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NATO ASI Series Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.
The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division
A Life Sciences B Physics
C Mathematical and Physical Sciences
D Behavioural and Social Sciences E Applied Sciences
F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change
NATO·PCa-DATA BASE
Plenum Publishing Corporation London and New York
Kluwer Academic Publishers Dordrecht, Boston and London
Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo
The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways:
- via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy.
- via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989).
The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium.
Series E: Applied Sciences - Vol. 203
Electrochemical and Optical Techniques for the Study and Monitoring of Metallic Corrosion edited by
Maria G. S. Ferreira Department of Chemical Engineering, Technical University of Lisbon, Portugal
and
Carlos A. Melendres Materials Science/Chemical Technology Divsion, Argonne National Laboratory, Illinois, U.S.A .
.. Springer Science+Business Media, B.V.
Proceedings of the NA TO Advanced Study Institute on Electrochemical and Optical Techniques for the Study and Monitoring of Metallic Corrosion Vienna do Castelo, Portugal 9-21 July 1989
Library of Congress Cataloging-in-Publication Data NArD Advanced Stuey InstItute on Electrochemlcal and Optlca1
Technlques for the Study and Monltorlng of Metal!1!: COrrQS10n (1989 Vlana do Castelo, Portuga!) Electrochenlcal and optIca! teChnlques far the study and
lIonltol"lng of metal1,c corraSlon proceedlngs of the NATD Advanced Study Institute on Electrochelilcai and Optlca1 TeCnnTQUeS for the Study and Monltorlng of Metal11c Corrosl0n, Vuna do Castelo. Partugal • .July 9-21, 1989 I edlted by Mărie O.S. Ferrelra and Carlas A. Melendres.
p. cm. -- <NATD ASI serles. Serles E. Applied Sela"CeS ; voI. 203)
"PublJshed In cooperat Ion wlth NATD SClentlf,C Affa,I"S Dlvlslon. Inc 1 udes 1 ndex. ISBN 978-94-010-5614-4 ISBN 978-94-011-3636-5 (eBook)
DOI 10.1007/978-94-011-3636-5 , _ Corros 10n and ant1-c:orros lves--Test tng--Congresses.
2. Elec:trolyt1c: c:orroslon--Testlng--Congresses. 1. Ferreu'a, Mârl0 G. S. II. Melendres. C. (Carlos). 1939- III. Nortn AtlantlC: Treaty Organ1zatl0n. SClentlfic Affalrs D1111510n. IV. Title. V. Serles: NAro ASI serleS. Serles E. Appl1ea SClences ; no. 203. TA462,N34 1989 620,1'623--dC20 91-612
ISBN 978-94-010-5614-4
Printed on acid-free paper
AII Rights Reserved © 1991 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1991 Softcover reprint of the hardcover 1 st edition 1991 No part of the material protected by this copyright notice may be reproduced or utilized in any ferm er by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner.
Preface
Organization
CONTENTS
List of Participants
List of Contributors
Marcel Pourbaix
Thermodynamics and Corrosion
D.D. Macdonald
Electrochemical Impedance Spectroscopy
M.M. Lohrengel
Principles and Applications of Pulse Techniques
to Corrosion Study
R.A. Cottis and S. Turgoose
Linear Electrochemical Techniques - Are
They All The Same?
C. Gabrielli, F. Huet and M. Keddam
Investigation of Metallic Corrosion by
Electrochemical Noise Techniques
M. da Cunha Bela
Photoelectrochemistry: Theoretical Basis
M. da Cunha Belo
Photoelectrochemistry: Application to the
Study of Passive Films
R.E. Hummel
Differential Reflectometry and Other optical
Techniques in Corrosion Research
IX
xi
xiii
xix
1
31
69
123
135
191
219
241
vi
Z. Szklarska-Smialowska and R. Krishnakumar
Ellipsometry in Studies of Metallic
Corrosion and Oxidation
C.A. Melendres
Laser Raman Spectroscopy: Principles and
Applications to Corrosion Studies
T.M. Devine
Use of Surface-Enhanced Raman Spectroscopy
in Studies of Electrode-Electrolyte
Interfaces
T.M. Devine
Infrared Spectroscopy at Electrode-Electrolyte
Interfaces
M.G.S. Ferreira and A.M.P. Simoes
Passivation and Localized Corrosion
F. Mansfeld
Inhibitors and Coatings
Z. Szklarska-Smialowska
Methods for Studying Corrosion
Inhibition
F. Mansfeld
Atmospheric Corrosion
R.C. Newman Stress-Corrosion Cracking and Corrosion Fatigue:
Application of Electrochemical Techniques
285
355
389
439
485
521
545
571
585
D.D. Macdonald
Material Corrosion in High Temperature Aqueous
Solutions in Power Generating Systems
M.A. Barbosa and R.A. Silva
Developments in the Study of Biomaterials
Degradation
R.G. Kelly and R.C. Newman
Advanced Materials: Corrosion and
Electrochemistry
Index
vii
611
651
665
697
PREFACE
In spite of considerable efforts over the years to
understand and combat materials degradation via corrosion
processes, many challenges still remain both in the
theoretical understanding of the phenomena and in seeking
pratical solutions to the perennial problem. Progress has
been slow due to the complexity of the processes and the
systems involved. Fortunately, in recent years there has been
a renaissance in the development of new electrochemical and
optical techniques, as well as advances in instrumentation,
which have greatly aided our quest to gain insight into the
complex mechanisms involved in metallic corrosion and
passivation. Numerous scientific meetings, symposia, and
workshops have been held allover the world which attest to
the frenzy of activities in corrosion science and technology.
However, most of these conferences have dealt mainly with
recent research results. There appeared to be a need to
assess and disseminate our present state of knowledge in the
field as regards measurement techniques, theory, and
instrumentation. The present NATO Advanced Study Institute
was therefore held in Viana do Castelo, Portugal from July 9
to 21, 1989. The Institute consisted of a series of tutorial
lectures, poster sessions, and round-table discussions
interspersed evenly over the two-week period. It was attended
by 75 participants from several countries representing
industry, government and university laboratories.
In the present volume, most of the lectures given at the
Institute have been collected. They cover the principles and
application of electrochemical and optical techniques to
different. aspects of metallic corrosion and passivation as
well as corrosion monitoring and protection. A purpose of
this book is to help those engaged in corrosion studies to be
more aware of the techniques presently available to
facilitate their work.
ix
x
We thank all the lecturers who contributed to this book
even those who have been impeded and too passivated to be
unable to prepare their manuscripts for printing. We deeply
appreciate the time they spent in preparing their lectures
and after-hours discussions with the participants. We also
thank all the participants for coming and making this ASI a
success.
Finally we thank the Scientific Affairs Division of NATO
(Belgium) , the portuguese councils, Junta Nacional de
Investiga9ao Cientifica e Tecnologica (JNICT) and Insti tuto
Nacional de Investiga9ao Cientifica (INIC), Funda9ao Calouste
Gulbenkian (Portugal), Haynes International (USA), Argonne
National Laboratory and the U. S. Department of Energy, as
well as the local authorities at Viana do Castelo for their
financial and logistic support.
Mario G.S. Ferreira
Carlos A. Melendres
ORGANIZATION
Director: Mario G,S, Ferreira
Department of Chemical Engineering
Instituto Superior T~cnico
1096 Lisboa Codex, Portugal
Co-Director: carlos A, Melendres
Materials Science/Chemical Technology Division
Argonne National Laboratory
Argonne, IL 60439, U,S,A,
Organizing Committee: M, da Cunha Belo, CNRS, Vitry-Sur-Seine, France
],L, Dawson, UMIST, Manchester, U,K,
M,G,S, Ferreira, Instituto Superior T~cnico, Lisbon, Portugal
C. Gabrielli, CNRS, Paris, France
D,D, MacDonald, SRI, Menlo Park, U,S,A,
C,A, Melendres, Argonne National Laboratory, Argonne, U,S,A,
],W, schultze, University of Dusseldorf, Dusseldorf, Germany
Z, Szklarska-Smialowska, Ohio State Univ" Columbus, U,S,A,
G, Trabanelli, University of Ferrara, Ferrara, Italy
xi
LIST OF PARTICIPANTS
ACHA, MIGUEL Instituto Eduardo Torroja de la Construccion y del Cemento, C/Serrano Galvache sin, 28033 Madrid, Espana
AKID, ROBERT University of Sheffield, Department of Mechanical & Process Engineering, Mappin St., Sheffield Sl 3JD, U.K.
ALMEIDA, ELISABETE L.N.E.T.I./S.C.P.M., Azinhaga dos Lameiros a Estrada Pa90 do Lumiar, 1699 Lisboa Codex, Portugal
ALVES, HELENA Instituto Superior Tecnico, Departamento de Engenharia Quimica, Laborat6rio de Electroquimica, Av. Rovisco Pais, 1096 Lisboa Codex, Portugal
ARNVIG, POUL-ERIK The Danish Corrosion Centre, Park Alle 345, DK-2065 Brondly, Denmark
BARBOSA, MARIO Department of Metallurgy, Faculty of Engineering, University of Oporto, Rua dos Bragas, 4099 Porto Codex, Portugal
BADE, KLAUS Institut fUr Physikalishe Chemie Und Elektrochemie II, Heinrich-HeineUniversitat, Universitatsstr. 1, D-4000 DUsseldorf 1, F.R.G.
BEREKET, GOZEN Faculty of Arts and Science, Chemistry Department, Univerity of Anatolia, Eskisehir, Turkey
BOISSEL, J. Souriau et Cie., BP 50, 72402 FerteBernard, France
BRETHERTON, NEIL Corrosion and Protection Centre, UMIST, P.O. BOX 88, Manchester, M60 1QD, U.K.
BROOKES, HUGH Chemistry Department, University of Natal, Durban 4001, South Africa
BUI, NAM Laboratoire de Metallurgie Physique, E.N.S. Chimie, 118 Route de Narbonne, 31077 Toulouse, France
xiii
CAHAN, BORIS Case Western Reserve University, Cleveland, Ohio, U.S.A.
CARVALHAL, VERONICA E.D.P. - Electricidade de.Portugal, Av. Mouzinho da Silveira, 10, 1200 Lisboa Codex, Portugal
CAVALCANTI, EDUARDO I.N.T., Corrosion Programme, Av. Venezuela, 82/614, 20081 Rio de Janeiro, RJ, Brasil
CETIN, INCI Yildiz University, Faculty of Science and Art, Chemistry Department, 80270 Sisli, Istambul, Turkey
COLINO, JOAQUIM J. Oficinas Gerais de Material Aeronautico, Gabinete de Engenharia da 2g Divisao, 2615 Alverca, Portugal
COTTIS, R.A. Corrosion and Protection Centre, UMIST, P.O. BOX 88, Manchester, M60 1QD, U.K.
DA CUNHA BELO, M. CNRS - CEMS, 15 rue Georges Urbain, 94400 Vitry-Sur-Seine, France
DARBY Jr., J.B. ER-131, G236, GTN, U.S. Department of Energy, Washington/DC 20545, U.S.A.
DAWSON, JOHN L. Corrosion and Protection Centre Industrial Services (CAPCIS), UMIST, Barinbridge House, Manchester M60 lQD, U.K.
DEVINE, THOMAS M.
EBLING, DIRK
Department of Materials Science and Mineral Engineering, University of California, Berkeley, CA 94720, U.S.A.
Institut flir Physikalishe Chemie lind Electrochemie, Universitats St. 1, 4000 Dlisseldorf, F.R.G.
FELIU, SEBASTIAN Jr. CENIM (CSIC), Av. Gregorio del Arno 8,
FERNANDES, JOAO
Ciudade Universitaria , Madrid 28040, Espana
Instituto Superior Tecnico, Departamento de Engenharia Quimica, Laboratorio de Electroquimica, Av. Rovisco Pais, 1096 Lisboa Codex, Portugal
FERREIRA, MARIO
FONSECA, ANT6NIO
FONSECA, INES
GABRIELLI, C.
GAGO, ISABEL M.M.
xv
Instituto Superior Tecnico, Departamento de Engenharia Quimica, Laborat6rio de Electroquimica, Av. Rovisco Pais, 1096 Lisboa Codex, Portugal
PETROGAL - Refinaria de Cabo Ruivo, Av. Infante D. Henrique, 1900 Lisboa Codex Portugal
Departamento de Quimica, Faculdade de Ciencias, Edificio C1, Cidade Universitaria, Lisboa, Portugal
LP 15 du CNRS, Physiques des Liguides et Electrochimie, Laboratoire de L'Universite Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75257 Paris Cedex, France
Instituto Superior Tecnico, Departamento de Engenharia Quimica, Laborat6rio de Electroquimica, Av. Rovisco Pais, 1096 Lisboa Codex, Portugal
GARCIA-TELLAECHE, PILAR INASMET, Barrio de Igara sin Camino de Portueche, 20009 San Sebastian, Espana
GEENEN, F.H.
GURBUZ, RIZA
HUMMEL, R.E.
IMER, FILIZ
IZQUIERDO, P.M.
JAFAR, M.I.
Division of Corrosion Technology and Electrochemistry, Lab. for Materials Science and Technology, Delft University of Technology, P.O. BOX 5052, 2600 GA Delft, The Netherlands
Metallurgical Engineering Department, Middle East Technical University, 06531 Ankara, Turkey
Department of Materials Science Engineering, University of Florida, Gainesville, Florida, Flo. 32611, U.S.A.
Yildiz University, Department of Chemistry, Faculty of Science and Art, 80270 Sisli, Istambul, Turkey
Escuela Tecnica Superior de Ingenieros Industriales, Apartado 62, 36200 Vigo, Espana
CAPCIS/UMIST, P.O.BOX 88, Manchester, M60 1QD, U.K.
JOHNSON, C.S.
JONES, R.D.
JUSTO, M.JULIA
KING, FRASER
KISSEL, JACQUES
KIRIAKIDIS, N.
KRISHANAKUMAR, R.
LAWSON, KEVIN
LEITAO, EUGENIA
LOHRENGEL, MANUEL
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, U.S.A.
University of Wales, Cardif, U.K.
LNETI/DTM, Az. dos Lameiros a Estrada Pa90 do Lumiar, 1699 Lisboa Codex, Portugal
Atomic Energy of Canada, Whiteshell Nuclear Research Establishment, Pinawa, Manitoba, Canada ROE lLO, Canada
CEBELCOR, Av. Paul Herger, Grille 2, 1050 Bruxelles, Belgique
Agricultural College of Athens, Athens, Greece (absent)
Fontana Corrosion Center, Department of Materials Science, The Ohio State University, Columbus, Ohio 43210, U.S.A.
Corrosion and Protection Centre, UMIST, Sacville St., Manchester M60 1QD, U.K.
LNETI/PORTO, Rua d~ Salazares, 842, 4100 Porto, Portugal
Institut fUr Physikalische Chemie, Universitat DUsseldorf, Universitatsstr. 1, GebaUde 26.32, 4000 DUsseldorf, F.R.G.
MACDONALD, DIGBY D. SRI International, 333 Ravenswood Avenue, Menlo Park, CA 94025, U.S.A.
MACDONALD, MYRNA
MANSFELD, FLORIAN
MELENDRES, CARLOS
MORI, ERIK
SRI International, 333 Ravenswood Avenue, Menlo Park, CA 94025, U.S.A.
Corrosion and Environment Effects Laboratory, Department of Materials Science, University of Southern California, Los Angeles, CA 90089-0241, U.S.A.
Materials Science and Chemical Technology Divisions, Argonne National Laboratory, Argonne, Illinois 60439, U.S.A.
Materials Science and Chemical Technology Division, Argonne National Laboratory, Argonne, Illinois 60439, U.S.A.
xvii
NEWMAN, ROGER C. Corrosion and Protection Centre, UMIST, P.O. BOX 88, Manchester M60 1QD, U.K.
PENA, U.G. Escuela Tecnica Superior de Ingenieros Industriales, Dept. Chemical Engineering Apartado 62, 36200 Vigo, Espana
PEREIRA, DULCINEA LNETI, Az. dos Lameiros a Estrada do Pa90 do Lumiar, 1699 Lisboa Codex, Portugal
PONTINHA, MANUELA ISEL - Instituto Superior de Engenharia de Lisboa, Laboratorio de Corrosao, Rua Conselheiro Emidio Navarro, 1800 Lisboa codex, Portugal
POURBAIX, MARCEL Belgium Centre for Corrosion Study, CEBELCOR, Av. Paul Heger, Grille 2, 1050 Brussels, Belgium
RANGEL, CARMEN M. LNETI/DTM, Az. dos Lameiros a Estrada do Pa90 do Lumiar, 22, 1699 Lisboa Codex, Portugal
ROBERGE, REAL IREQ - Institut de Recherche d'HydroQuebec, 1800 Montee Ste-Julie, Varennes (Quebec) JOL 2PO, Canada
SALTA, MANUELA R. LNEC - Laboratorio Nacional de Engenharia Civil, Av do Brasil, 101, 1799 Lisboa Codex, Portugal
SARA~, A.S. Technical University of Istambul, Department of Chemistry, ITU Fer-Eded. Fak. Kimya Bolunu, Maslak 80626, Istambul, Turkey
SCANTLEBURY, DAVID Corrosion and Protection Centre UMIST, P.O. BOX 88, Manchester M60 1QD, U.K.
SILVA, FERNANDO Faculdade de Ciencias da Universidade do Porto, Porto, Portugal
SILVA, TERESA O.M. Instituto Superior Tecnico, Laboratorio de Electroquimica, Av. Rovisco Pais, 1096 Lisboa Codex, Portugal
SIMOES, ALDA M.P. Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal
SIMPLICIO, H. LNETI/DTM, Az. dos Lameiros a Estrada do Pa90 do Lumiar, 1699 Lisboa Codex, Portugal
xviii
SOUSA, SUSANA M. FEUP, Departamento de Metalurgia, Rua dos Bragas, 4099 Porto Codex, Portugal
STATHEROPOULOS, M. Laboratory of Inorganic and Anal. Chemistry, Department of Chemical Engineering, National Technical Uni. of Athens, 42 Patissiov Str., 10682, Athens, Greece
SZKLARSKA-SMIALOWSKA, Z. Fontana Corrosion Center, Department of Materials Science, The Ohio State University, Columbus, Ohio, U.S.A.
TASSINARI, MICHELA Centro Studi Corrosione "A. Dacco", Chemistry Department, University of Ferrara, Via L. Borsari, 46/44100 Ferrara, Italy
TRUJILLO, M. CNRS-CEMS, 15 rue Georges Urbain,94400 Vitry-Sur-Seine, France
TRAVASSOS, MARIA LNETI, Az. dos Lameiros a Estrada Pa90 do Lumiar, 1699 Lisboa Codex, Portugal
WATKINS, KEN G. Department of Materials Science and Eng., The University of Liverpool, P.O. BOX 147 Liverpool, L69 3BX, U.K.
WEBSTER, BARBARA Corrosion and Protection Centre, UMIST, P.O. BOX 88, Manchester M60 1QD, U.K.
WEST, ALAN Department of Chemical Engineering, University of California, Berkeley, CA 94709, U.S.A.
ZDUNEK, ALAN Illinois Institute of Technology, 10 W. 33 rd St., hall room 105, Perlstein, Chicago,
List of Contributors BARBOSA, M.A.
COTTIS, R.A.
DA CUNHA BELO, M.
DEVINE, T.M.
FERREIRA, M.G.S.
GABRIELLI, C.
HUET, F
HUMMEL, R.E.
KEDDAM, M.
Department of Metallurgy, Faculty of Engineering, University of Oporto, Rua dos Bragas, 4099 Porto Codex, Portugal
Corrosion and Protection Centre, UMIST, Manchester M60 1QD, U.K.
CNRS - CECM, 15 rue Georges Urbain, 94400 Vitry-Sur-Seine, France
Department of Materials Science and Mineral Engineering, University of California, Berkeley, CA 94720, U.S.A.
Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal
LP 15 du CNRS, Physiques des Liquides et Electrochimie, Laboratoire de L'Universite Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75257 Paris Cedex 05, France
LP 15 du CNRS, Physiques des Liquides et Electrochimie, Laboratoire de L'Universite Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75257 Paris Cedex 05, France
Department of Materials Science Engineering, University of Florida, GAINESVILLE, Florida, Flo. 32611, U.S.A.
LP 15 du CNRS, Physiques des Liquides et Electrochimie, Laboratoire de L'Universite Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75257 Paris Cedex 05, France
xix
xx
KELLY, R.G.
KRISHANAKUMAR, R.
LOHRENGEL, M.M.
MACDONALD, D.D.
MANSFELD, F.
MELENDRES, C.A.
NEWMAN, R.C.
POURBAIX, M.
SILVA, R.A.
SIMOES, A.M.P.
Corrosion and Protection Centre, UMIST, P.O. BOX 88, Sackville St., Manchester M60 lQD, U.K.
Fontana Corrosion Center, Department of Materials Science, The Ohio State University, Columbus, Ohio 43210, U.S.A.
Institut flir Physikalische Chemie und Elektrochemie, Heinrich-Heine Universitat DUsseldorf, Universitatsstr. 1, D-4000 DUsseldorf 1, Germany
SRI International, 333 Ravenswood Avenue, Menlo Park, CA 94025, U.S.A.
Corrosion and Environmental Effects Laboratory, Department of Materials Science, University of Southern California, Los Angeles, CA 90089 -0241, U.S.A.
Materials Science and Chemical Technology Divisions, Argonne National Laboratory, Argonne, Illinois 60439, U.S.A.
Corrosion and Protection Centre, UMIST, P.O. BOX 88, Manchester M60 lQD, U.K.
Belgium Centre for Corrosion Study, CEBELCOR, Av. Paul Heger, Grille 2, 1050 Brussels, Belgium
Department of Metallurgy, Faculty of Engineering, University of Oporto, Rua dos Bragas, 4099 Porto Codex, Portugal
Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal
SZKLARSKA-SMIALOWSKA, Z. Fontana Corrosion Center, Department of Materials Science, The Ohio State University, Columbus, Ohio, U.S.A.
TURGOOSE, M.A. Corrosion and Protection Centre, UMIST, Manchester M60 lQD, U.K.
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