CÉSAR A. C. SEQUEIRA, PHD, has been a member of the faculty staff of Instituto Superior Técnico (Univ. of Lisbon), maintaining his academic career in fundamental and technological electrochemistry for more than 40 years. He is the author/co-author of over 250 professional papers, 500 scientific communications, 20 book chapters, and 12 books in the areas of corrosion science and technology, electrochemistry, and materials science. He has directed numerous workshops, including three on Microbial Corrosion of the European Federation of Corrosion. He is a Fellow of the Royal Society of Chemistry (U.K.) and of the Institute of Materials (U.K.), and is an Active Member of the Electrochemical Society. Currently, he is the Senior Research Leader on Electrochemistry of Materials at CeFEMA (Center of Physics and Engineering of Advanced Materials) in Lisbon.

Preface xi

Acknowledgments xvii

1 Introduction 1

1.1 Definition of High Temperature Corrosion 1

1.2 Historical Development 1

1.3 High Temperature Corrosion Phenomena 3

1.4 High Temperature Materials 3

1.5 Corrosive Environments 27

1.6 Films and Scales 31

1.7 Academic Impact of High Temperature Corrosion 33

1.8 Industrial Impact of High Temperature Corrosion 38

1.9 Questions 46

References 46

Further Reading 47

2 Metallurgical Structure and Metals 48

2.1 Imperfections in an Essentially Perfect Structure 48

2.2 Solidification 56

2.3 Alloys 62

2.4 Iron and Steel 72

2.5 Deformation and Recrystallization 79

2.6 Fracture and Fatigue 91

2.7 Questions and Problems 97

References 98

Further Reading 99

3 High Temperature Equilibria 100

3.1 Introduction 100

3.2 Thermochemical Analysis 100

3.3 Electrochemical Analysis 119

References 128

Further Reading 129

4 Lattice Defects in Metal Compounds 130

4.1 Introduction 130

4.2 Defect Reactions 133

4.3 Defect Equilibria 135

4.4 Equilibrium Constants 141

4.5 Questions 144

References 144

Further Reading 145

5 Diffusion in Solid-State Systems 146

5.1 Introduction 146

5.2 General Theory of Diffusion 146

5.3 Diffusion Coefficients 150

5.4 Matano–Boltzmann Analysis 153

5.5 Kirkendall Effect 154

5.6 Darken Analysis 155

5.7 Factors Influencing Diffusion 156

5.8 Impurity Diffusion in Metals 158

5.9 Grain Boundary Diffusion in Metals 158

5.10 Diffusion in Solid Oxides 160

5.11 Morphology of Reaction Products 163

5.12 Measurement of Diffusion Parameters 164

5.13 Questions and Problems 168

References 168

Further Reading 169

6 High Temperature Electrochemistry 171

6.1 Introduction 171

6.2 Electrochemical Nature of Molten Salt Corrosion 171

6.3 The Single Potential of an Electrode 172

6.4 Equilibrium Diagrams 173

6.5 The Tafel Relationship 173

6.6 Corrosion Potential–pO2−Relationship 175

6.7 Electrochemical Polarization and Monitoring 177

6.8 Electrochemical Nature of Metal Oxidation 179

6.9 Usefulness of Electrochemical Cells 181

6.10 Current–Potential Measurements on Solid Electrodes 182

6.11 Simple Concepts of Oxide Semiconductors 183

6.12 Conduction Processes in Ionic Oxides 186

6.13 Common Solid-State Electrochemical Situations 190

References 194

Further Reading 195

7 Oxidation 196

7.1 Introduction 196

7.2 Thermodynamic Considerations 197

7.3 Kinetic Considerations 199

7.4 Defect Structures 201

7.5 Compact Scale Growth 208

7.6 Multilayered Scale Growth 212

7.7 Oxidation Resistance 214

7.8 Oxidation of Engineering Materials 224

7.9 Conclusions 228

7.10 Questions 229

References 229

Further Reading 231

8 Sulfidation 233

8.1 Introduction 233

8.2 The Process of Sulfidation 233

8.3 Sulfidation Kinetics 235

8.4 Sulfidation of Selected Materials 236

8.5 Defect Structures of Metal Sulfides 240

8.6 Questions 243

References 243

Further Reading 244

9 Carburization and Metal Dusting 245

9.1 Introduction 245

9.2 Carburization 245

9.3 Alloy Resistance to Carburization 251

9.4 Metal Dusting Problem 255

9.5 Metal Dusting Mechanisms 256

9.6 Alloy Resistance to Metal Dusting 260

References 262

Further Reading 263

10 Nitridation 264

10.1 Introduction 264

10.2 Nitridation Mechanisms 264

10.3 Nitridation in Industrial Media 265

10.4 Questions and Problems 273

References 274

Further Reading 275

11 Halogenation 276

11.1 Introduction 276

11.2 Metal–Halogen Reactions 277

11.3 Alloy–Halogen Reactions 279

11.4 Laboratory Studies 280

11.5 Conclusions 282

11.6 Questions 282

References 282

Further Reading 283

12 Corrosion by Hydrogen and Water Vapor 284

12.1 Introduction 284

12.2 Corrosion by Hydrogen 284

12.3 Corrosion by Water Vapor 290

12.4 Conclusions 293

References 294

Further Reading 295

13 Corrosion in Molten Salts 296

13.1 Introduction 296

13.2 Corrosion Process 296

13.3 Thermodynamic Diagrams 298

13.4 Corrosion Rate Measurements 299

13.5 Test Methods 299

13.6 Fluorides 303

13.7 Chlorides 304

13.8 Nitrates/nitrites 305

13.9 Hydroxides 309

13.10 Carbonates 309

13.11 Vanadates 312

13.12 Sulfates 314

13.13 Prevention of Molten Salt Corrosion 321

13.14 Summary 321

References 322

Further Reading 324

14 Corrosion in Molten Metals 325

14.1 Introduction 325

14.2 Corrosive Processes 326

14.3 Industrial Liquid Metals 332

14.4 Conclusions 338

References 339

Further Reading 339

15 Hot Corrosion 340

15.1 Introduction 340

15.2 Engine Description and Materials 340

15.3 Early Studies 341

15.4 Mechanisms of Hot Corrosion 349

15.5 Hot Corrosion of Gas Turbine Alloys 351

15.6 Methods of Evaluating Hot Corrosion 354

15.7 Prevention of Corrosion 356

15.8 Conclusions 358

15.9 Questions 358

References 359

Further Reading 360

16 Fireside Corrosion 361

16.1 Introduction 361

16.2 Coal-Fired Boilers 362

16.3 Coal-ash Corrosion 371

16.4 Oil-Fired Boilers 373

16.5 Corrosion in Waste Incinerators 379

16.6 Plant Experience with Fireside Corrosion 380

16.7 Conclusions 388

References 389

Further Reading 389

17 Testing and Evaluation 391

17.1 Introduction 391

17.2 Testing Equipment and Monitoring 392

17.3 Optical Microscopy 394

17.4 Thermogravimetry 395

17.5 Spectroscopy 398

17.6 Diffraction Techniques 402

17.7 Electron Microscopy 409

17.8 Electron Spectroscopy and Ion Scattering 416

17.9 Surface Microscopy 424

17.10 Optical Spectroscopy 428

17.11 Nondestructive Inspection Techniques 439

17.12 Traditional Electrochemical Methods 445

17.13 Nontraditional Electrochemical Methods 453

17.14 Combined Electrochemical Methods 459

References 472

Further Reading 475

18 Protective Coatings 477

18.1 Introduction 477

18.2 Coating Systems 477

18.3 Coating Processes 480

18.4 Coating Degradation 496

18.5 Summary and Future Trends 499

18.6 Questions 500

References 500

Further Reading 501

19 Examples of Engineering Importance 502

19.1 Introduction 502

19.2 Molten Carbonate Fuel Cells 504

19.3 Solid Oxide Fuel Cells 516

19.4 Direct Carbon Fuel Cells 524

19.5 Nuclear Power Plants 531

References 546

Further Reading 549

20 Case Studies 551

20.1 Making Stainless Steels 551

20.2 Corrosion Protection of Turbine Blades 551

20.3 Oxidation of Silicides for VLSI Applications 556

20.4 Naphthenic Acid Corrosion in Petrochemical Plants 560

20.5 Oxidation of Ceramic Matrix Composites 562

20.6 Shell Corrosion of Rotary Cement Kilns 563

20.7 Corrosion of Steels in a Linear 𝛼Olefin Plant 564

References 565

Further Reading 565

Appendix A 566

List of Acronyms 591

Glossary of Selected Terms Used in High Temperature Corrosion 596

Author Index 615

Subject Index 629

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