5 wi t h the i mport ant except i on of
the number and t ype of el ect rodes used. A react i on kettle wi t h a l i d coul d al so be used. A
wor ki ng el ect r ode pair, one reference (or pseudoreference i dent i cal to the worki ng el ect r ode
pai r) el ect rode, gas i nl et and outlet tubes, and a t her momet er are to be mount ed in t he cel l .
The pr el i mi nar y round robi n results shown in Fig. 6 were from a pai r of 5- mm- di amet er
steel rods, each wi t h an exposed area of 12.5 cm 2, and a fl ow-j unct i on t ype sat urat ed cal omel
reference el ect rode.
Dat a for the AI SI 1018 steel in ci t ri c aci d syst em were obt ai ned usi ng a commer ci al
pot ent i ost at and cust omi zed soft ware to acqui re current and pot ent i al si gnal si mul t aneousl y.
The speci fi cat i ons for di gi t al signal processi ng were as fol l ows: The current and pot ent i al
ci rcui t s of a commer ci al pot ent i ost at were bandwi dt h l i mi t ed to (below) 5.3 Hz by l ow-pass
filters. Each measur ement (current and pot ent i al ) was per f or med at a frequency of 1 Hz.
Af t er col l ect i on of 256 measurement s of bot h current and pot ent i al , the RMS val ues for the
ECNM and EPNM were comput ed and r ecor ded al ong with the t i me (as durat i on of the
exper i ment in seconds). Mean values for t he coupl i ng current and open ci rcui t pot ent i al over
7 Zircadyne is a registered trademark of Teledyne Wah Chang Division of Teledyne Industries, Inc.
KEARNS ET AL. ON ASTM STANDARDI ZATI ON OF ENM 457
r ~
518-6
4]E-6
$ ~ E - 6
2, ~6
ll~-6
OEO
i i , i , i ,
' 1 0 ' 2 0 3 0 4 0
Ti me, hours
- 3B- 5
--4JB-5
- ~R- $
~ B - 5
-TJ~5
- 8 ~ 5
~ E - 5
5O
0.0035
0.0030
9 ~ 0~025
Z
0.0020
0.0015
O'1
0.0010
0.0005
' o 2 ' o ~ ' o
Ti me, hours
-0.$3
0
,.O.56
0
0
-0,57
0
-0.58
0
,0.$9 ~
50
FIG. 6--ENM data for AISI 1018 steel in O.1M citric acid. The ECNM and coupling current data
(top) were obtained simultaneously with the EPNM and corrosion potential data (bottom).
a 256-s per i od were al so measured concurrent l y wi t h the ENM data. The results over a 45-
h per i od appear in Fi g. 6. The R, values were cal cul at ed as the rat i o of the mean RMS
EPNM val ue to the mean RMS ECNM val ue [19].
Dat a obt ai ned for the AI SI 1018 steel in ci t ri c aci d syst em are present ed in Fi gs. 6 and
7. The RMS val ues for the ECNM and EPNM dat a over a 45-h per i od are present ed in Fi g.
6 al ong wi t h coupl i ng current and open ci rcui t pot ent i al records, all of whi ch were measured
si mul t aneousl y.
Test System B- - AI SI Type 430 stainless steel in sulfuric acid-sulfate solution: The speci -
fications for sol ut i on and sampl e preparat i on and speci men mount i ng were t he same as
ASTM Pract i ce G 106. The pri nci pal di fference is that t hree Type 430 test speci mens were
used, each mount ed on the el ect r ode hol der shown in Fi g. 3 of ASTM Test Met hod G 5.
Three nomi nal l y i dent i cal Type 430 el ect rodes were pl aced in the cel l in the posi t i ons mar ked
WE1, WE2, and pseudoreference el ect rode, as shown in Fi g. 5B. The i nst rument and met hods
used in this eval uat i on are descr i bed el sewhere in this vol ume (see Rei chert , in this vol ume).
One represent at i ve dat a set is present ed in Fi g. 8. Each dat a set consi st ed of 1024 poi nt s
acqui red at a rat e of 1 Hz once every hour over a 48-h peri od. Corrosi on rates were cal cul at ed
from the R, val ues by the fol l owi ng equation:
MPY = 9289/ {R, * 5/ [ ( 2) ,/2)]}
458 E L E C T R O C H E MI C A L N O I S E ME A S U R E ME N T
! 1 0 0 0
10000
~ . 9OOO
o gooo
o ~ 7 0 0 0
9 = s o o o
i ~ 4 0 0 0
=O 3OO0
, = o
1 0 0 0
! 0 3 40
Time, hours
5' 0
FIG. 7--Electrochemical noise resistance f or AISI 1018 steel in O. I M citric acid as calculated from
the data in Fig. 6.
4 . 8 5 ' ' ' = ' ' ' = ' ' ' = ' ' ' I ' ' ' I ' ' '
4 . 8 -
' ~ 4 . 7 5 -
z
o 4. 7-
4 . 6 5 -
4 . 6
0 2 0 0 4 0 0
~ f q q q q ~ J [ q ~ ~ ~
6 0 0 8 0 0 1 0 0 0 1 2 0 0
T i me , s e c
- 0 . 2
> - 0 . 4
E
I ~ - 0 . 6
Z
n
LU - 0 . 8
-1
- 1 . 2
0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0
T i me , s e c
FIG. 8- - ENM data f or AISI Type 430 stainless steel in 0.495M NazSO 4 + 0.005~/1 H2SO 4 (specimen
and solution per ASTM Practice G 106). The ECNM data ( t op) were obtained simultaneously with the
EPNM data ( bot t om) .
Di scussi on
The initial goal of the ASTM ENM task group was to develop consensus on: (1) termi-
nology, (2) specifications and configurations for laboratory instrumentation, (3) laboratory
apparatus, (4) reference data sets t o which measurements can be compared, and (5) data
analysis methods: The first three items have been presented above. Results representing the
first step toward establishing reference data sets are discussed below along with an overview
of the most popular methods for data processi ng/ anal ysi s and presentation.
Preliminary Round Robin Testing
The purpose of the evaluation of the t wo systems discussed below was to develop test
met hodol ogy (Appendix X3) and reference data sets (Figs. 6 t hrough 8) for a larger round
robin testing program to be sponsored by ASTM. The evaluations should therefore be con-
sidered work in progress.
Test System A- - AI SI 1018 Steel in Citric Aci d- - The variations in the EPN in the first few
hours of the experiment (see Fig. 6) reflect the dissolution of a rough, irregular steel rod
surface. The electrodes were gradually coated with a black corrosion product, which resulted
in a decrease in EPN. The trends in the current correlated with the potential signals. The
signals appeared fairly random, as woul d be expected of an alloy undergoing a general mode
of corrosion. (The steplike appearance of the mean potential data is due to the relatively
low, 1-mV resolution of the potential measuring circuit.) The ECN values shown in Fig. 6
are steady during the experiment, as would be expected in uniform corrosion. The mean
current flowing between the two electrodes increases toward a constant current value. The
fact that the mean current is not zero may be a result of a slight bias applied between the
two electrodes by the measuring instrument or it may be a galvanic current flowing between
the t wo discrete but nominally identical electrodes. A similar study of the active dissolution
of mild steel in diluted sulfuric acid demonstrated good agreement between the electrochem-
ical noise measurements, electrochemical impedance and weight loss [6].
The resistance noise shown in Fig. 7 was comput ed by dividing the potential noise by the
current noise. The overall shape of the resistance noise curve is dominated by the shape of
the EPN curve because the ECN curve is essentially constant. Close inspection of the po-
tential noise shows a correlation of high EPN with both steps in the mean potential and with
the frequency of those steps. The potential and resistance noise would appear to be biased
by the 1-mV resolution of the measuring instrument (that is, 1-mV quantization error). How-
ever, the resistance noise is consistent with independent measurements of polarization resis-
tance by linear polarization and EIS techniques. All three results are consistent with corrosion
rates of 2 mm/ ye a r as determined by mass loss measurements.
Test System B- - ASTM Electrochemical Test Standard: AISI Type 430 Stainless Steel in
Sulfuric Acid-Sulfate Solution--The baseline EPNM and ECNM from the monitoring equip-
ment were both t wo orders of magnitude lower than the electrochemical noise generated by
the corrosion Type 430. The baseline ENM data were collected by leaving the potential leads
as an open circuit and short circuiting the current leads.
The average corrosion rate calculated from R, values over the 48-h test period was 6.9
MPY. The range was from a maxi mum 68.3 MPY during the third hour of exposure t o a
mi ni mum of 0.102 MPY during Hour 39. The corrosion rates determined by mass loss for
the three electrodes after the 48-h exposure were 45, 46, and 46 MPY. Obviously, more
work is required t o better correlate the corrosion rates determined by mass loss and ENM
in this system. It is useful to consider that in the round robin conducted on this same system
for ASTM Practice G 106, it was also found that the corrosion rates as calculated from the
Rp values did not agree with those based on mass loss measurements.
Analysis of Electrochemical Noise Measurement Data
As previously stated, the scope of the task group is to describe instruments and methods
for making and analyzing ENM. The interpretation of ENM data was regarded as too con-
troversial an area to standardize. This section rfierely attempts to summarize some trends
apparent in the work on the analysis of ENM data. A few of these methods may eventually
prove to be preferred for certain systems and, therefore, suitable for standardization. Until
then, an appropriate recommendat i on is to try a variety of analysis techniques to find one
most suited for a given system.
Analysis of ENM data involves the characterization of low-amplitude, low-frequency, ran-
dom fluctuations of current and potential signals from electrochemical systems [11,20-27].
The sources of the noise signals have been ascribed to various processes including diffusion
within electrolytes [26] or membranes, diffusion through oxide films, electronic effects within
the film [24,28], and hydrogen gas bubble release [2]. The most important data represent the
current and potential transients related to metal dissolution or cathodic processes or both that
constitute a corrosion process [2,25-27,29-32]. ENM has been used for a variety of purposes
from determining general corrosion rates to discriminating the initiation and propagation of
localized corrosion [33].
The methods for signal analysis and conventions for data display have undergone consid-
erable development over the past decade. The ongoi ng effort to improve the visualization of
ENM data is done, in part, to improve the interpretation of ENM data. In addition, the
commercial electronic instruments often used for ENM, such as digital multimeters, are
continually being improved in quality and reduced in price. This is also true of the personal
computers and software available for interfacing of such instruments for efficient data col-
lection and analysis. The apparatus and data analysis techniques must be designed to meet
specific requirements depending on the application.
Results obtained by following the standard procedure in the standard guide can be pre-
sented in many ways, such as the following:
(1) mean coupling current (Ic~) and corrosion potential (Eeoc) versus time;
(2) electrochemical current noise (I,) and electrochemical potential noise (V,) versus time;
(3) root mean square (RMS) current ( ~) and RMS potential (~rv) versus time;
(4) electronically filtered analog or digital current and potential signals versus time;
(5) spectral analysis: using an appropriate mathematical transfer function, such as an FFF
or the MEM, signals are converted from the time to the frequency domain to produce
power spectral density (PSD) plots; and
(6) noise parametersS--noise resistance (R,), pitting index (Pin), noise impedance (Zn),
and degree of localization (DoL).
The following is a brief discussion of the major data analysis techniques that have been
applied to ENM. The reader is referred to the cited references for details of the met hodol ogy
and assessment of the limitations of these methods. Some examples of the use of these
techniques in corrosion applications are also provided.
* Some terms, methods, and devices may be associated with patents, for example, UK Patent Appl.
8611518, UMIST, Manchester UK.
Electronic Filtering--Most high-resolution measuring instruments involve electronic ill-
tering to avoid problems such as aliasing (see Appendix X2, It em X2.2). Beyond the use of
filtering to enhance resolution, it can be used as an online data-processing technique. For
instance, the signal can be filtered through a bandpass system centered at 50 mHz _+ 10
mHz, and, subsequently, the root mean square of the filtered signal can be calculated [6].
The type (for example, lower cut off frequency, upper cut off frequency), format (for example,
Bessel, Butterworth, Constant Phase), and order of the bandpass filter have to be determined
for the system of interest. (The selection of the correct filter for a given application is a
complex topic and is beyond the scope of this paper.) Alternatively, the RMS values of the
EPNM and ECNM over time can be used directly to measure corrosion processes [6,11].
Pattern Recognition and Correlation of Trends--The most basic type of data analysis from
a three-electrode system for which current and potential are measured simultaneously is
recognizing a pattern or correlating trends in the current and potential signals. In the case
of a general mode of corrosion, the noise signal is fairly random. There may be good
correlation ( >90%) between the coupling current noise and the corrosion potential noise,
although there is no distinctive shape or any real evidence of individual transients.
In the case of a stable passive alloy, the electrochemical noise, both current and potential,
observed in the presence of passive films is typically of a small amplitude [2,11,12,33], and
a slow drift in the corrosion potential is typically observed. Al t hough the current and potential
correlate, the passive current characteristic of the system has a low-level noise signal. The
fine structure observed in many time records suggests that the current flow is random because
of electronic or ionic diffusion within the film.
Statistical Analysis--The RMS values, standard deviation values, or bandpass-filtered
noise from digital instrumentation for both V, and the I , can be related using Ohm' s law to
produce a resistance noise value (termed R,o) as the frequency approaches zero Hertz. In
performing RMS calculations, the number of data points, acquisition rate, length of time,
the standard deviation formula, and prefiltering are to be determined by the user.
Much of the initial research on pitting using ENM involved the potentiostatic technique
[34,35]. Current transients were obtained by sweeping anodically into the region of pitting
potential. The pitting and metastable pitting processes were then characterized by extensive
statistical analysis to identify the influence of alloying additions such as mol ybdenum on the
corrosion resistance of stainless steel.
Spectral Analysis--Power spectral density (PSD) plots are frequently used by electrical
engineers to analyze the noise of a signal. (See Appendix X1 Item XI . 11 for a definition of
the term.) In performing spectral density calculations, parameters such as the number of data
points, acquisition rate, length of acquisition time, the standard deviation formula, and pre-
filtering are to be determined by the user, who in this way influences the calculated result.
A certain type of PSD plot that shows a continuous increase in power spectral density
with decreasing frequency is referred to as 1/ f plot and is generally taken to represent the
random noise associated with a signal. In corrosion studies, 1/f-type behavior has been
interpreted as evidence of a process occurring randoml y over a specific period of time and
a given space (such as a working electrode surface area) coupled to a process described by
principals of chemical kinetics [25,26,33,36]. This leads to a caution about the use and
interpretation of PSD plots: since the PSD is based on a signal-averaging met hod (such as
the FFT), it represents an average of system behavior during the selected data acquisition
period rather than discrete or localized events. For this reason, a PSD is not particularly
useful for corrosion monitoring in comparison to a ENM-t i me plot. However, a PSD plot is
very useful for det ermi ni ng/ vi sual i zi ng how the amplitude of an ENM varies as a function
of frequency. From this, one might deduce the relative contribution to the overall ENM of
a slowly occurring corrosion process versus that of a more frequently occurring event. In
the studies of passivity and localized corrosion, workers have used potentiostatic measure-
ments to obtain PSDs of ECN [2,9,10,11,32,34] and galvanostatic measurements t o obtain
PSDs of EPN [9,33].
In addition to the PSD type of spectral analysis, a noise impedance ( 7 . 1 ) can be described
as a function of frequency by correlating I , and V, using frequency response analysis.
The Z, value has been related to both the charge transfer resistance and polarization resistance
[2,37].
Transient Anal ysi s--Mechani st i c information can be also obtained by analysis of the in-
dividual transients marking up the noise signal because these are influenced by the electro-
chemical parameters controlling the metal dissolution and cathodic reduction reactions. The
shape of a transient can be shown to be the result of specific events associated with localized
corrosion. Recently, some workers [38~11] have applied techniques developed from chaos
theory and fractal analysis [42] to ENM data. Wavelet transforms from neural network anal-
ysis would appear to be useful for identifying the significant segments within long, compl ex
data sets. The use of any of these techniques for practical corrosion applications is an ongoi ng
effort directed, in part, toward reducing the vast amount of data obtained during continuous
monitoring to a few sensitive parameters.
Noise Paramet ers--The type of noise or transient shape observed in the time records has
been related to the form of corrosion [12,19,36,37,39,41,43~19], and it is also possible to
correlate potential and current noise signals to obtain a "noi se" resistance, R,. This can be
used in an analogous manner as the DC-polarization resistance, Rp, or the AC-charge transfer
resistance, Rc~ or the Stern-Geary approach for corrosion rate measurement. The Rn value is
determined by a polarization method in which the perturbation is generated by the corrodi ng
system rather than an external instrument. Naturally occurring transients are used to comput e
an electrochemical interfacial resistance instead of the imposed galvanostatic or potentiostatic
signal used for the determination of the linear polarization resistance, R e .
The ratio of standard deviations of the electrochemical noise signals provide the noise
resistance value, R~ = trv/~r i [37,50]. The variance of the noise signals (that is, the standard
devi at i on/ RMS) has been found to indicate the "degree of localization" (DoL) of the cor-
rosion [6]. In many instances, the mean coupl i ng current follows a similar trend as the change
in corrosion rate determined by EIS and R~ estimations [51]. Similar relationships of Rp and
R n have been found.
Summary
1. The increasing use of electrochemical noise measurements in corrosion research and
industrial process monitoring prompt ed the formation of an ASTM task group to "De-
velop standards that describe instruments and methods for making and analyzing elec-
trochemical noise measurements. " The task group members agreed that the availability
of a standard procedure and round robin data on a variety of systems would facilitate
the qualification of equipment and experimental techniques. This would eventually lead
to the generation of ENM data in various laboratories that could be compared with
confidence.
2. A standard guide to three methods is being developed: (a) electrochemical current noise
measurement at open circuit potential, (b) electrochemical potential noise measurement
at open circuit potential, and (c) potentiostatic noise measurement, which involves the
measurement of ECNM at an applied potential.
3. The standard guide is to include an extensive list of terminology related to ENM and
will provide recommendations for (a) electronic measuring instrument specifications,
(b) configuration of laboratory apparatus, (c) calibration and validation of instrumen-
tation, and (d) data analysis methods.
4. Procedures and reference data are being developed in an interlaboratory testing program
for four combinations of alloy and test environment including mild steel in citric acid,
the ASTM electrochemical test standard (Type 430 stainless steel) in sulfuric acid plus
sulfate, a zirconium alloy in hydrochloric acid with ferric ion additions, and an alu-
mi num alloy in a salt solution.
APPENDI X X1
Terminology for Electrochemical Noise Measurement
The following terms are unique to ASTM Commi t t ee G1 in the context used in the ENM
standard guide and do not appear in ASTM Terminology G 15. The reader is advised that
none of these terms, or any of the other parts of the standard guide described in this paper,
have as yet been approved by the ASTM Commi t t ee GI . The first official Subcommittee
GI . 11 ballot for the standard guide on ENM was issued in March of 1994. For more infor-
mation, the reader may want t o refer t o the IEEE Standard Dictionary of Electrical and
Electronics Terms [1].
Not e that certain "noi se parameters" and technologies for ENM are associated with patents
or patent applications. Appropriate acknowl edgment of the patent holder is recommended
when used in publication or discussion.
XI . I Coupling current Current between two galvanically coupled electrodes
X1. 2 Electrochemical current noise
(ECN)
X1.3 Electrochemical noise
X 1.4 Electrochemical noise meas-
urement (ENM)
Xl . 5 Electrochemical potential
noise (EPN)
Xl . 6 Galvanostatic noise
measurement
Xl . 7 Noise resistance (R,)
measured as a function of time
Fluctuations of current during a corrosion process
Fluctuations of potential or current, typically of low fre-
quency ( <10 Hz) and low amplitude. Electrochemical
noise originates, in part, from natural variations in elec-
trochemical rate kinetics during a corrosion process.
Electrochemical noise is often regarded as a ran-
dom (stochastic) phenomena coupled to deterministic
kinetics
Technique involving the acquisition and analysis of
electrochemical noise data. Data are typically acquired
by monitoring the evolution of a corrosion process with-
out the application of an external signal. Alternatively,
potentiostatic or galvanostatic methods can be used to
measure electrochemical potential or current noise, re-
spectively. Various methods of analysis of the electro-
chemical noise data can provide information concerning
the nature of the corrosion processes and the magnitude
of the corrosion rate for a given system
Fluctuations of potential during a corrosion process
Technique involving the measurement of EPN made on
a system that is under an applied current
Comparison or correlation of the electrochemical poten-
tial noise to the electrochemical current noise
X1. 8 Noi se I mpedance ([Z,,[)
X1. 9 Open ci rcui t noi se meas-
urement
X I . I O Pot ent i ost at i c noi se meas-
urement
XI. 11 Power spect ral densi t y (PSD)
pl ot
X 1.12 Worki ng el ect rode pai r
X1.13 Zer o resi st ance ammet er
( ZRA)
XI . 14 " 1 / f ' noi se behavi or
APPENDI X X2
Rat i o of the I , and V, in the frequency domai n, when
each is det er mi ned by a t ransform function, such as an
FFT or MEM. Thi s val ue has been rel at ed to bot h the
charge t ransfer resi st ance and pol ari zat i on resi st ance
Techni que i nvol vi ng t he measur ement of ei t her or bot h
ECN and EPN on a syst em that is under no appl i ed
pot ent i al (that is, at open ci rcui t pot ent i al for the gi ven
al l oy/ el ect r ol yt e syst em)
Techni que i nvol vi ng the measur ement of ECN made on
a syst em that is under an appl i ed pot ent i al
A pr eci se defi ni t i on is the Four i er t ransform of the au-
t ocorrel at i on funct i on of a dat a set. In more accessi bl e
l anguage, a PSD descri bes how the power of a signal
is di st ri but ed among di fferent frequenci es. Dat a are gen-
er at ed usi ng st andard al gori t hms (for exampl e, t he FFF)
and are di spl ayed in the f or mat of power versus fre-
quency. The most appropri at e units for the el ect r ochem-
i cal noi se power ampl i t ude in corrosi on studies are still
cont roversi al : the fol l owi ng are some exampl es that
have been used for EPNM: l og V2Hz -~, dB V Hz -~
and dB mV 2
Two el ect rodes of nomi nal l y i dent i cal di mensi on fab-
ri cat ed from the same mat eri al , mount ed in the same
manner, and gi ven the same pret reat ment s bef or e ex-
posure in the t est el ect rol yt e
El ect roni c devi ce used to measure the current bet ween
a pai r of el ect r odes whi l e the el ect rodes are mai nt ai ned
wi t h negl i gi bl e pot ent i al di fference bet ween the el ec-
trodes. Moder n ZRAs i ncorporat e a low vol t age offset
( < 1 I~V), l ow-noi se operat i onal ampl i fi es, and a feed-
back ci rcui t
For general corrosi on in whi ch the di st ri but i on of the
current and pot ent i al noi se signals t end to be gaussi an,
the t ransformat i on of raw t i me series dat a i nt o t he fre-
quency domai n produces a spect rum char act er i zed by
the ampl i t ude bei ng i nversel y proport i onal to the fre-
quency rai sed such as to the power a( f ") . 1/fa noi se
behavi or is referred to as "fl i cker noi se" when a = 1.
Terminology for Electronic Instrumentation
The f ol l owi ng t erms are i mport ant to an underst andi ng of ENM t echnol ogy and are offered
for the conveni ence of t he reader.
X2.1 Accur acy Maxi mum error in the measurement of a physi cal quan-
t i t y in t erms of the i nput of an i nst rument when referred
to t he i ndi vi dual i nst rument cal i brat i on. The accuracy
of an i nst rument is usual l y expr essed as a percent age
of full scale. In mor e general terms, accuracy is defi ned
as the degr ee to whi ch a measured or cal cul at ed val ue
conforms to the accept ed st andard or rul e
X2. 2 Aliasing
X2.3 Analog-to-digital ( A/ D)
converter
X2.4 Bit
X2.5 Digital voltmeter (DVM)
X2. 6 Digital multimeter (DMM)
X2. 7 Digital filter
X2.8 Drift
X2. 9 Electronic noise
X2. 10 Electronic noise analysis
X2.11 Electronic noise figure
X2. 12 Filter (passive type)
X2.13 Frequency response curve
Introduction of error into the Fourier analysis of a dis-
crete sampling of continuous data when component s
with frequencies too great to be analyzed with the sam-
piing interval being used contribute to the amplitudes
of lower-frequency component s
Circuit that changes a continuously varying potential or
current into a digital output. The input may be AC or
DC, and the output may be serial or parallel, binary, or
decimal
Abbreviation for binary digit. A unit of information
equal to one binary decision or the designation of one
or two possible and equally likely states (such as 1 or
0). When a number of bits is specified, this refers to a
binary number with the specified number of binary
digits. Thus a 16-bit A/ D converter produces a 16-bit
binary number and can represent 216 (65 536) different
values
Electronic device capable of measuring the potential of
an electrical signal in a digital format
Electronic device capable of measuring the potential,
current and other attributes of an electrical signal in a
digital format
Computational process in whi ch the sequence of input
numbers is converted into a sequence of output numbers
representing the alteration of the data in some pre-
scribed manner. A common example is the process of
filtering out a certain range of frequencies in a signal
while rejecting all other frequencies, which is one of
the foremost classical approaches to analog filter design.
In the classical continuous time case, this filtering is
achieved by a suitable choice of inductors, capacitors,
and resistors arranged to provide the required transmis-
sion characteristics. However, in the digital case, this
can be achieved completely by the process of digital
addition, multiplication by constants, and delay
Change in either absolute level or slope of an input-
output characteristic. In a DC amplifier, the change in
output with constant input signal, usually measured in
terms of the DC input signal required to restore normal
output with units of millivolts or millivolts per hour
Any unwanted electrical disturbance or spurious signal
originating within electronic component s that modifies
the transmitting, indicating, or recording of desired data
Determination of the frequency component s that
makeup the noise being studied
For a given bandwidth, the ratio of the total noise power
at the output to the noise at the input
Selective network of resistor, inductor, or capacitor el-
ements that offers comparatively little opposition to cer-
tain frequencies to direct current while blocking or at-
tenuating other frequencies
Graphical representation of the gain or loss of a device
in response to different frequencies within its operating
range
X2. 14 Input i mpedance
X2.15 Input offset pot ent i al
X2. 16 Nul l i ng
X2. 17 Operat i onal ampl i f i er
X2. 18 Quant i zat i on
X2. 19 Quant i zat i on error
X2. 20 Resol ut i on
Effect i ve i mpedance that a t r ansducer / ampl i f i er pres-
ent s to a source at t he i nput t ermi nal ; t he ci rcui t det ai l s,
si gnal level, and frequency must be speci fi ed
Voltage that must be appl i ed bet ween the t wo i nput ter-
mi nal s of an operat i onal ampl i fi er to pr oduce an out put
of zero
Met hod of measur ement in whi ch the output of a devi ce
or syst em, whi ch is not zero, is opposed so as to return
it to zero (al so referred to as null met hod or zero
met hod)
Al so cal l ed an op amp) el ect roni c devi ce, consi st i ng
essent i al l y of t wo i nput t ermi nal s ( e+ and e - ) and one
out put t ermi nal (eou,) that behaves accordi ng to the gai n
equat i on: eou t = A*( e + - e - ) ; where A represent s var-
i ous mat hemat i cal operat i ons. Operat i onal ampl i f i er cir-
cui t s can be used to add, subtract, average, integrate,
and di fferent i at e by t he pr oper sel ect i on of associ at ed
f eedback component
Process wher eby t he range of val ues of a wavef or m is
di vi ded i nt o a finite number of subranges, each repre-
sent ed by an assi gned value. Anal og values are sai d to
be quant i zed when expressed in t erms of the nearest one
of a di scret e set of presel ect ed val ues
Di fference bet ween the actual val ues of dat a and the
cor r espondi ng di scret e values resul t i ng f r om quan-
t i zat i on
Degr ee to whi ch nearl y equal values of a quant i t y can
be di scri mi nat ed. The measure of t he smal l est possi bl e
i ncrement of change in the vari abl e out put of a devi ce
APPENDI X X3
Gui de to the Constructi on of a Zero Resi stance Ammet er (ZRA) for El ectrochemi cal
Current Noi se Measurement
X3.1 An ZRA confi gurat i on appr opr i at e for ECNM is shown in Fi g. 9. The range of
resi st ors can be varied: the maxi mum current expect ed wi l l be onl y _+ 20 mA. The 10-kl~
resi st or wi l l be adequat e for most cor r odi ng syst ems, and the 100-kgl and I-MI~ resi st ors
are r ecommended for syst ems wi t h very l ow corrosi on rates. Resi st or pr eci si on of 1% is
r ecommended. The capaci t or shown in Fig. X3 shoul d el i mi nat e spuri ous hi gh-frequency
noise: it shoul d be a nonpol ar i zed t ype wi t h a val ue of 1 wE
X3. 2 Two 9-V bat t eri es are r ecommended as a power source. A swi t ch shoul d be i ncl uded
for i sol at i on of t he power source when not in use. The gr ound shoul d be connect ed to the
0 V (mi dpoi nt ) of the power supply. The vol t age out put should be measured from t he out put
of t he op- amp referenced to the 0-V ground. Voltage swi ngs shoul d then be symmet r i c
around 0 V.
X3.3 The maxi mum vol t age out put swi ng of the op- amp wi l l be around ___7.5 V, so a 10-
klq resi st or wi l l gi ve a maxi mum current capabi l i t y of appr oxi mat el y _+ 750/ xA. Thi s con-
di t i on is referred to as s at ur at i on. When sat urat i on occurs, it is necessary to swi t ch to a
l ower val ue of current measuri ng resistor.
X3. 4 Testing t he ZRA.
K E A R N S ET AL . O N A S T M S T A N D A R D I Z A T I O N O F E N M 4 6 7
~ ' Z 1
V +
'li"
W Z 2
O V
f o r t est i . ~r
FIG. X3--Schematic diagram of a ZRA using an operational amplifier.
X3.4.1 The output should be measured with a 51/z-digit DVM when conducting this
test. Such a device will provide excellent resolution, particularly when operating in an au-
toranging mode.
X3.4.2 Measure the output voltage with nothing connect ed at the input. This should be
equal to or less than 100 I~V. Adjust the offset null circuitry of the op-amp to give 1 ixV or
less. This establishes the lower limit of current resolution.
X3.4.3 Input a current into the WE1 terminal (for example, a 9-V battery in series with
a 100-kfl resistor to give a nominal 90-1~A current). Check the output voltage of ZRA: with
a 10+kgl resistor, this should be 0.9 V. The output should be measured with a 51/e-digit DVM
when conducting this test. Such a device will provide excellent resolution, particularly when
operating in an autoranging mode.
APPENDI X X4
Procedure for ENM of System A: AISI 1018 Steel in 0.1M Citric Acid
X4.1 Electrode Preparation
X4.1.1 Obtain two pieces of AI SI 1018 steel rod, 0. 635-cm (0.25-in.) diameter by 25.4
cm (10 in.) long. Finish the surface by bead or sand blasting. Note: The surface finish of
the rod is not critical because the specimen will corrode at a high rate. Protect machined
rods from corrosion in air by storing in a desiccator.
X4.1.2 Optional--Mark the electrodes with a stamp or an engraver to identify top and
bot t om as well as working Electrode 1 and working Electrode 2.
X4. 2 Experimental Procedure
X4.2.1 Prepare a solution of 0.1M citric acid from reagent grade acid and Type I V distilled
water per D1193. In a 2-L beaker, for example, weight 17.29 g of citric acid monohydrat e
(formula weight 192.12 g/ mol e) and add 900-mL distilled water. Place a lid on the vessel
and allow the crystals to dissolve for at least 30 min at room temperature. (Note: Storing
this solution for long periods of time is not recommended because it supports growth
of bacteria.)
X4. 2. 2 Prepare all the el ect roni c i nst rument at i on so the measur ement can be made i m-
medi at el y after the wor ki ng el ect rodes are i mmersed.
X4. 2. 4 Wei gh samples.
X4.2.5 Pl ace worki ng el ect rodes i nt o hol ders.
X4.2.5.1 In usi ng an ASTM Test Met hod G 5 t ype cel l , the wor ki ng el ect r ode pai r is hel d
in pl ace by O-ri ngs within t wo ground gl ass j oi nt s (size 24/ 40 j oi nt s are t ypi cal for the
auxi l i ary el ect r ode posi t i ons in ASTM Test Met hod G 5.
X4. 2. 5. 2 The length of the el ect r ode that ext ends bel ow the j oi nt i nt o the cel l body is 10
cm: this wi l l result in 6. 35-cm length of el ect rode exposed to the el ect rol yt e. A 6. 35-cm
i mmersi on dept h for a nomi nal 0. 6-cm (0. 25-in) di amet er rod. (Note: The mi ni mum area of
exposed el ect rode wi l l depend on the syst em and the goal s of the investigator. A smal l
el ect rode size may be appropri at e to i ncrease the magni t ude of the ENM si gnal . )
X4. 2. 6 Transfer 900 mL of sol ut i on to t he el ect rochemi cal cel l and cont rol the t emperat ure
of the sol ut i on to 25 _+ 2~
X4.2.7 Pl ace the worki ng el ect rode pair, the reference el ect rode, and the t her momet er in
the test cel l , as shown in Fig. 5A. The t wo worki ng el ect rodes are al i gned across t he base
of an equi l at eral t ri angl e wi t h t he reference el ect r ode at t he apex appr oxi mat el y 5.5 cm away
from the base. Cl ose all t he ot her openi ngs with gl ass or rubber st oppers.
X4.3 El ect r ochemi cal Measurement s
X4.3.1 Connect t he measuri ng i nst rument s and the cel l as appr opr i at e for t he avai l abl e
inputs and the manner in whi ch the dat a acqui si t i on soft ware addresses such inputs.
X4. 3. 2 Measure the current flowing bet ween the t wo steel el ect rodes when t hey are cou-
pl ed wi t h a current measuri ng devi ce l i ke a zero resi st ance ammet er and the pot ent i al be-
t ween t he t wo el ect rodes and the reference el ect rode. The two measurement s shoul d be
measured si mul t aneousl y to the ext ent possi bl e as l i mi t ed by the measuri ng equi pment . The
speci fi cat i ons for signal processi ng, such as filtering, sampl i ng frequency, and number of
dat a points, depend on the goal s of the user and the t ype of dat a anal ysi s met hod that is to
be subsequent l y used.
X4.3.3 Measure and r ecor d the final mass of each el ect rode to the nearest 0.1 mg. A l -
mg / c m 2 mass loss is expect ed in the first 4 h, and 2 and 3 mg / c m 2 in 20 h. Cal cul at e the
corrosi on rate accordi ng to:
C R = 11 1 3 8 * m* A * t
where
CR = corrosi on rate in mi l l i met er s per year;
m = mass l oss in grams;
A = area in square cent i met ers; and
t = t i me in hours.
The sol ut i on turns pal e yel l ow after 24 h as a result of t he corrosi on of AI SI 1018 steel.
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the El ect rochemi cal Society, Vol. 115, No. 6, 1968, pp. 617-618.
[23] Barker, G. C., "Faradaic Reaction Noise," Journal o f Electroanalytical Chemistry, Vol. 82, 1977,
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[25] Blanc, G., Epelhoin, I., Gabrielli, C., and Keddam, M., "Etude des Comportements Deterministe
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[26] Blanc, G., Epelboin, I., Gabrielli, C., and Keddam, M., "Electrochemical Noise Generated by
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[27] Blanc, G., Gabrielli, C., Ksouri, M., and Wiart, R., "Experimental Study of the Relationships
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[28] Hooge, E N. and Hoppenbrouwers, A. M. H., "Amplitude Distribution of 1/ f Noise: Gaussian
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[29] Blanc, G., Gabrielli, C., and Keddam, M., "Measurement of the Electrochemical Noise by a Cross
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[30] Epelboin, I., Gabrielli, C., Keddam, M., and Raillon, L, "Measurement of the Power Spectral
Density of Electrochemical Noise: Direct Two-Channel Method," Journal o f Electroanalytical
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[31] Bertocci, U. and Kruger, J., "Studies of Passive Film Breakdown by Detection and Analysis of
Electrochemical Noise," Surface Science, Vol. 101, 1980, pp. 608-618.
[32] Bertocci, U., "Separation between Deterministic Response and Random Fluctuations by Means of
the Cross-Power Spectrum in the Study of Electrochemical Noise," Journal of the Electrochemical
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[33] Hladky, K. and Dawson, J. L., "The Measurement of Corrosion Using Electrochemical 1/ f Noise,"
Corrosion Science, Vol. 22, No. 3, 1982, pp. 231-237.
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Stainless St eet s- - l . Modeling of the Initiation and Growth of Pits at Constant Potential," Journal
[35] Williams, D. E., Westcott, C., and Fleischmann, M., "Stochastic Model of Pitting Corrosion of
Stainless St eel s--II. Measurement and Interpretation of Data at Constant Potential," Journal of the
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[36] Uruchurtu, J. C. and Dawson, J. L., "Noi se Analysis of Pure Aluminium Under Different Pitting
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[42] Nicolis, G. and Prigogine, I., Exploring Complexity: An Introduction, W.H. Freeman & Co., New
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[43] Balkwill, P. H., Westcott, C., and Williams, D. E., "Stochastic Approach to the Initiation of Pitting
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[44] Cottis, R. A. and Loto, C. A., "Electrochemical Noise Generation During Stress Corrosion Crack-
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[45] Dawson, J. L. and Ferreira, M. G. S., "Electrochemical Studies of the Pitting of Austenitic Stainless
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[46] Eden, D. A., Rothwell, A. N., and Dawson, J. L., "Electrochemical Noise for Detection of Sus-
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Cincinnati, OH, 1991.
[47] Loto, C. A. and Cottis, R. A., "Electrochemical Noise Generation During Stress Corrosion Cracking
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[48] Simoes, A. M. P. and Ferreira, M. G. S., "Crevice Corrosion Studies of Stainless Steel Using
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[49] Williams, D. E., Fleischmann, M., and Stewart, J., "Some Characteristics of the Initiation Phase
of Pitting Corrosion of Stainless Steel," in Electrochemical Methods in Corrosion Research, M.
Duprat, Ed., Trans Tech Publications Ltd., Switzerland, 1986, Vol. 8, pp. 151-166.
[50] Mansfeld, E and Xiao, H., "Electrochemical Noise Analysis of Iron Exposed to NaCI Solutions of
Different Corrosivity," Journal of the Electrochemical Society, Vol. 140, No. 8, 1993, pp.
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[51] A1-Zanki, A. I., Gill, J. S., and Dawson, J. L, "' Electrochemical Noise Measurements on Mild Steel
in 0.5 M Sulfuric Acid," in Electrochemical Methods in Corrosion Research, M. Duprat, Ed., Trans
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STP1277- EB/Sep. 1996
Author Index
A
Almeida, Mafia E. Moreira de, 411
B
Baroux, Bernard, 332
Barton, Thomas E, 157
Beaunier, Luc, 114
Bertocci, Ugo, 39
Bierwagen, Gordon P., 427
Boulleret, Claire, 332
Brennenstuhl, A. M., 186, 266
C
Chapey, Brigitte, 361
Chavarin, Jorge Uruchurtu, 411
Claudi, Renata, 186
Cottis, R. A., 93
Cox, William M., 173
D
Dawson, John L., ix, 3
DeBruyn, Hennie J., 214
de Damborenea, Juan, 398
Doherty, P. E., 288
E
Eden, David A., 201, 446
Fahey, Jefferson V., 446
Fernandez, Bernardo, 398
Frydman, Joel, 114
G
Gabrielli, Claude, 114
Gonzalez, E S., 266
Gorse, Dominique, 332
Govekar, Edvard, 129
I-I
Harper, S. L., 288
Heaver, Edward E., 214
Hudson, Jack L., 307
Hudson, John L., 101
Huet, Francois, 361, 375, 114
Inman, Maria E., 101
Jacko, Richard J., 201
Jer6me, Michel, 375
K
Kearns, Jeffery R., ix, 446
Keddam, Michel, 114
Kelly, Robert G., 101
L
Lawson, Kevin, 214
Legat, Andraz, 129
Liu, Chun, 247
M
Macdonald, Digby D., 247
Malo, Jose M., 387
Manahan, Michael E, Sr., 247
Manolatos, Panagiotis, 375
Mansfield, Florian, 59
Mariaca, Liboria, 411
Mendoza-Flores, J., 93
Mickalonis, John I., 201
Mills, Douglas J., 427
N
Nichols, Henry E, 230
O
Oltra, Roland, 361
P
Palumbo, G., 266
Pistorius, R Chris, 343
Pride, Sheldon T., 307
Psaila-Dombrowski, M. J., 288
471
www.astm.org
4 7 2 ZIRCONIUM IN THE NUCLEAR INDUSTRY: ELEVENTH SYMPOSIUM
Q T
Quirk, Graham E, 201, 266
R
Reichert, David L., ix, 79, 446
Renaud, Lionel, 361
Roberge, Pierre R., ix, 142
Rodriguez, Abelardo, 411
S
Schneider, W. G., 288
Scully, John R., ix, 307
Silverman, David C., 446
Sim, Blair, 186
Skerry, Brian S., 427
Stokes, Patrick S. N., 230
Syrett, Barry C., 173
Tallman, Dennis E., 427
Tuck, Darud L., 157
Turgoose, S., 93
V
Velazco, Octavio, 387
Veloz, Maria A., 411
W
Wells, D. Brett, 157
Wenger, Francois, 375
Winters, Michael A., 230
Xiao, Hong, 59
Yaffe, Max R., 446
X
Y
Subject Index
STP1277- EB/Sep. 1996
A
AA 2024-T3, metastable pitting, 307
Absorption, hydrogen, effect on
electrochemical potential noise, 375
Acoustic emission, coupling with
el ectrochemical current noise, 361
Alloy heat exchangers, corrosion resistance,
266
Al uminum
corrosion, electrochemical noise, 142
exfoliation, electrochemical noise
measurements, 398
metastable pitting, 307
Al uminum-l ithium alloy, exfoliation, 398
ASTM G 34, 398
ASTM standardization, electrochemical
noise measurement, 446
Atmospheric corrosion, 411
B
Bubble, hydrogen, electrode potential and
electrolyte resistance, 375
C
Capacitance, role in corrosion potential
during metastable pitting, 343
Carbon steel
corrosion resistance, effects of zebra
mussel attachment, 186
electrochemical noise measurements in
high subcritical and supercritical
aqueous environments, 247
nuclear waste tanks, 201
prerusted, characterization in Ibero-
American atmospheres, 411
stress corrosion cracking, 214
Chaotic analysis, 129
Coatings, 3
electrochemical noise and impedance, 59
reproducibility of electrochemical noise
data, 427
CO--CO2--H20 systems, on-line
monitoring, 214
Concrete, reinforced, electrochemical noise
and electrochemical impedance
spectroscopy, 39
Constituent particles, 307
Cool ing water systems, corrosion and
fouling monitoring, 230
Copper-depl eted zones, metastable
aluminum, 307
Corrosion
ASTM standardization of electrochemical
noise measurement, 446
electrochemical noise under
hydrodynamic conditions, 387
high subcritical and supercritical aqueous
environments, 247
hydrogen absorption effect on
localized (see Localized corrosion)
online evaluation, 173
reproducibility of electrochemical noise
data, 427
uniform (see Uniform corrosion)
Corrosion monitoring, 186
heat transfer in cooling water systems,
230
in-situ technique, 3
steam generators, 288
Corrosion rate measurement
electrochemical noise measurement, 79
solution resistance effects on
electrochemical noise resistance, 93
Corrosion resistance, effects of zebra
Coupling current, 186
metastable pitting in aluminum, 307
Crevice corrosion
identification using artificial neural
network, 157
steam generator materials, 288
D
Data analysis techniques, 114
Degree of localization, 186
nuclear heat exchanger tubes, 266
Depassivation, 142
Diffusion, 387
E
Electric Power Research Institute, review of
proj ects since 1984, 173
El ectrochemical current noise, 114, 186
coupling with acoustic emission, 361
metastable pitting in al uminum, 307
473
4 7 4 ZIRCONIUM IN THE NUCLEAR INDUSTRY: ELEVENTH SYMPOSIUM
Electrochemical current noise--continued
steel under hydrodynamic conditions,
387
Electrochemical impedance spectroscopy,
142
comparison with electrochemical noise
measurements, 39
exfoliation of aluminum alloys, 398
iron in chloride media, 59
Electrochemical noise
analysis, iron in chloride media, 59
corrosion resistance, nuclear heat
exchanger tubes, 266
network, 157
impedance, 3
in-situ technique, 3
metastable pitting, 307
reproducibility of data from coated metal
systems, 427
spontaneous, 142
stainless steel in chloride solutions, 101
387
use in investigating effects of zebra
Electrochemical noise measurement
ASTM standardization, 446
comparison of spectral and chaotic
analysis, 129
comparison with impedance
spectroscopy, 39
corrosion rate determination, 79
during exfoliation of aluminum alloys,
398
effect of metallurgical factors, 332
evaluation of steam generator materials,
288
on-line monitoring, 214
potentiostatic, 114
prerusted steel, characterization in Ibero-
American atmospheres, 411
simultaneous corrosion and fouling
monitoring, 230
steels in high subcritical and supercritical
stochastic behavior, 142
Electrochemical noise resistance, solution
resistance effects, 93
Electrochemical potential noise, 79, 186
metastable pitting in aluminum, 307
387
Electrochemical tests, standardization, 446
Electrolyte resistance, 375
EXCO test, 398
Exfoliation corrosion, electrochemical noise
measurements
aluminum, 398
aluminum alloys, 398
F
Fast Fourier transform, comparison with
spectral analysis using maximum
entropy method, 114
Forced convection, 387
Fouling monitoring, heat transfer in cooling
water systems, 230
Fractal analysis, 129
G
Galvanostatic electrochemical noise
measurement, 375
l-I
Heat exchangers, corrosion and fouling
monitoring, 230
Heat tint, 343
Hydrogen, absorption effect on
Impedance, interfacial, 3
Impedance spectroscopy
comparison with electrochemical noise
measurements, 39
Inclusions, 332
Inhibitor, 59
corrosion, 201
Instrumentation, electrochemical noise, 173
Intergranular corrosion
aluminum alloys, 398
Iron, in chloride media, electrochemical
noise and impedance analysis, 59
Iron electrode, hydrogen absorption effect
on electrochemical potential noise,
375
SUBJECT INDEX 475
L
Laboratory testing, standardization, 446
Linear circuit model, 93
Linear polarization resistance, 79
Localized corrosion
heat exchangers, 230
in-situ measurement, 3
molybdenum implantation role, stainless
steel, 114
particle impacts, 361
M
Manganese sulfide, effect on
electrochemical noise, 332
Marine coatings, reproducibility of
electrochemical noise data, 427
Mass loss measurements, 79
Maximum entropy method
comparison with spectral analysis using
fast Fourier transform, 114
metastable aluminum, 307
Metallurgical factors, effect on
electrochemical noise, 332
MICAT project, 411
Microstructure, nuclear heat exchanger
tubes, 266
Molybdenum, implantation and localized
corrosion on stainless steel, 114
Monitoring, corrosion and fouling, 230
Multilayer feedforward network, 157
N
Neural network, artificial, pitting and
crevice corrosion, spectra
identification, 157
Nitrates, pitting induction, 201
Noise resistance, 79
Nuclear heat exchanger tubes
corrosion resistance, 266
Nuclear power, steam generator materials,
288
Nuclear waste tanks, electrochemical noise
measurements, 201
O
Oil industry, stress corrosion cracking, on-
line monitoring, 214
On-line monitoring, stress corrosion
cracking, 214
Oxides, 411
Permeation, electrochemical, 375
Pit stabilization factor, 307
Pitting, 3
effect of metallurgical factors, 332
environments, 247
network, 157
metastable, 307, 332, 343
stainless steel, 101, 114, 343
Polarization resistance
Polymer coatings, electrochemical noise
and impedance, 59
Potentiostatic electrochemical noise
measurement, 114, 332
Power spectral density, 114, 129
exfoliation of aluminum alloys, 398
slurry erosion-corrosion studies, 361
R
Repassivation, 307
Reproducibility, of data, 427
Resistance noise, 186
Rotating disk electrode, 387
Shot noise model, 93
Slurry erosion-corrosion studies, coupling
of acoustic emission and
electrochemical current noise, 361
Solution resistance, effects on
electrochemical noise resistance, 93
S' particles, 307
Spectral analysis, 129
comparison of fast Fourier transform and
maximum entropy method, 114
Spectral noise resistance, iron in chloride
media, 59
Stainless steel
in chloride solution, metallurgical factor
effect on electrochemical noise, 332
476 ZIRCONIUM IN THE NUCLEAR INDUSTRY: ELEVENTH SYMPOSIUM
Stainless steel--continued
in chloride solutions, electrochemical
noise, 101
corrosion identification using artificial
neural network, 157
corrosion resistance, effects of zebra
electrochemical noise measurements in
high subcritical and supercritical
localized corrosion, molybdenum
implantation role, 114
pitting corrosion, 343
Steam generators
corrosion monitoring, 288
corrosion resistance, 266
Steel
electrochemical noise under
hydrodynamic conditions, 387 (see
also Carbon steel)
Stochastic behavior, electrochemical noise
measurement, 142
Stress corrosion cracking, 3
environments, 247
on-line monitoring, 214
Sulfate-reducing bacteria, 186
Sulfuric acid, 375
slurry erosion-corrosion studies, 361
Supercritical aqueous system, 247
Surveillance instrumentation, corrosion, 173
T
Technology demonstrations, 173
Test standards, 446
Time analysis, slurry erosion-corrosion
studies, 361
Titanium, effect on electrochemical noise,
332
Twin-electrode probe, 343
U
Underdeposit corrosion, 230
Uniform corrosion
in-situ measurement, 3
UNS N 04400, 266
Z
Zebra mussels, effects on corrosion
resistance, 186

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