Heterogeneous Electrode Processes and Localized Corrosion

262 Pages·2013·4.353 MB·English

by  Yongjun Tan(auth.), R. Winston Revie(eds.)

Heterogeneous Electrode
Processes and
Localized Corrosion
WILEY SERIES IN CORROSION
R. Winston Revie,Series Editor
Corrosion Inspection and Monitoring · Pierre R. Roberge
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and Testing · Edward Ghali
Microbiologically Influenced Corrosion · Brenda J. Little and Jason S. Lee
Corrosion Resistance of Aluminum and Magnesium Alloys · Edward Ghali
Metallurgy and Corrosion Control in Oil and Gas Production · Robert Heidersbach
Green Corrosion Inhibitors: Theory and Practice · V. S. Sastri
Heterogenous Electode Processes and Localized Corrosion · Yongjun Tan
Heterogeneous Electrode
Processes and
Localized Corrosion
YONGJUN TAN
AJOHNWILEY&SONS,INC.,PUBLICATION
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LibraryofCongressCataloging-in-PublicationData:
Tan,Yongjun,1963–
Heterogeneouselectrodeprocessesandlocalizedcorrosion/YongjunTan.
pagescm.–(Wileyseriesincorrosion)
Includesbibliographicalreferencesandindex.
ISBN978-0-470-64795-0(hardback)
1. Corrosionandanti-corrosives.2. Heterogeneouscatalysis.3.
Electrocatalysis. I.Title.
TA418.74.T362013
620.1(cid:2)1223–dc23
2012020902
PrintedintheUnitedStatesofAmerica
10987654321
Contents
Preface ix
1. Homogeneous Electrode Models and Uniform Corrosion
Measurements 1
1.1 Homogeneous Electrodes and Traditional Electrochemical
Methods / 3
1.2 Mixed Electrodes and Uniform Corrosion Models / 7
1.3 Mixed Potential Theory and Electrochemical Corrosion
Measurement / 10
1.4 Electrochemical Impedance Investigation of an Electrode–Solution
Interface / 19
1.5 Electrochemical Noise Monitoring of Rapid Electrode
Processes / 26
1.6 Issues and Difficulties in Traditional Electrochemical
Methods / 31
References / 32
2. Probing Electrode Inhomogeneity, Electrochemical
Heterogeneity, and Localized Corrosion 37
2.1 Probing Electrode Inhomogeneity / 39
2.2 Probing Electrochemical Heterogeneity and Localized
Corrosion / 44
v
vi CONTENTS
2.3 Overview of Various Techniques for Probing Localized
Corrosion / 48
References / 61
3. Visualizing Localized Corrosion Using Electrochemically
Integrated Multielectrode Arrays 67
3.1 An Electrochemically Integrated Multielectrode Array: The
Wire Beam Electrode / 70
3.2 Visualizing the Progression of Localized Corrosion in an Evans
Water Drop / 76
3.3 Visualizing Localized Corrosion in Nonuniform Environments
with Ion Concentration Gradients / 84
3.4 Visualizing Localized Corrosion by a WBE in Conjunction with
Scanning Probes / 91
References / 99
4. Measuring Thermodynamic and Kinetic Parameters from
Localized Corrosion Processes 101
4.1 Methods of Probing Localized Corrosion Thermodynamics and
Kinetics / 103
4.2 Measuring Localized Corrosion Using the Overpotential–Galvanic
Current Method / 109
4.3 Measuring Localized Corrosion Using the Galvanic Current
Method / 120
4.4 Measuring Localized Corrosion Using the R –WBE Method / 125
n
References / 131
5. Characterizing Inhomogeneity and Localized Corrosion on Coated
Electrode Surfaces 135
5.1 Characterizing Inhomogeneities in Organic Coatings and Inhibitor
Films / 137
5.2 Characterizing Inhomogeneity in Organic Coatings Using the
WBE Method / 141
5.3 The Effects of Coating Inhomogeneity on Electrochemical
Measurement / 145
5.4 Visualizing Underfilm Corrosion and the Effects of Cathodic
Protection / 148
5.5 Studying Corrosion Protection by Coatings and Cathodic
Protection / 155
CONTENTS vii
References / 157
6. Designing Experiments for Studying Localized Corrosion and Its
Inhibition in Inhomogeneous Media 161
6.1 Basic Issues in Localized Corrosion and Inhibitor Test
Design / 162
6.2 Fundamental Considerations in Selecting Corrosion Measurement
Techniques / 165
6.3 Designing Corrosion Tests in Highly Resistive and Inhomogeneous
Media / 168
6.4 Case Studies: Designing Crevice Corrosion Tests by Means of a
WBE / 181
6.5 Case Study: Designing Experiments for Localized Corrosion
Inhibitor Discovery / 186
References / 190
7. Sensing Localized Electrodeposition and Electrodissolution 195
7.1 Experimental Methods for Sensing Localized Electrodeposition
and Dissolution / 197
7.2 Sensing Localized Electrodeposition Using a WBE / 200
7.3 Sensing Localized Electrodissolution Using a WBE / 204
7.4 Sensing Nonuniform Electrochemical Deposition of Organic
Coatings / 211
References / 216
8. Versatile Heterogeneous Electrode Processes 219
8.1 Scanning and Modeling Various Heterogeneous Electrode
Processes / 222
8.2 Electrochemical Noise Generation from Electrochemical
Heterogeneity / 225
8.3 Harvesting Electrical Power from Electrochemical Heterogeneity
Using a WBE / 231
8.4 Further Research Issues in Electrochemical Heterogeneity / 237
References / 238
Index 243
Preface
Electrochemistry is an enabling science that since Galvani’s 1780s experiment on
frog legs and Volta’s nineteenth-century invention of the battery has facilitated
a wide spectrum of scientific discoveries and industrial processes. These include
electrolysis, electroplating, metal winning, hydrometallurgy, corrosion prevention,
passivation, batteries, fuel cells, solar cells, environmental and biological sensors,
organic and inorganic electrosynthesis, electrophoresis, effluent remediation, and
neurochemistry. Electrochemical theories and models have also been developed,
including the most fundamental relationships, such as Faraday’s law, the Nernst
equation,andtheBulter–Volmerformulation.However,traditionalelectrochemistry
hasamajorweakness—thereisa“missinglink”betweenitsidealuniformelectrode
modelandpracticalheterogeneouselectrodeprocessesbecauseofthephenomenon
of electrochemical heterogeneity.
Electrochemical heterogeneity refers to the localization of chemical and elec-
trochemical reactions over an electrode surface. In electrochemical reactions the
reactants do not need to be near each other spatially as normal chemical reac-
tionsdo;theycollideseparatelywithspatiallyseparatedelectronicconductors.This
characteristic permits distinct separation of electrode reactions over an electrode
surface, leading to the localization of electrode chemistry, reaction thermodynam-
ics, and kinetics. Most frequently, Electrochemical heterogeneity is initiated from
preexisting electrode inhomogeneity (i.e., spatial, physical, compositional, metal-
lurgical, or chemical nonuniformities existing on electrode surfaces). It could also
be initiated from an ideally homogeneous surface, especially if the surface were
exposed to a nonuniform environment. Electrochemical heterogeneity is a ubiqui-
tous phenomenon that plays critical roles in many difficult but important issues
in electrochemical science and engineering, such as localized corrosion, porous
ix
x PREFACE
electrodeposition, uneven electrodissolution, electrochemical noise, and various
forms of dispersion in voltammetry.
Electrochemical heterogeneity has not been confronted effectively in traditional
electrochemical science research and has not been covered sufficiently in the elec-
trochemical and corrosion science literature. It is evident that classical theories
describing the Faradaic electron transfer processes in dynamic electrochemistry
and traditional methods of electrochemical measurement are based on the assump-
tion that the electrode surface is homogeneous. Initial experimental studies used
to validate traditional electrochemical theories and methods commonly employed
mercury drop electrodes, where a truly homogeneous surface is indeed likely to
be achieved. However, solid electrodes that are in practical use today generally
have inhomogeneous surfaces, where electrochemical heterogeneity could initiate,
propagate, or terminate dynamically. Indeed, there is a major theoretical and tech-
nological gap between conventional electrochemistry over uniform surfaces and
heterogeneous electrochemistry over inhomogeneous surfaces.
I was first attracted to the issue of electrochemical heterogeneity in 1988 when
I was mystified by difficulties in repeating my impedance spectra of coated elec-
trodes. Over the past two decades I have been fortunate to be able to continue my
thinking and research on this issue, leading to the development and application
of an electrochemically integrated multielectrode array: the wire beam electrode.
My colleagues and I have carried out numerous experiments to study a variety of
heterogeneous electrode processes. Our experimental findings indicate that elec-
trochemists may need to recognize more widely the fundamental significance of
electrode inhomogeneity and electrochemical heterogeneity.
This book is probably the first to focus on electrode inhomogeneity, elec-
trochemical heterogeneity, and their effects on nonuniform electrode processes.
Attempts are made to critically review various forms of techniques that have been
appliedforprobinglocalizedelectrode–electrolyteinterfaces,inparticularscanning
probe techniques such as the scanning Kelvin probe, the scanning Kelvin probe
forcemicroscopy,thescanningvibratingelectrodetechnique,localelectrochemical
impedance spectroscopy, and scanning electrochemical microscopy. Special atten-
tion is focused on localized corrosion experiments designed using the wire beam
electrode as a key tool. Case studies presented in this book to illustrate innovative
experiments are based primarily on published data with which I have substantial
firsthandexperience.Iacknowledgeworkbyseveralotherresearchgroupsthathave
reported innovative and interesting experiments using various forms of electrode
arrays.
Iexpressmysincerethankstocolleaguesandco-workerswhohavecollaborated
with me over the past two decades, especially (in chronological order) Cuilan Wu,
Xuejun Zhou, Shiti Yu, Stuart Bailey, Yadran Marinovich, Brian Kinsella, Alex
Lowe, Tie Liu, Naing Naing Aung, Ting Wang, Kim Yong Lim, Bernice Zee,
PREFACE xi
Alan Bond, Chong Yong Lee, Mauro Mocerino, Tristan Paterson, Young Fwu,
Kriti Bhardwaj, Bruce Hinton, and Maria Forsyth. I thank them and many other
colleagues who have taught me patiently over the years. I also thank my family
for giving me encouragement, time, and support throughout the years.
YoungjunTan