Fundamentals of Ceramics

Prof. Michel W. Barsoum is Distinguished Professor in the Department of Materials Science and Engineering at Drexel University. As the author of two entries on the MAX phases in the Encyclopedia of Materials Science, and the book MAX Phases published in 2013, he is an internationally recognized leader in the area of MAX phases. In 2011, he and colleagues at Drexel, selectively etched the A-group layers from the MAX phases to produce an entirely new family of 2D solids that they labeled MXenes, that have sparked global interest because of their potential in a multitude of applications. He has authored the book MAX Phases: Properties of Machinable Carbides and Nitrides, published by Wiley VCH in 2013. He has published over 450 refereed papers, including ones in top-tier journals such as Nature and Science. According to Google Scholar his h-index is >100 with over 44,000 citations. He made ISI’s most cited researchers list in 2018 and 2019. He is a foreign member of the Royal Swedish Academy of Engineering Sciences, a fellow of the American Ceramic Society and the World Academy of Ceramics. The latter awarded him the quadrennial International Ceramics Prize 2020, one of the highest honors in the field. In 2000, he was awarded a Humboldt-Max Planck Research Award for Senior US Research Scientists and spent a sabbatical year at the Max Planck Institute in Stuttgart, Germany. In 2008, he spent a sabbatical at the Los Alamos National Laboratory as the prestigious Wheatly Scholar. He has been a visiting professor at Linkoping University in Sweden since 2008. In 2017, he received a Chair of Excellence from the Nanoscience Foundation in Grenoble, France. He is co-editor of Materials Research Letters, published by Taylor & Francis.

CONTENTS

Series Preface xi

Preface to the Second Edition xiii

Preface to First Edition xv

Author xix

1 Introduction 1

1.1 Introduction 1

1.2 Definition of Ceramics 2

1.3 Elementary Crystallography 3

1.4 Ceramic Microstructures 6

1.5 Traditional versus Advanced Ceramics 6

1.6 General Characteristics of Ceramics 7

1.7 Applications 7

1.8 The Future 9

Additional Reading 11

2 Bonding in Ceramics 13

2.1 Introduction 13

2.2 Structure of Atoms 14

2.3 Ionic versus Covalent Bonding 23

2.4 Ionic Bonding 23

2.5 Ionically Bonded Solids 28

2.6 Covalent Bond Formation 34

2.7 Covalently Bonded Solids 37

2.8 Band Theory of Solids 37

2.9 Summary 49

Appendix 2A: Kinetic Energy of Free Electrons 50

Additional Reading 52

Other References 53

3 Structure of Ceramics 55

3.1 Introduction 55

3.2 Ceramic Structures 57

3.3 Binary Ionic Compounds 62

3.4 Composite Crystal Structures 67

3.5 Structure of Covalent Ceramics 70

3.6 Structure of Layered Ceramics 70

3.7 Structure of Silicates 71

3.8 Lattice Parameters and Density 77

3.9 Summary 85

Appendix 3A 86

Additional Reading 92

Other References 92

4 Effect of Chemical Forces on Physical

Properties 93

4.1 Introduction 93

4.2 Melting Points 94

4.3 Thermal Expansion 99

4.4 Young’s Modulus and the Strength of

Perfect Solids 100

4.5 Surface Energy 106

4.6 Frequencies of Atomic Vibrations 108

4.7 Summary 113

Additional Reading 116

Multimedia References and Databases 116

5 Thermodynamic and Kinetic

Considerations 117

5.1 Introduction 117

5.2 Free Energy 118

5.3 Chemical Equilibrium and the Mass Action

Expression 129

5.4 Chemical Stability Domains 130

5.5 Electrochemical Potentials 133

5.6 Charged Interfaces, Double Layers and

Debye Lengths 134

5.7 Gibbs–Duhem Relation for Binary Oxides 135

5.8 Kinetic Considerations 138

5.9 Summary 142

Appendix 5A: Derivation of Eq. (5.27) 142

Additional Reading 145

Thermodynamic Data 145

6 Defects in Ceramics 147

6.1 Introduction 147

6.2 Point Defects 148

6.3 Linear Defects 176

6.4 Planar Defects 178

6.5 Summary 184

Additional Reading 187

7 Diffusion and Electrical Conductivity 189

7.1 Introduction 189

7.2 Diffusion 190

7.3 Electrical Conductivity 206

7.4 Ambipolar Diffusion 224

7.5 Relationships between Self-, Tracer,

Chemical, Ambipolar and Defect Diffusion

Coefficients 236

7.6 Summary 243

Appendix 7A: Relationship between Fick’s First

Law and Eq. (7.30) 245

Appendix 7B: Effective Mass and Density of States 246

Appendix 7C: Derivation of Eq. (7.79) 248

Appendix 7D: Derivation of Eq. (7.92) 248

Additional Reading 255

Other References 255

8 Phase Equilibria 257

8.1 Introduction 257

8.2 Phase Rule 258

8.3 One-Component Systems 259

8.4 Binary Systems 262

8.5 Ternary Systems 270

8.6 Free-Energy Composition and Temperature

Diagrams 271

8.7 Summary 276

Additional Reading 277

Phase Diagram Information 278

9 Formation, Structure and Properties of

Glasses 279

9.1 Introduction 279

9.2 Glass Formation 280

9.3 Glass Structure 293

9.4 Glass Properties 295

9.5 Summary 309

Appendix 9A: Derivation of Eq. (9.7) 310

Additional Reading 313

Other References 314

10 Sintering and Grain Growth 315

10.1 Introduction 315

10.2 Solid-State Sintering 317

10.3 Solid-State Sintering Kinetics 327

10.4 Liquid-Phase Sintering 349

10.5 Hot Pressing and Hot Isostatic Pressing 355

10.6 Summary 359

Appendix 10A: Derivation of the Gibbs–

Thompson Equation 360

Appendix 10B: Radii of Curvature 361

Appendix 10C: Derivation of Eq. (10.20) 362

Appendix 10D: Derivation of Eq. (10.22) 363

Additional Reading 367

Other References 368

11 Mechanical Properties: Fast Fracture 369

11.1 Introduction 369

11.2 Fracture Toughness 373

11.3 Atomistic Aspects of Fracture 383

11.4 Strength of Ceramics 385

11.5 Toughening Mechanisms 392

11.6 Designing with Ceramics 399

11.7 Summary 408

Additional Reading 413

12 Creep, Subcritical Crack Growth and

Fatigue 415

12.1 Introduction 415

12.2 Creep 416

12.3 Subcritical Crack Growth 430

12.4 Fatigue of Ceramics 436

12.5 Lifetime Predictions 439

12.6 Summary 450

Appendix 12A: Derivation of Eq. (12.24) 451

Additional Reading 456

13 Thermal Properties 459

13.1 Introduction 459

13.2 Thermal Stresses 460

13.3 Thermal Shock 464

13.4 Spontaneous Microcracking of Ceramics 469

13.5 Thermal Tempering of Glass 472

13.6 Thermal Conductivity 473

13.7 Summary 479

Additional Reading 482

Other Resources 482

14 Linear Dielectric Properties 483

14.1 Introduction 483

14.2 Basic Theory 484

14.3 Equivalent Circuit Description of Linear

Dielectrics 489

14.4 Polarization Mechanisms 494

14.5 Dielectric Loss 513

14.6 Dielectric Breakdown 514

14.7 Capacitors and Insulators 515

14.8 Summary 520

Appendix 14A: Local Electric Field 521

Additional Reading 527

15 Magnetic and Nonlinear Dielectric

Properties 529

15.1 Introduction 529

15.2 Basic Theory 530

15.3 Microscopic Theory 536

15.4 Para-, Ferro-, Antiferro-, and

Ferrimagnetism 540

15.5 Magnetic Domains and Hysteresis Curves 548

15.6 Magnetic Ceramics and Their Applications 552

15.7 Piezo- and Ferroelectric Ceramics 559

15.8 Summary 572

Appendix 15A: Orbital Magnetic Quantum

Number 573

Additional Reading 576

16 Optical Properties 577

16.1 Introduction 577

16.2 Basic Principles 579

16.3 Absorption and Transmission 590

16.4 Scattering and Opacity 596

16.6 Summary 605

Appendix 16A: Coherence 606

Appendix 16B: Assumptions Made in Deriving

Eq. (16.24) 606

Additional Reading 610

Index 611