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 Olefin 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
