Electrochemical and Optical Techniques for the Study and Monitoring of Metallic Corrosion

NATO ASI Series Advanced Science Institutes Series

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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.