Engineering Materials

The “Engineering Materials” series provides topical information on innovative,

structural and functional materials and composites with applications in optical,
electronical, mechanical, civil, aeronautical, medical, bio and nano engineering.
The individual volumes are complete, comprehensive monographs covering the
structure, properties, manufacturing process and applications of these materials.
This multidisciplinary series is devoted to professionals, students and all those
interested in the latest developments in the Materials Science field.

More information about this series at http://www.springer.com/series/4288

Pietro Pedeferri

Corrosion Science
and Engineering
Edited by Luciano Lazzari and MariaPia Pedeferri

In Cooperation with Marco Ormellese, Andrea Brenna,

Silvia Beretta, Fabio Bolzoni, Maria Vittoria Diamanti

123
Pietro Pedeferri (Deceased)
Politecnico di Milano
Milan, Italy

ISSN 1612-1317 ISSN 1868-1212 (electronic)

Engineering Materials
ISBN 978-3-319-97624-2 ISBN 978-3-319-97625-9 (eBook)
https://doi.org/10.1007/978-3-319-97625-9

Library of Congress Control Number: 2018950812

© Springer Nature Switzerland AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein or
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface

This Pedeferri’s Corrosion Science and Engineering textbook is the English edition
of Pietro Pedeferri’s Corrosione e Protezione dei Materiali, Polipress, Milano
(2007), with many integrations made by his collaborators of the PoliLaPP, the
Laboratory of Corrosion of Materials that Pedeferri founded. The main goal while
translating and integrating the original Italian book, so far very appreciated in Italy
with about 2000 copies printed, is to give a modern and updated handbook on
corrosion and corrosion prevention for a twofold use: as a teaching textbook and a
modern, technical support for industrial applications. This textbook stands as an
ideal learning resource for students of corrosion courses in chemical, mechanical,
energy and materials engineering at graduate and advanced undergraduate levels, as
well as a valuable reference for engineers.
This English edition, integrated and updated, contains 30 chapters, dealing with
corrosion theory (9 chapters), forms of corrosion (7), corrosion control and pre-
vention methods (3), applications in different environments as waters, air, soil,
concrete (4), and industrial applications as petrochemical plants, refinery and high
temperature (2) as well as corrosion of implants in the human body. Four chapters
are dedicated to design, corrosion monitoring, laboratory tests and the statistical
processing of corrosion data. Chapters dedicated to the on-field applications pro-
pose an overview of the most used metals and relevant case histories. Emphasis has
been devoted to cathodic protection and corrosion of reinforced concrete to give
merit to the pioneering works carried out by Pietro Pedeferri. Each chapter is
enriched by pictures of corrosion case studies analysed by PoliLaPP; most of the
samples are actually available at the “Corrosion Museum”, where Pietro Pedeferri
and his school have collected the most significant corrosion case studies.
The book offers the reader and the user many case histories and an important
number of questions and exercises to help check the acquired knowledge. Questions
and exercises included in each chapter represent the experience gathered by
Pedeferri and his school over the last 50 years as a fruit of teaching, research,
consultancy on material selection, failure analysis and corrosion engineering.
Answers and solutions of exercises for readers will be available on PoliLaPP
website (http://polilapp.chem.polimi.it).

v
vi Preface

Finally, a warm thank to all collaborators Andrea Brenna Silvia Beretta, Fabio
Bolzoni, Maria Vittoria Diamanti for their hard, precious and tenacious work in
contributing to the translation, integration and revision of the chapters and the effort
spent on collecting more than 300 exercises. Special mention to Marco Ormellese
for the unparalleled contribution. Thanks to Roberto Chiesa for reviewing the
chapter related to corrosion in the human body, Giorgio Re for the suggestions on
chapters dedicated to environmental-assisted cracking, Eleonora Faccioli for the
drawing of figures and tables and Davide Prando for the collection of the original
pictures.

Milan, Italy Luciano Lazzari

June 2018 MariaPia Pedeferri
Contents

1 General Principles of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Corrosion as Metallurgy in Reverse . . . . . . . . . . . . . . . . . . . . 2
1.2 The Economic Impact of Corrosion . . . . . . . . . . . . . . . . . . . . 3
1.3 Corrosion Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.1 Uniform or Generalized Corrosion . . . . . . . . . . . . . . 5
1.3.2 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.3 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . 7
1.4 Corrosion Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4.1 Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4.2 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 Corrosion Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2 Electrochemical Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1 Electrochemical Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2 Historical Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1 Evans’s Experiences . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3 Local Cell Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3.1 Mixed Potential Theory . . . . . . . . . . . . . . . . . . . . . . 24
2.4 Corrosion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.1 Anodic Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.2 Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.4.3 Other Cathodic Processes . . . . . . . . . . . . . . . . . . . . 27
2.4.4 Complementary Processes . . . . . . . . . . . . . . . . . . . . 27
2.5 Stoichiometry (Faraday Law) . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5.1 Corrosion Current Density . . . . . . . . . . . . . . . . . . . . 28
2.6 Change of the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

vii
viii Contents

3 Thermodynamics of Aqueous Corrosion . . . . . . . . . . . . . . . . . . . . . 37

3.1 Driving Voltage and Free Energy . . . . . . . . . . . . . . . . . . . . . . 38
3.2 Corrosion and Immunity Condition . . . . . . . . . . . . . . . . . . . . 39
3.3 Standard Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.4 Potential of an Electrochemical Reaction . . . . . . . . . . . . . . . . 43
3.5 Potential of Metal Dissolution Reaction . . . . . . . . . . . . . . . . . 44
3.5.1 Corrosion and Immunity Conditions . . . . . . . . . . . . 45
3.6 Potential of Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . 45
3.6.1 Potential of Hydrogen Evolution Reaction . . . . . . . . 46
3.6.2 Potential of Oxygen Reduction Reaction . . . . . . . . . 47
3.6.3 Applications of Thermodynamic Criteria . . . . . . . . . 48
3.7 Insoluble Products and Complexing Species . . . . . . . . . . . . . . 50
3.8 Reference Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.9 Electrochemical Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.9.1 Concentration Cells . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.10 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4 Pourbaix Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.1 Oxygen Reduction and Hydrogen Evolution . . . . . . . . . . . . . . 58
4.2 Metal Immunity, Corrosion and Passivation . . . . . . . . . . . . . . 58
4.2.1 Equilibrium Between Immunity and Corrosion . . . . . 59
4.2.2 Equilibrium Between Immunity and Passivation . . . . 61
4.2.3 Equilibrium Between Corrosion and Passivation . . . . 62
4.3 Amphoteric Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.3.1 Electrochemical Dissolution in Alkaline Solution . . . 63
4.3.2 Chemical Dissolution in Alkaline Solution . . . . . . . . 64
4.4 Pourbaix Diagrams of Some Metals at 25 °C . . . . . . . . . . . . . 64
4.5 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5 Kinetics of Aqueous Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.1 Driving Force and Corrosion Rate . . . . . . . . . . . . . . . . . . . . . 74
5.2 Dissipations in Corrosion Systems . . . . . . . . . . . . . . . . . . . . . 75
5.3 Activation Overvoltage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.3.1 Exchange Current Density and Tafel Law . . . . . . . . 76
5.3.2 Potential-Current Density Diagrams (or
Characteristic Curves) . . . . . . . . . . . . . . . . . . . . . . . 79
5.3.3 Oxidation or Reduction of a Metal . . . . . . . . . . . . . . 81
5.3.4 Hydrogen Evolution (Activation Overvoltage) . . . . . 82
5.3.5 Oxygen Reduction (Activation Overvoltage) . . . . . . . 85
5.4 Concentration Overvoltage . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.4.1 Oxygen Reduction: Limiting Current . . . . . . . . . . . . 87
Contents ix

5.4.2 Total Oxygen Overvoltage . . . . . . . . . . . . . . . . . . . 89

5.5 Other Cathodic Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.6 Passivation and Passivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.6.1 Film Formation Mechanisms . . . . . . . . . . . . . . . . . . 92
5.6.2 Oxide Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.6.3 Active-Passive Metals . . . . . . . . . . . . . . . . . . . . . . . 95
5.6.4 Passivity-Related Parameters . . . . . . . . . . . . . . . . . . 97
5.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
6 Evans Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 103
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 104
6.2 Evans Diagrams of Active Metals . . . . . . . . . . . . ....... . . 104
6.3 Corrosion Conditions in the Presence of an Ohmic Drop . . . . . 108
6.4 Multiple Cathodic Processes . . . . . . . . . . . . . . . . ....... . . 110
6.5 Imposed Polarization . . . . . . . . . . . . . . . . . . . . . . ....... . . 111
6.6 Experimental Polarization Curves . . . . . . . . . . . . . ....... . . 112
6.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . ....... . . 115
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... . . 118
7 Corrosion Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7.1 Metal Affecting Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7.1.1 Modification of Metal Surface Composition . . . . . . . 120
7.1.2 Nobility by Alloying . . . . . . . . . . . . . . . . . . . . . . . . 121
7.1.3 Overvoltage of Cathodic Processes . . . . . . . . . . . . . 122
7.1.4 Cathodic Alloying . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.1.5 Reduction of Anodic Areas . . . . . . . . . . . . . . . . . . . 124
7.1.6 Passivation Induced by Alloying . . . . . . . . . . . . . . . 124
7.2 Environment Affecting Factors . . . . . . . . . . . . . . . . . . . . . . . . 124
7.2.1 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7.2.2 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7.2.3 Differential Aeration . . . . . . . . . . . . . . . . . . . . . . . . 126
7.2.4 Salt Formation/Precipitation . . . . . . . . . . . . . . . . . . . 128
7.2.5 Cation Displacement . . . . . . . . . . . . . . . . . . . . . . . . 129
7.2.6 Microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
7.3 Metal/Environment Affecting Factors . . . . . . . . . . . . . . . . . . . 133
7.3.1 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
7.3.2 Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
7.3.3 Corrosion Products and Deposits . . . . . . . . . . . . . . . 135
7.3.4 Flow Regime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
7.3.5 Active–Passive Related Parameters . . . . . . . . . . . . . 135
7.4 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
x Contents

8 Uniform Corrosion in Acidic and Aerated Solutions . . . . . . . . . . . . 145

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
8.2 Acidic Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
8.2.1 Strong Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.2.2 Carbonic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.2.3 Hydrogen Sulphide . . . . . . . . . . . . . . . . . . . . . . . . . 154
8.2.4 Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
8.2.5 Corrosion of Passive Metals . . . . . . . . . . . . . . . . . . 155
8.3 Aerated Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
8.3.1 Oxygen Limiting Diffusion Current . . . . . . . . . . . . . 157
8.3.2 Presence of Chlorine . . . . . . . . . . . . . . . . . . . . . . . . 158
8.3.3 Dimensionless Number Approach . . . . . . . . . . . . . . 159
8.3.4 Corrosion of Noble Metals . . . . . . . . . . . . . . . . . . . 160
8.3.5 Corrosion of Non-noble Metals . . . . . . . . . . . . . . . . 160
8.3.6 Corrosion of Passive Metals . . . . . . . . . . . . . . . . . . 162
8.4 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
9 Macrocell Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
9.1 Electrical Field in Uniform Corrosion . . . . . . . . . . . . . . . . . . . 170
9.2 Electrical Field in a Macrocell . . . . . . . . . . . . . . . . . . . . . . . . 170
9.2.1 Pure Ohmic Systems . . . . . . . . . . . . . . . . . . . . . . . . 171
9.2.2 Two-Electrode Macrocell . . . . . . . . . . . . . . . . . . . . 172
9.3 Current Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
9.3.1 Primary Current Distribution . . . . . . . . . . . . . . . . . . 173
9.3.2 Secondary Current Distribution . . . . . . . . . . . . . . . . 173
9.4 Throwing Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
9.5 Typical Geometries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9.5.1 Inside a Pipe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9.5.2 Outside a Pipeline . . . . . . . . . . . . . . . . . . . . . . . . . . 178
9.5.3 On a Plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
9.6 Maximum Surface Area Ratio . . . . . . . . . . . . . . . . . . . . . . . . 180
9.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
10 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
10.1 Effects on Metal Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 184
10.2 Galvanic Effects on Less Noble Metal . . . . . . . . . . . . . . . . . . 188
10.3 Galvanic Effects on More Noble Metal . . . . . . . . . . . . . . . . . . 189
10.4 Galvanic Coupling Representation by Evans Diagrams . . . . . . 192
10.5 Four Main Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
10.5.1 Practical Nobility . . . . . . . . . . . . . . . . . . . . . . . . . . 195
10.5.2 Cathodic Overvoltage on More Noble Metal . . . . . . 197
10.5.3 Surface Area Ratio and Maximum
Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Contents xi

10.5.4 Electrolyte Resistivity . . . . . . . . . . . . . . . . . . . . . . . 198

10.5.5 Geometry of the Domain . . . . . . . . . . . . . . . . . . . . . 199
10.6 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
10.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
11 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
11.1 Pitting Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
11.2 Pitting Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
11.2.1 Pit Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
11.2.2 Propagation of Stable Pits . . . . . . . . . . . . . . . . . . . . 215
11.2.3 Corrosion Rate of Stable Pits . . . . . . . . . . . . . . . . . . 216
11.3 Pitting on Stainless Steels in Chloride-Containing
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
11.3.1 PREN Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
11.3.2 Free Corrosion Potential . . . . . . . . . . . . . . . . . . . . . 218
11.3.3 Pitting Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
11.3.4 Repassivation Potential . . . . . . . . . . . . . . . . . . . . . . 218
11.3.5 Pedeferri’s Diagram . . . . . . . . . . . . . . . . . . . . . . . . 220
11.3.6 Pitting Induction Time . . . . . . . . . . . . . . . . . . . . . . 220
11.4 Pitting Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
11.4.1 Critical Pitting Temperature and Critical
Pitting Chloride Concentration . . . . . . . . . . . . . . . . . 223
11.5 Pitting on Carbon Steel in Chloride-Contaminated
Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
11.6 Pitting on Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 224
11.7 Pitting as Markovian Process or Prevention of Pitting . . . . . . . 225
11.8 Prevention of Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . 227
11.9 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
11.10 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
12 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
12.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
12.2 Crevice Critical Gap Size (CCGS) . . . . . . . . . . . . . . . . . . . . . 232
12.3 Mechanism of Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . 233
12.3.1 First Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.3.2 Second Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.3.3 Third Stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
12.4 Metal Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
12.5 Environmental Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
12.6 Prevention of Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . 237
12.7 Crevice-Like Corrosion of Active Metals . . . . . . . . . . . . . . . . 238
xii Contents

12.7.1 Corrosion Under Insulation . . . . . . . . . . . . . . . . . . . 238

12.7.2 Automotive Related Corrosion . . . . . . . . . . . . . . . . . 238
12.7.3 Riveted Structures . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.7.4 Stored Plates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.8 Filiform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
12.9 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
12.10 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
13 Stress Corrosion Cracking and Corrosion-Fatigue . . . . . . . . . . . . . 243
13.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
13.2 SCC Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
13.3 Morphology and Conditions of Occurrence . . . . . . . . . . . . . . . 247
13.3.1 Crack Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
13.3.2 Crack Propagation . . . . . . . . . . . . . . . . . . . . . . . . . 249
13.4 Mechanical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
13.4.1 Stress Intensity Factor, KI, and Fracture
Toughness, KIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
13.4.2 Crack Growth and KISCC . . . . . . . . . . . . . . . . . . . . . 251
13.4.3 Crack Growth Rate and KI . . . . . . . . . . . . . . . . . . . 252
13.4.4 Crack Growth and Strain Rate . . . . . . . . . . . . . . . . . 253
13.4.5 Test Methods—SSRT . . . . . . . . . . . . . . . . . . . . . . . 253
13.5 Environment-Related Parameters . . . . . . . . . . . . . . . . . . . . . . 255
13.6 Metallurgical Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
13.6.1 Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
13.6.2 Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . 259
13.6.3 Sensitization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
13.7 SCC Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
13.7.1 Reduction of Stress and Defect Size . . . . . . . . . . . . 261
13.7.2 Control of Environment, Metallurgy
and Polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
13.8 Corrosion-Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
13.8.1 Mechanical Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . 262
13.8.2 Influencing Factors . . . . . . . . . . . . . . . . . . . . . . . . . 264
13.8.3 Corrosion-Fatigue and Fracture Mechanics . . . . . . . . 265
13.8.4 True Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . . . 265
13.8.5 Stress Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . . 267
13.8.6 Prevention of Corrosion-Fatigue . . . . . . . . . . . . . . . 268
13.9 Some Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
13.10 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
13.11 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Contents xiii

14 Hydrogen-Induced Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

14.1 Hydrogen Induced Damage . . . . . . . . . . . . . . . . . . . . . . . . . . 276
14.1.1 Adsorption, Dissolution and Trapping . . . . . . . . . . . 276
14.1.2 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
14.1.3 Atomic Hydrogen Produced by a Cathodic
Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
14.1.4 Decomposition and Solubility of Hydrogen
at High Temperature . . . . . . . . . . . . . . . . . . . . . . . . 283
14.2 HT-HID or Hydrogen Attack . . . . . . . . . . . . . . . . . . . . . . . . . 283
14.3 LT-HID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
14.3.1 Delayed Fracture . . . . . . . . . . . . . . . . . . . . . . . . . . 286
14.3.2 HIC and Blistering . . . . . . . . . . . . . . . . . . . . . . . . . 287
14.3.3 HE Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
14.3.4 Failure Mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
14.3.5 HE by Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
14.3.6 Sulphide Stress Cracking (SSC) . . . . . . . . . . . . . . . . 292
14.4 Prevention of LT-HID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
14.4.1 Prevention of HIC and Blistering . . . . . . . . . . . . . . . 293
14.4.2 Materials for Sour Service . . . . . . . . . . . . . . . . . . . . 293
14.5 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
14.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
15 Intergranular and Selective Corrosion . . . . . . . . . . . . . . . . . . . . . . 297
15.1 Impurities and Segregations . . . . . . . . . . . . . . . . . . . . . . . . . . 298
15.2 Sensitization of Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . 298
15.3 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
15.4 Prevention of Intergranular Corrosion . . . . . . . . . . . . . . . . . . . 301
15.5 Weld Decay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
15.5.1 Knife-Line Attack . . . . . . . . . . . . . . . . . . . . . . . . . . 303
15.6 Intergranular Corrosion of Nickel Alloys . . . . . . . . . . . . . . . . 303
15.7 Intergranular Corrosion Without Sensitization . . . . . . . . . . . . . 304
15.8 Exfoliation of Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . 306
15.9 Intergranular Corrosion Tests . . . . . . . . . . . . . . . . . . . . . . . . . 307
15.10 Selective Corrosion of an Alloying Element . . . . . . . . . . . . . . 307
15.10.1 Dezincification of Brass . . . . . . . . . . . . . . . . . . . . . 308
15.10.2 Cast Iron Graphitization . . . . . . . . . . . . . . . . . . . . . 309
15.11 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
15.12 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
16 Erosion-Corrosion and Fretting . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
16.1 Erosion-Corrosion Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
16.1.1 Corrosion by Turbulence . . . . . . . . . . . . . . . . . . . . . 315
xiv Contents

16.1.2 Cavitation Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 317

16.1.3 Metal Affecting Properties . . . . . . . . . . . . . . . . . . . . 319
16.1.4 Environment Affecting Properties . . . . . . . . . . . . . . 320
16.1.5 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
16.2 Fretting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
16.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
16.2.2 Main Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
16.2.3 Fretting Corrosion Fatigue . . . . . . . . . . . . . . . . . . . . 322
16.2.4 Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
16.2.5 Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
16.3 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
16.4 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
17 Corrosion Prevention by Coatings . . . . . . . . . . . . . . . . . . . . . . . . . 327
17.1 Metallic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.1 Coating Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.2 Cathodic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . 328
17.1.3 Anodic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
17.1.4 Multilayer Coatings . . . . . . . . . . . . . . . . . . . . . . . . 330
17.1.5 Methods for Obtaining Metallic Coatings . . . . . . . . . 333
17.1.6 Zinc Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
17.1.7 Tin Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
17.1.8 Nickel Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
17.1.9 Chromium Coatings . . . . . . . . . . . . . . . . . . . . . . . . 338
17.1.10 Copper Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
17.1.11 Precious Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2 Conversion Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2.1 Phosphate Coatings . . . . . . . . . . . . . . . . . . . . . . . . . 339
17.2.2 Chromate Filming . . . . . . . . . . . . . . . . . . . . . . . . . . 340
17.2.3 Anodic Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 341
17.3 Other Inorganic Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
17.3.1 Hot Enamels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
17.3.2 Thick Cementitious Coatings . . . . . . . . . . . . . . . . . . 344
17.3.3 Thick Corrosion Resistant Coatings . . . . . . . . . . . . . 344
17.4 Paintings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
17.4.1 Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
17.4.2 Corrosion Under Paintings . . . . . . . . . . . . . . . . . . . 349
17.4.3 Protective Action of Paints . . . . . . . . . . . . . . . . . . . 350
17.4.4 Paint Film Properties . . . . . . . . . . . . . . . . . . . . . . . . 353
17.4.5 Painting Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
17.4.6 Pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
17.4.7 Paint Application . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Contents xv

17.4.8 Painting Maintenance . . . . . . . . . . . . . . . . . . . . . . . 358

17.4.9 Threats at the Workplace . . . . . . . . . . . . . . . . . . . . . 358
17.5 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
17.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
18 Environmental Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
18.1 pH Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
18.2 Oxygen Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
18.3 Corrosion Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
18.3.1 Classification of Inhibitors . . . . . . . . . . . . . . . . . . . . 368
18.3.2 Cathodic Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . 369
18.3.3 Anodic Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . 369
18.3.4 Mixed Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
18.3.5 Inhibitor Adsorption Mechanism . . . . . . . . . . . . . . . 373
18.3.6 Adsorption Isotherm . . . . . . . . . . . . . . . . . . . . . . . . 374
18.3.7 Inhibitor Effectiveness . . . . . . . . . . . . . . . . . . . . . . . 375
18.4 Biocides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
18.5 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
19 Cathodic and Anodic Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
19.1 Cathodic Protection (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
19.1.1 Protection Potential . . . . . . . . . . . . . . . . . . . . . . . . . 384
19.1.2 Thermodynamic Effect . . . . . . . . . . . . . . . . . . . . . . 385
19.1.3 Kinetic Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
19.1.4 Protection Criteria and Overprotection . . . . . . . . . . . 386
19.1.5 Protection Current Density . . . . . . . . . . . . . . . . . . . 387
19.1.6 Anodic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 388
19.1.7 Coatings and Scales . . . . . . . . . . . . . . . . . . . . . . . . 389
19.1.8 Current Distribution . . . . . . . . . . . . . . . . . . . . . . . . 390
19.2 CP Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
19.2.1 Galvanic Anodes Cathodic Protection Systems
(GACP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
19.2.2 Impressed Current Cathodic Protection Systems
(ICCP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
19.2.3 CP Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
19.3 Anodic Protection (AP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
19.3.1 Electrode Reactions . . . . . . . . . . . . . . . . . . . . . . . . 408
19.3.2 AP Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
19.3.3 AP Versus Active-Passive Metals . . . . . . . . . . . . . . 409
19.3.4 Throwing Power of AP . . . . . . . . . . . . . . . . . . . . . . 411
19.3.5 Potentiostatic Feeding . . . . . . . . . . . . . . . . . . . . . . . 412
19.3.6 CP-AP Comparison . . . . . . . . . . . . . . . . . . . . . . . . . 413
xvi Contents

19.4 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414

19.5 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
20 Corrosion in Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
20.1 Types of Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
20.2 Factors Influencing Corrosion Likelihood . . . . . . . . . . . . . . . . 425
20.2.1 Oxygen Content . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
20.2.2 Water Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
20.2.3 Scaling Tendency . . . . . . . . . . . . . . . . . . . . . . . . . . 426
20.2.4 Water Resistivity . . . . . . . . . . . . . . . . . . . . . . . . . . 429
20.2.5 Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
20.2.6 Other Cathodic Reactant . . . . . . . . . . . . . . . . . . . . . 429
20.3 Uniform Corrosion Rate Evaluation . . . . . . . . . . . . . . . . . . . . 430
20.4 Metals for Freshwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
20.4.1 Steel and Cast Iron . . . . . . . . . . . . . . . . . . . . . . . . . 432
20.4.2 Galvanized Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
20.4.3 Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
20.4.4 Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
20.5 Brackish Water and Seawater . . . . . . . . . . . . . . . . . . . . . . . . . 438
20.5.1 Corrosion Zones in Seawater . . . . . . . . . . . . . . . . . . 439
20.5.2 Materials for Seawater . . . . . . . . . . . . . . . . . . . . . . 440
20.6 Applicable Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
20.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
21 Corrosion in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
21.1 Soil Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
21.2 Corrosion in Aerated Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
21.2.1 Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 449
21.2.2 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 450
21.2.3 Corrosion Index . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
21.2.4 Differential Aeration Corrosion . . . . . . . . . . . . . . . . 451
21.2.5 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 452
21.2.6 Effect of Soil Resistivity . . . . . . . . . . . . . . . . . . . . . 457
21.3 Microbial Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
21.4 Corrosion by Stray Currents . . . . . . . . . . . . . . . . . . . . . . . . . 461
21.4.1 Electrochemical Reactions on the Interfered
Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
21.4.2 Interference Current . . . . . . . . . . . . . . . . . . . . . . . . 464
21.4.3 Interference assessment . . . . . . . . . . . . . . . . . . . . . . 466
21.4.4 Criteria for Interference Acceptance . . . . . . . . . . . . . 467
21.4.5 Prevention and Control of Stray Current
Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
Contents xvii

21.4.6 Alternating Current Interference . . . . . . . . . . . . . . . . 471

21.4.7 Typical Cases of Improbable Interference . . . . . . . . . 474
21.5 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
21.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
22 Atmospheric Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
22.1 Liquid Film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2 Factors Affecting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2.1 Relative Humidity . . . . . . . . . . . . . . . . . . . . . . . . . . 480
22.2.2 Time of Wetness . . . . . . . . . . . . . . . . . . . . . . . . . . 481
22.2.3 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
22.2.4 Atmosphere Composition . . . . . . . . . . . . . . . . . . . . 483
22.2.5 Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
22.3 Classification of Environments . . . . . . . . . . . . . . . . . . . . . . . . 485
22.3.1 Microenvironments . . . . . . . . . . . . . . . . . . . . . . . . . 486
22.3.2 Classification of Atmospheric Corrosiveness . . . . . . . 487
22.3.3 Indoor Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . 488
22.4 Corrosion Behaviour of Most Used Metals . . . . . . . . . . . . . . . 490
22.4.1 Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
22.4.2 Weathering Steels (Cor-Ten) . . . . . . . . . . . . . . . . . . 494
22.4.3 Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
22.4.4 Copper and Copper-Alloys . . . . . . . . . . . . . . . . . . . 501
22.4.5 Aluminium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
22.4.6 Other Metallic Materials . . . . . . . . . . . . . . . . . . . . . 502
22.5 Corrosion and Protection of Metallic Cultural Heritage . . . . . . 505
22.6 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
22.7 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
23 Corrosion in Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
23.1 Initiation, Propagation and Morphology of Corrosion . . . . . . . 510
23.2 Corrosion by Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
23.2.1 Carbonation Depth . . . . . . . . . . . . . . . . . . . . . . . . . 513
23.2.2 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
23.3 Chloride-Induced Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 516
23.3.1 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
23.3.2 Structures at a Risk . . . . . . . . . . . . . . . . . . . . . . . . . 519
23.4 Hydrogen Embrittlement . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
23.5 Corrosion by Stray Currents . . . . . . . . . . . . . . . . . . . . . . . . . 525
23.6 Prevention of Reinforcement Corrosion . . . . . . . . . . . . . . . . . 525
23.6.1 Quality of Concrete . . . . . . . . . . . . . . . . . . . . . . . . 526
23.6.2 Cover Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
23.6.3 Common Mistakes . . . . . . . . . . . . . . . . . . . . . . . . . 528
xviii Contents

23.7 Additional Protections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529

23.7.1 Concrete Surface Treatments . . . . . . . . . . . . . . . . . . 531
23.7.2 Corrosion Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . 532
23.7.3 Stainless Steel Reinforcements . . . . . . . . . . . . . . . . . 532
23.7.4 Galvanized Steel Reinforcements . . . . . . . . . . . . . . . 534
23.7.5 Cathodic Prevention (CPrev) . . . . . . . . . . . . . . . . . . 535
23.7.6 Comparison of Additional Protections . . . . . . . . . . . 535
23.7.7 Evaluation of service life by performance based
methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
23.8 Diagnosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
23.8.1 Concrete Cover Thickness Measurements
and Rebar Identification . . . . . . . . . . . . . . . . . . . . . 538
23.8.2 Analysis of Concrete . . . . . . . . . . . . . . . . . . . . . . . . 538
23.8.3 Electrochemical Techniques . . . . . . . . . . . . . . . . . . . 539
23.9 Repair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
23.9.1 Traditional Repair . . . . . . . . . . . . . . . . . . . . . . . . . . 541
23.9.2 Electrochemical Repair Techniques . . . . . . . . . . . . . 543
23.10 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
23.11 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
24 Corrosion in Petrochemical Plant . . . . . . . . . . . . . . . . . . . . . . . . . . 549
24.1 Petrochemical Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
24.2 The Corroding Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
24.3 Water Wetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
24.4 Corrosion Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
24.5 CO2-Related Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
24.5.1 Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . 556
24.5.2 Corrosion Rate Evaluation . . . . . . . . . . . . . . . . . . . . 557
24.5.3 Metals for Sweet Condition . . . . . . . . . . . . . . . . . . . 558
24.6 H2S-Related Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
24.6.1 Corrosion Mechanism . . . . . . . . . . . . . . . . . . . . . . . 562
24.6.2 Generalized Corrosion . . . . . . . . . . . . . . . . . . . . . . . 563
24.6.3 Hydrogen Induced Cracking (HIC) . . . . . . . . . . . . . 563
24.6.4 Sulphide Stress Cracking (SSC) . . . . . . . . . . . . . . . . 564
24.6.5 Metals for Sour Service Condition . . . . . . . . . . . . . . 565
24.7 Downstream Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
24.7.1 Corrosion by S/H2S Atmosphere . . . . . . . . . . . . . . . 566
24.7.2 Corrosion by Sulphur . . . . . . . . . . . . . . . . . . . . . . . 567
24.7.3 Corrosion by H2/H2S . . . . . . . . . . . . . . . . . . . . . . . 568
24.7.4 Corrosion by Naphthenic Acid . . . . . . . . . . . . . . . . 568
24.7.5 Hydrogen Attack . . . . . . . . . . . . . . . . . . . . . . . . . . 569
24.7.6 Organic Acid Corrosion . . . . . . . . . . . . . . . . . . . . . 569
24.7.7 Polythionic Acid Stress Corrosion Cracking . . . . . . . 570
Contents xix

24.7.8 High Temperature Sulphidation . . . . . . . . . . . . . . . . 570

24.8 International Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
24.9 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
25 Corrosion in the Human Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
25.1 Characteristics of Metals for Orthopaedic Purpose . . . . . . . . . . 576
25.1.1 Mechanical Resistance . . . . . . . . . . . . . . . . . . . . . . 576
25.1.2 Fatigue Resistance . . . . . . . . . . . . . . . . . . . . . . . . . 576
25.1.3 Resistance to Generalized Corrosion . . . . . . . . . . . . 577
25.1.4 Resistance to Crevice Corrosion . . . . . . . . . . . . . . . 577
25.1.5 Resistance to Fretting Corrosion . . . . . . . . . . . . . . . 577
25.1.6 Corrosion for Galvanic Coupling . . . . . . . . . . . . . . . 578
25.1.7 Biocompatibility . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
25.2 Classes of Metals Employed in Orthopaedics . . . . . . . . . . . . . 579
25.2.1 Austenitic Stainless Steels . . . . . . . . . . . . . . . . . . . . 579
25.2.2 Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
25.2.3 Titanium and Titanium Alloys . . . . . . . . . . . . . . . . . 581
25.3 Surface Finishing Treatments . . . . . . . . . . . . . . . . . . . . . . . . . 581
25.3.1 Barrel Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
25.3.2 Electropolishing . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
25.3.3 Passivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
25.3.4 Titanium Anodising . . . . . . . . . . . . . . . . . . . . . . . . 582
25.4 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
25.5 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
26 High Temperature Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
26.1 Corrosive Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
26.2 Thermodynamics and Kinetics . . . . . . . . . . . . . . . . . . . . . . . . 590
26.3 Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
26.3.1 Non Protective Oxides . . . . . . . . . . . . . . . . . . . . . . 592
26.3.2 Protective Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 593
26.4 Wagner Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
26.4.1 Oxide Conductivity and Lattice Defects . . . . . . . . . . 595
26.5 Morphology of Oxide Films . . . . . . . . . . . . . . . . . . . . . . . . . 597
26.6 Oxidation of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
26.7 Oxidation of Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
26.7.1 Oxidation of Only One of Two Metals
in Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
26.7.2 Oxidation of Both Metals in Alloy . . . . . . . . . . . . . 603
26.8 Other Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.1 Sulphidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.2 Carburization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
26.8.3 Halogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
xx Contents

26.9 Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606

26.9.1 Oxygen and Air . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.2 Steam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.3 Sulphur Compounds . . . . . . . . . . . . . . . . . . . . . . . . 606
26.9.4 Combustion Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
26.9.5 Nitridation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
26.10 Materials for Use at High Temperatures . . . . . . . . . . . . . . . . . 608
26.11 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
27 Prevention of Corrosion in Design . . . . . . . . . . . . . . . . . . . . . . . . . 611
27.1 Design Life and Reliability . . . . . . . . . . . . . . . . . . . . . . . . . . 612
27.1.1 How to Choose Reliability and Related
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
27.2 Prevention in Design Phase . . . . . . . . . . . . . . . . . . . . . . . . . . 613
27.2.1 Evaluation of Aggressiveness . . . . . . . . . . . . . . . . . 613
27.2.2 Reduction of Aggressiveness . . . . . . . . . . . . . . . . . . 613
27.2.3 Local Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . 614
27.2.4 Homogeneity Is Preferred . . . . . . . . . . . . . . . . . . . . 614
27.2.5 Change of Aggressiveness in Space
and with Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
27.3 Metal Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
27.3.1 Basic Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
27.3.2 Technological Criteria . . . . . . . . . . . . . . . . . . . . . . . 616
27.4 Some General Features of Used Metals . . . . . . . . . . . . . . . . . 616
27.4.1 Carbon and Low Alloy Steels . . . . . . . . . . . . . . . . . 616
27.4.2 Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
27.4.3 Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
27.4.4 Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 621
27.4.5 Copper Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
27.4.6 Titanium and Its Alloys . . . . . . . . . . . . . . . . . . . . . 622
27.5 General Philosophy for Metal Selection in Industry . . . . . . . . . 622
27.5.1 Alkaline Solutions . . . . . . . . . . . . . . . . . . . . . . . . . 623
27.5.2 Chloride-Free Acidic Solutions . . . . . . . . . . . . . . . . 624
27.5.3 Chloride-Containing Environments . . . . . . . . . . . . . 625
27.6 Prevention by Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
27.7 Prevention in Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
27.8 Prevention in Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
27.9 Commissioning and Start-up . . . . . . . . . . . . . . . . . . . . . . . . . 628
27.10 Prevention During Operation . . . . . . . . . . . . . . . . . . . . . . . . . 631
27.11 Planned Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631
27.12 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
Contents xxi

28 Monitoring and Inspections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635

28.1 Corrosion Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
28.1.1 Selection of Monitoring Locations . . . . . . . . . . . . . . 637
28.2 Common Monitoring Methods . . . . . . . . . . . . . . . . . . . . . . . . 637
28.2.1 Corrosion Coupon . . . . . . . . . . . . . . . . . . . . . . . . . 637
28.2.2 Corrosion Spool . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
28.2.3 Electrical Resistance Probe . . . . . . . . . . . . . . . . . . . 639
28.2.4 Linear Polarisation Resistance . . . . . . . . . . . . . . . . . 639
28.2.5 Galvanic Probe . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
28.2.6 Potential Measurement . . . . . . . . . . . . . . . . . . . . . . 641
28.2.7 Bio-probe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
28.2.8 Hydrogen Probe . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
28.3 Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
28.3.1 Electrochemical Noise . . . . . . . . . . . . . . . . . . . . . . . 646
28.3.2 EIS (Electrochemical Impedance Spectroscopy) . . . . 646
28.3.3 Acoustic Emission . . . . . . . . . . . . . . . . . . . . . . . . . 646
28.4 Plant Inspection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
28.4.1 Liquid Penetrant . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.2 Magnetic Particles . . . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.3 Radiographic Testing . . . . . . . . . . . . . . . . . . . . . . . 647
28.4.4 Ultrasonic Testing . . . . . . . . . . . . . . . . . . . . . . . . . 648
28.4.5 Eddy Current Method . . . . . . . . . . . . . . . . . . . . . . . 649
28.5 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
28.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
29 Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
29.1 Test Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
29.2 Accelerated Tests and Statistics . . . . . . . . . . . . . . . . . . . . . . . 653
29.3 Exposure Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
29.3.1 Mass Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
29.3.2 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 655
29.3.3 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 656
29.3.4 Galvanic Coupling . . . . . . . . . . . . . . . . . . . . . . . . . 659
29.3.5 Integranular Corrosion . . . . . . . . . . . . . . . . . . . . . . 660
29.3.6 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . 661
29.3.7 Erosion, Cavitation and Fretting . . . . . . . . . . . . . . . 664
29.3.8 Artificial Atmosphere—Cabinet Test . . . . . . . . . . . . 664
29.4 Electrochemical Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
29.4.1 Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 668
29.4.2 Pitting Potential and Repassivation Potential . . . . . . 672
29.4.3 Galvanic Coupling . . . . . . . . . . . . . . . . . . . . . . . . . 672
29.4.4 Intergranular Corrosion . . . . . . . . . . . . . . . . . . . . . . 673
xxii Contents

29.4.5 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . 674

29.4.6 Other Electrochemical Techniques . . . . . . . . . . . . . . 674
29.5 Applicable Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
29.6 Questions and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
30 Statistical Analysis of Corrosion Data . . . . . . . . . . . . . . . . . . . . . . . 679
30.1 Fundamentals of Statistics . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
30.1.1 Mean and Variability of Data Distribution . . . . . . . . 680
30.1.2 Statistical Distributions of Scatter Data . . . . . . . . . . 681
30.1.3 Reliability and Hazard Functions . . . . . . . . . . . . . . . 682
30.2 Probability Distributions Observed in Corrosion . . . . . . . . . . . 682
30.2.1 Normal (Gaussian) Distribution . . . . . . . . . . . . . . . . 683
30.2.2 Lognormal Distribution . . . . . . . . . . . . . . . . . . . . . . 685
30.2.3 Poisson and Exponential Distributions . . . . . . . . . . . 685
30.2.4 Generalized Extreme Value Statistics . . . . . . . . . . . . 687
30.2.5 Gumbel Extreme Value Statistics . . . . . . . . . . . . . . . 688
30.2.6 Weibull Extreme Value Statistics . . . . . . . . . . . . . . . 691
30.3 Sample Size and Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . . 694
30.3.1 Sample Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
30.3.2 Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
30.4 International Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
About the Author
Pietro Pedeferri (1938–2008)
… ‘I see that water, nay, I see
that fire and air and earth, and all their mixtures
become corrupt, and but a little while
endure; and yet created things were these!
Dante, The Divine Comedy, Paradise VII
Born “valtellinese”, adopted “milanese”, with heart
and spirit in Nestrelli
Pietro Pedeferri
Pietro Pedeferri was a Full Professor in Corrosion and
Protection of Materials at the School of Engineering at
Politecnico di Milano, Italy.
He graduated in chemical engineering (cum laude) at
Politecnico di Milano as Montecatini gold medal holder
and won the De Nora Award with a thesis on electro-
chemistry under the supervision of Professor Roberto
Piontelli. His career started and continued at Politecnico
di Milano, as an Assistant Professor first and then Full
Professor in electrochemistry and later in corrosion and
protection of materials. In 1968, he was appointed as
lecturer of the first ever course on corrosion and pro-
tection at an Italian university. He was a Visiting
Professor at the University of Cambridge, UK, and the
University of Connecticut, USA. From 1993 to 1999,
he was Head of the Department of Applied Physical
Chemistry at the Politecnico di Milano.
His first academic activity was electrochemistry
research; then, in the 1963, he moved on to the corro-
sion field focusing on industrial and engineering
aspects. His topics of study in electrochemistry were
overvoltage in sulphamic solutions, anodic effects in Al
production cells, anodic oxidation of Ti and so-called
xxiii
xxiv About the Author

valve metals and relevant chromatic effects. His

research in corrosion started with cold-worked stainless
steels and continued with implanted metals in simulated
physiological solutions, corrosion of bronze artefacts
and cathodic protection. Since 1985, he dealt with
corrosion of steel reinforcements in concrete, indicating
factors and conditions for initiation and propagation. In
1991, he invented and proposed a new technique called
cathodic prevention for concrete structures destined to
be chloride contaminated, nowadays included in oper-
ative international standards. From the study of the
corrosion behaviour of stainless steel reinforcements,
he proposed a potential-to-chloride diagram for inter-
pretation: this diagram is now called the Pedeferri
Diagram.
Meanwhile, he continued his studies on Ti colour-
ing, winning an award in 1988 in Paris, within the
international event Science pour l’art, and displaying
his work in the Fondazione Corrente Gallery in Milan,
Italy. He revisited the publications of Alessandro Volta
and Leopoldo Nobili and then rewrote several chapters
of the history of electrochemistry. Some of the
Pedeferri’s findings on Volta priorities in corrosion are
reported in this book.
He published 388 papers and 34 books, and took out
8 patents.
Symbols and Abbreviations

aMz þ Activity (or concentration) of ions of metal M in a solution (mol/L)

a Coefficient (adimensional)
b Tafel slope (module) (V/decade)
ba Tafel slope of the anodic curve (module) (V/decade)
bc Tafel slope of the cathodic curve (module) (V/decade)
bFe Tafel slope of iron dissolution reaction (V/decade)
bH 2 Tafel slope of hydrogen evolution reaction (V/decade)
bO 2 Tafel slope of oxygen reduction reaction (V/decade)
C Concentration (mol/L)
Crate Corrosion rate (mm/y)
Crate,m Mass loss rate (mdd)
CCGS Critical crevice gap size (µm)
CCT Critical crevice temperature (°C)
CIPP Close interval potential profile
CP Cathodic protection
CPrev Cathodic prevention
CPCC Critical pitting chloride concentration
CPT Critical pitting temperature (°C)
CSE Saturated copper sulphate electrode (+0.32 V SHE)
d Distance (m)
deq Diameter of the coating equivalent defect (m)
D Diffusion coefficient (m2/s)
DL Design life
d Diffusion layer thickness (m)
e− Electron
E Electrode potential (V)
EXY Potential difference between electrode X and Y (V)
E0 Standard potential (V)
Ea Anodic potential (V)
Ec Cathodic potential (V)

xxv
xxvi Symbols and Abbreviations

Ecorr Free corrosion potential (V)

Eeq Equilibrium potential given by Nernst equation (V)
EIR-free Potential free of the ohmic drop in CP applications (V)
Eoff Off-potential in CP applications (V)
Eon On-potential in CP applications (V)
Ep Passivation potential (V)
Epit Pitting potential or passivity breakdown potential (V)
Epp Primary passivation potential (V)
Eprot Protection potential (V)
Erp Repassivation potential (V)
Etr Transpassive potential (V)
EMF Electromotive force (V)
DE Driving voltage or potential difference (V)
e Efficiency (unitary fraction)
F Faraday constant (96,485 C)
FEM Finite element method
/ Diameter (m)
G Gibbs free energy (J/mol)
GACP Galvanic anode cathodic protection
c Mass density (g/cm3)
DG Standard Gibbs free energy variation (J/mol)
H Activation energy (J/mol)
HE Hydrogen embrittlement
HIC Hydrogen-induced cracking
HID Hydrogen-induced damage
g Overvoltage (with respect to the equilibrium potential) (V)
ga Anodic overvoltage (V)
gact; O2 Activation overvoltage of oxygen reduction (V)
gc Cathodic overvoltage (V)
gconc; O2 Concentration overvoltage of oxygen reduction (V)
gH2 Activation overvoltage of hydrogen evolution reaction (V)
gM Activation overvoltage of metal dissolution reaction (V)
gO2 Overvoltage of oxygen reduction (V)
i Current density (mA/m2)
ia Anodic current density (mA/m2)
ic Cathodic current density (mA/m2)
icorr Corrosion current density (mA/m2)
icp Critical passivation current density (mA/m2)
iGC Current density in galvanic coupling (mA/m2)
iL Oxygen limiting current density (mA/m2)
i0 Exchange current density (mA/m2)
i0; H2 Exchange current density of hydrogen evolution (mA/m2)
i0,M Exchange current density of metal M (mA/m2)
Symbols and Abbreviations xxvii

i0; O2 Exchange current density of oxygen (mA/m2)

ip Passivity current density (mA/m2)
iprot Protection current density (mA/m2)
I Current (A)
Ia Anodic current (A)
Ic Cathodic current (A)
Ie External current (A)
Iel Current in the electrolyte (A)
Iinterf Interference current (A)
Iprot Protection current (A)
ICCP Impressed current cathodic protection
k Constant (generic)
j Conductivity of an electrolyte (S/m)
Ks Complex stability constant
L Length (m)
Lmax Throwing power (m)
LSI Langelier saturation index
m Mass (g)
M Generic metal, less noble metal in a coupling
Mz+ Oxidised metal species
MIC Microbiologically influenced corrosion
MOB Manganese oxidising bacteria
MMO Mixed metal oxides (of noble metals Ir, Rh, Ru)
MW Atomic or molecular weight (g/mol)
N More noble metal in a coupling
Na Anode number
p Porosity of a scale (unitary fraction)
pCO2 Partial pressure of CO2 (bar)
pH 2 S Partial pressure of H2S (bar)
P Pressure of a gas (bar)
PREN Pitting resistance equivalent number
Q Flux of electrical charges (C)
R Generic ohmic resistance (X)
R Gas constant (1.987 cal/mol K = 8.314 J/mol K)
R0 Coating insulation resistance (X m2)
Ra Anode resistance (X)
Rc Cathode resistance (X)
Rcable Resistance of feeding cables (X)
Rtot Total resistance (X)
RH Relative humidity
RSI Ryznar saturation index
q Resistivity (X m)
qel Electrolyte resistivity (X m)
qmet Metal resistivity (X m)
xxviii Symbols and Abbreviations

s Thickness (m)
S Surface (m2)
Sa Anodic surface (m2)
Sc Cathodic surface (m2)
SM Surface of the less noble metal in a coupling (m2)
SN Surface of the more noble metal in a coupling (m2)
SHE Standard hydrogen electrode
SCC Stress corrosion cracking
SCE Saturated calomel electrode (+0.24 V SHE)
SOHIC Stress-oriented hydrogen-induced cracking
SRB Sulphate-reducing bacteria
SSC Silver/silver chloride reference electrode (+0.25 V SHE)
SSC Sulphide stress cracking
r Conductivity (S/m)
t Time (s)
T Temperature (°C; K)
T/R Transformer/rectifier
TDS Total dissolved solids or salinity (g/L or mg/L)
v Velocity (m/s)
V Voltage or feeding voltage (V)
DV Voltage drop or ohmic drop (V)
n Coating efficiency (unitary fraction)
w Anode consumption (kg/A y)
w Polarisation or potential shift from the free corrosion potential (V)
w* Thermodynamic and kinetic contribution of electrode reactions (V)
z Valence, number of electrons in an electrodic reaction (adimensional)
ZN Zinc/sea water reference electrode (−0.8 V SHE)

Units
A Ampere
cal Calorie
C Coulomb
°C Degree centigrade
h Hour
J Joule
K Degree Kelvin
L Litre
m Metre
M Molar
mol Mole
X Ohm
s Second
Symbols and Abbreviations xxix

S Siemens
V Volt
W Watt