E.

McCafferty

Introduction to Corrosion Science

Springer
Contents

1 Societal Aspects of Corrosion 1

We Live in a Metals-Based Society 1
Why Study Corrosion? 1
Corrosion and Human Life and Safety 1
Economics of Corrosion 4
Corrosion and the Conservation of Materials 5
The Study of Corrosion 6
Corrosion Science vs. Corrosion Engineering 8
Challenges for Today's Corrosion Scientist 9
Problems 10
References 10

2 Getting Started on the Basics 13

Introduction 13
What is Corrosion? 13
Physical Processes of Degradation 13
Environmentally Assisted Degradation Processes 14
Electrochemical Reactions 15
Half-Cell Reactions 15
Anodic Reactions 15
Cathodic Reactions 16
Coupled Electrochemical Reactions 17
A Note About Atmospheric Corrosion 18
Secondary Effects of Cathodic Reactions 19
Three Simple Properties of Solutions 21
The Faraday and Faraday's Law 23
Units for Corrosion Rates 24
Uniform vs. Localized Corrosion 25
The Eight Forms of Corrosion 27
Problems 28
References 31

3 Charged Interfaces 33
Introduction 33

Electrolytes 33
The Interior of an Electrolyte 33
Interfaces 35

vii
vjjj Contents

Encountering an Interface 35
The Solution/Air Interface 36
The Metal/Solution Interface 37
Metal Ions in Two Different Chemical Environments 38
The Electrical Double
Layer 39
The Gouy-Chapman Model of the Electrical Double Layer 40
The Electrostatic Potential and Potential Difference 40
The Stern Model of the Electrical Double Layer 41
The Bockris-Devanathan-Muller Model of the Electrical Double Layer 42

Significance of the Electrical Double Layer to Corrosion 43

Electrode Potentials 44
The Potential Difference Across a Metal/Solution Interface 44
Relative Electrode Potentials 45
The Electromotive Force Series 46
Reference Electrodes for the Laboratory and the Field 48
Measurement of Electrode Potentials 52
Problems 53
References 55

4 A Brief Review of Thermodynamics 57

Introduction 57
Thermodynamic State Functions 57
Internal Energy 57
Entropy 58
Enthalpy 59
Helmholtz and Gibbs Free Energies 59
Free Energy and Spontaneity 60
Relationships Between Thermodynamic Functions 61
The Chemical Potential and Standard States 63
More About the Chemical Potential 63
A Note About Units for AG" or AG 64
The Free Energy and Electrode Potentials 65
The Nernst Equation 66
Standard Free Energy Change and the Equilibrium Constant 67
A Quandary The Sign of Electrode Potentials
-

68
Factors Affecting Electrode Potentials 69
Problems 70
References 72

5 Thermodynamics of Corrosion: Electrochemical Cells

and Galvanic Corrosion 73
Introduction 73
Electrochemical Cells 73
Electrochemical Cells on the Same Surface 75
Galvanic Corrosion 76
Galvanic Series 76
Cathodic Protection 79
Two Types of Metallic Coatings 80
Titanium Coatings on Steel: A Research Study 82
Contents ix

Protection Against Galvanic Corrosion 83

Differential Concentration Cells 84
Metal Ion Concentration Cells 84
Oxygen Concentration Cells 86
The Evans Water Drop Experiment 88
Waterline Corrosion 88
Crevice Corrosion: A Preview 89
Problems 89
References 93

6 Thermodynamics of Corrosion: Pourbaix Diagrams 95

Introduction 95
Pourbaix Diagram for Aluminum 96
Construction of the PourbaixDiagram for Aluminum 96
Comparison of
Thermodynamic and Kinetic Data for Aluminum 101
Pourbaix Diagram for Water 101
Pourbaix Diagrams for Other Metals 103
Pourbaix Diagram for Zinc 103
Pourbaix Diagram for Iron 103
Pourbaix Diagrams for Additional Metals 106
Applications of Pourbaix Diagrams to Corrosion 108
Limitations of Pourbaix Diagrams Ill
Pourbaix Diagrams for Alloys Ill
Pourbaix Diagrams at Elevated Temperatures 112
Problems 114
References 116

7 Kinetics of Corrosion 119

Introduction 119
Units for Corrosion Rates 119
Methods of Determining Corrosion Rates 119
Weight Loss Method 120
Weight Gain Method 120
Chemical Analysis of Solution 121
Gasometric Techniques 122
Thickness Measurements 124
Electrical Resistance Method 124
Inert Marker Method 124
Electrochemical Techniques 126
Electrochemical Polarization 127
Anodic and Cathodic Polarization 127
Visualization of Cathodic Polarization 127
Visualization of Anodic Polarization 128
Ohmic Polarization 130
Electrode Kinetics for Activation Polarization 131

Absolute Reaction Rate Theory 131

Electrode Kinetics for Non-Corroding Metals 132
How to Plot Polarization Curves? 136
The Tafel Equation 138
x Contents

Reversible and Irreversible Potentials 139

Mixed Potential Theory (Wagner and Traud) 140

Electrode Kinetic Parameters 144

Applications of Mixed Potential Theory 146

Metals in Acid Solutions 146
Tafel Extrapolation 148
Verification of Corrosion Rates Obtained by Tafel Extrapolation 150
Cathodic Protection of Iron in Acids 150
Effect of the Cathodic Reaction 154
Effect of Cathode Area on Galvanic Corrosion 154

Multiple Oxidation-Reduction Reactions 156

Anodic or Cathodic Control 158
The Linear Polarization Method (Stern and Geary) 159

Advantages and Possible Errors for the Linear Polarization Technique 162

Applications of the Linear Polarization Technique 163

Small-Amplitude Cyclic Voltammetry 164

Experimental Techniques for Determination of Polarization Curves 165

Electrode Samples 165
Electrode Holders 166
Electrochemical Cells 167
Instrumentation and Procedures 168
Problems 169
References 173

8 Concentration Polarization and Diffusion 177

Introduction 177
Where Oxygen Reduction Occurs 177
Concentration Polarization in Current Density-Potential Plots 178
Solubility and Diffusion 179
Solubility of Oxygen in Aqueous Solutions 179
Fick's First Law of Diffusion 181
Diffusion and Random Walks 183
Electrode Kinetics for Concentration Polarization 186
Concentration Profile Near an Electrode Surface 186

Limiting Diffusion Current

Density 187
Diffusion Layer vs. The Diffuse Layer 189
Current-Potential Relationship for Concentration Polarization 189
Wagner-Traud Theory for Concentration Polarization 191
Effect of Environmental Factors on Concentration Polarization and Corrosion 192
Effect of Oxygen Concentration 193
Effect of Solution Velocity 194
Effect of Temperature 196
Further Applications of Concentration Polarization Curves 197
Cathodic Protection 197
Area Effects in Galvanic Corrosion 199
Linear Polarization 199
Concentration Polarization in Acid Solutions 200
Combined Activation and Concentration Polarization 202
Contents xi

The Rotating Disc Electrode

202
Problems 205
References 208

9 Passivity 209
Introduction 209
Aluminum: An Example 209
What is Passivity? 210
Early History of Passivity 210
Thickness of Passive Oxide Films 210
Purpose of This
Chapter 211
Electrochemical Basis for Passivity 211
Theories of Passivity 215
Adsorption Theory 215
Oxide Film Theory 216
Film Sequence Theory 218
Surface Analysis Techniques for the Examination of Passive Films 218
X-ray Photoelectron Spectroscopy (XPS) 220
X-ray Absorption Spectroscopy 222
Scanning Tunneling Microscopy 223
Models for the Passive Oxide Film on Iron 224
Bilayer Model 224

Hydrous Oxide Model 227

Bipolar-Fixed Charge Model 228

Spinel/Defect Model 229

What Do These Various Models Mean? 230
Passive Oxide Films on Aluminum 230
Air-Formed Oxide Films 231
Films Formed in Aqueous Solutions 231

Properties of Passive Oxide Films 232

Thickness 233
Electronic and Ionic Conductivity 233
Chemical Stability 233
Mechanical Properties 234
Structure of Passive Films 235

Passivity Binary Alloys

in 237
Electron Configuration Theory 238
Oxide Film Properties 241

Percolation Theory 242

Graph Theory Model 243

Passivity in Stainless Steels 249

Electrochemical Aspects 250

Composition of Passive Films on Stainless Steels 252

Passivity by Alloying with Noble Metals 254

Anodic Protection 255

Problems 257

References 260
xjj Contents

10 Crevice Corrosion and Pitting 263

Introduction 263
Crevice Corrosion 263
Initiation of Crevice Corrosion 264

Propagation of Crevice Corrosion 269

Crevice Corrosion Testing 272
Area Effects in Crevice Corrosion 274
Protection Against Crevice Corrosion 275

Pitting 277
CriticalPitting Potential 278

Experimental Determination of Pitting Potentials 280

Effect of Chloride Ions on the Pitting Potential 282
Effect of Inhibitors on the Pitting Potential 283
Mechanism of Pit Initiation 283
Mechanism of Pit Propagation 286
Protection Potential 288
Metastable Pits and Repassivation 290
Experimental Pourbaix Diagrams for Pitting 291
Effect of Molybdenum on the Pitting of Stainless Steels 293
Effect of Sulfide Inclusions on the Pitting of Stainless Steels 294
Effect of Temperature 294
Protection Against Pitting 296
Pitting of Aluminum 297
Occluded Corrosion Cells 300
Occluded Corrosion Cell (OCC) on Iron 301
Occluded Corrosion Cells on Copper and Aluminum 303
Differences Between Pitting and Crevice Corrosion 306
Detection of Corrosion Pits 306
Problems 308
References 311

11 Mechanically Assisted Corrosion 315

Introduction 315
Stress-Corrosion Cracking 318
Mechanical Metallurgy 318
Characteristics of Stress-Corrosion Cracking 319
Stages of Stress-Corrosion Cracking 320
Fracture Mechanics and SCC 323
SCC Testing 331
Interpretation of SCC Test Data 334
Metallurgical Effects in SCC 335
Environmental Effects on SCC 336
Mechanisms of SCC 339
Protection Against Stress-Corrosion Cracking 345
Corrosion Fatigue 346
Corrosion Fatigue Data 347
Protection Against Corrosion Fatigue 348
Cavitation Corrosion 349
Contents
xiii

Erosion Corrosion and Fretting Corrosion 352

Problems 353
References 354

12 Corrosion Inhibitors 357

Introduction 357
Types of Inhibitors 359
Acidic Solutions 360
Chemisorption of Inhibitors 361
Effect of Inhibitor Concentration 362
Chemical Factors in the Effectiveness of Chemisorbed Inhibitors 363
Involvement of Water 367
Competitive vs.Co-operative Adsorption 369
Effect of the Electrical Double Layer 370
The Potential of Zero Charge 372
Effect of Molecular Structure 373
Adsorption Isotherms 376
Nearly Neutral Solutions 379
Effect of Oxide Films 379
Chelating Compounds as Corrosion Inhibitors 380
Chromates and Chromate Replacements 381
Inhibition of Localized Corrosion 382
Pitting Corrosion 382
Crevice Corrosion 386
Stress-Corrosion Cracking and Corrosion Fatigue 387
New Approaches to Corrosion Inhibition 389
Biological Molecules 390

Langmuir-Blodgett Films and Self-assembled Monolayers 393

Vapor-Phase Inhibitors 396

Problems 398
References 400

13 Corrosion Under Organic Coatings 403

Introduction 403
Paints and Organic Coatings 404
Underlilm Corrosion 405
Water Permeation into Organic Coating
an 406
Permeation of Oxygen and Ions into an Organic Coating 410
Breakdown of an Organic Coating 411
Adhesion of Organic Coatings 412

Improved Corrosion Prevention by Coatings 416

Filiform Corrosion 417
Corrosion Tests for Organic Coatings 419
Accelerated Tests 419

Cathodic Delamination 419

AC Impedance Techniques A Brief Comment
- 422
Recent Directions and New Challenges 422

Problems 423

References ^25
14 AC Impedance
Introduction
Relaxation Processes

Experimental Setup
Complex Numbers and AC Circuit Analysis
The Metal/Solution Interface

Impedance Analysis
Additional Methods of Plotting Impedance Data . . .

Multiple Time Constants and the Effect of Diffusion .

Kramers-Kronig Transforms
Application to Corrosion Inhibition
Organic Coatings
Oxide Films and Surface Treatments

Concluding Remarks
Problems
References

15 High-Temperature Gaseous Oxidation

Introduction

Thermodynamics of High-Temperature Oxidation ....

Ellingham Diagrams
Equilibrium Pressure of Oxygen
Theory of High-Temperature Oxidation
Oxidation Rate Laws
Linear Rate Law
Parabolic Rate Law

Logarithmic Rate Law

Comparison of Rate Laws
The Wagner Mechanism and the Parabolic Rate Law .

Effect of Temperature on the Oxidation Rate

Defect Nature of Oxides
Semiconductor Nature of Oxides
Hauffe Rules for Oxidation
Effect of Oxygen Pressure on Parabolic Rate Constants
Non-uniformity of Oxide Films
Protective vs. Non-protective Oxides

Pilling-Bedworth Ratio
Properties of Protective High-Temperature Oxides . .

Problems
References .

16 Selected Topics in Corrosion Science

Introduction
Electrode Kinetics of Iron Dissolution in Acids

Bockris-Kelly Mechanism
Heusler Mechanism
Reconciliation of the Two Mechanisms
Additional Work on Electrode Kinetics
Distribution of Current and Potential
Contents
xv

Laplace's Equation 483

Circular Corrosion Cells
483
Parametric Study 486
Application to the Experiments of Rozenfeld and Pavlutskaya 488
Large Structures and Scaling Rules
489
Modeling of the Cathodic Protection System of a Ship 491
Scaling Rules
492
Acid-Base Properties of Oxide Films 494
Surface Hydroxyl Groups 494
Nature of Acidic and Basic Surface Sites 495
Isoelectric Points of Oxides 495
Surface Charge and Pitting 497
Pitting Potential of Aluminum as a Function of pH 498
Surface Modification by Directed Energy Beams 499
Ion Implantation and Related Processes 499
Applications of Ion Implantation 501
Laser-Surface Processing Techniques 505
Applications of Laser-Surface Processing 507
Comparison of Ion Implantation and Laser-Surface Processing 509
Problems 510
References 512

17 Beneficial Aspects of Corrosion 515

Introduction 515
Rust Is Beautiful 515
Copper Patinas Are Also Beautiful 515
Cathodic Protection 517
Electrochemical Machining 517
Metal Cleaning 517

Etching 517
Batteries 517

Passivity 517

Anodizing 518
Titanium Jewelry and Art 518
Caution to Inexperienced Artisans: 518
References 518

Answers to Selected Problems 521

Chapter 2 521

Chapter 3 521

Chapter 4 522

Chapter 5 522

Chapter 6 523

Chapter 7 524

Chapters 524

Chapter 9 524

Chapter 10 525

Chapter 11 526

Chapter 12 526
xvi Contents

Chapter 13 527

Chapter 14 528

Chapter 15 528

Chapter 16 528

Appendix A: Some Properties of Various Elemental Metals 531

Appendix B: Thermodynamic Relationships for Use in Constructing Pourbaix

Diagrams at High Temperatures 533

References 534

Appendix C: Relationship Between the Rate Constant and the Activation

Energy for a Chemical Reaction 535

Appendix D: Random Walks in Two Dimensions 537

Appendix E: Uhlig's Explanation for the Flade Potential on Iron 541

Appendix F: Calculation of the Randic Index X(G) for the Passive Film
on Fe-Cr Alloys 543
References 545

Appendix G: Acid Dissociation Constants pKa of Bases and the Base Strength 547

Appendix H: The Langmuir Adsorption Isotherm 549

Appendix I: The Temkin Adsorption Isotherm 551

Appendix J: The Temkin Adsorption Isotherm for a Charged Interface 553

Appendix K: Effect ofCoating Thickness on the Transmission Rate

of a Molecule Permeating Through a Free-Standing Organic Coating 557

Appendix L: The Impedance for a Capacitor 559

Reference 559

Appendix M: Use of L'Hospital's Rule to Evaluate |Z| for the Metal/Solution

Interface for Large Values of Angular Frequency w 561

Appendix N: Derivation of the Arc Chord Equation for Cole-Cole plots 563
References 565

Appendix O: Laplace's Equation 567

Reference 569

Index 571