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Chemistry and Physics of Mechanical Hardness
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Table of Contents

Preface xi 1 Introduction 1 1.1 Why Hardness Matters (A Short History) 1 1.2 Purpose of This Book 5 1.3 The Nature of Hardness 7 2 Indentation 11 2.1 Introduction 11 2.2 The Chin-Gilman Parameter 14 2.3 What Does Indentation Hardness Measure? 14 2.4 Indentation Size Effect 20 2.5 Indentation Size (From Macro to Nano) 22 2.6 Indentation vs. Scratch Hardness 23 2.7 Blunt or Soft Indenters 24 2.8 Anisotropy 24 2.9 Indenter and Specimen Surfaces 25 3 Chemical Bonding 27 3.1 Forms of Bonding 27 3.2 Atoms 28 3.3 State Symmetries 29 3.4 Molecular Bonding (Hydrogen) 31 3.5 Covalent Bonds 36 3.6 Bonding in Solids 41 3.7 Electrodynamic Bonding 45 3.8 Polarizability 47 4 Plastic Deformation 51 4.1 Introduction 51 4.2 Dislocation Movement 52 4.3 Importance of Symmetry 55 4.4 Local Inelastic Shearing of Atoms 56 4.5 Dislocation Multiplication 57 4.6 Individual Dislocation Velocities (Microscopic Distances) 59 4.7 Viscous Drag 60 4.8 Deformation-Softening and Elastic Relaxation 62 4.9 Macroscopic Plastic Deformation 63 5 Covalent Semiconductors 67 5.1 Introduction 67 5.2 Octahedral Shear Stiffness 69 5.3 Chemical Bonds and Dislocation Mobility 71 5.4 Behavior of Kinks 75 5.5 Effect of Polarity 77 5.6 Photoplasticity 79 5.7 Surface Environments 80 5.8 Effect of Temperature 80 5.9 Doping Effects 80 6 Simple Metals and Alloys 83 6.1 Intrinsic Behavior 83 6.2 Extrinsic Sources of Plastic Resistance 85 7 Transition Metals 99 7.1 Introduction 99 7.2 Rare Earth Metals 101 8 Intermetallic Compounds 103 8.1 Introduction 103 8.2 Crystal Structures 104 8.3 Calculated Hardness of NiAl 112 8.4 Superconducting Intermetallic Compounds 113 8.5 Transition Metal Compounds 115 9 Ionic Crystals 119 9.1 Alkali Halides 119 9.2 Glide in the NaCl Structure 120 9.3 Alkali Halide Alloys 123 9.4 Glide in CsCl Structure 124 9.5 Effect of Imputities 124 9.6 Alkaline Earth Fluorides 126 9.7 Alkaline Earth Sulfi des 128 9.8 Photomechanical Effects 128 9.9 Effects of Applied Electric Fields 129 9.10 Magneto-Plasticity 129 10 Metal-Metalloids (Hard Metals) 131 10.1 Introduction 131 10.2 Carbides 132 10.3 Tungsten Carbide 134 10.4 Borides 136 10.5 Titanium Diboride 137 10.6 Rare Metal Diborides 138 10.7 Hexaborides 138 10.8 Boron Carbide (Carbon Quasi-Hexaboride) 140 10.9 Nitrides 141 11 Oxides 143 11.1 Introduction 143 11.2 Silicates 143 11.3 Cubic Oxides 147 11.4 Hexagonal (Rhombohedral) Oxides 152 11.5 Comparison of Transition Metal Oxides with "Hard Metals" 155 12 Molecular Crystals 157 12.1 Introduction 157 12.2 Anthracene 158 12.3 Sucrose 159 12.4 Amino Acids 159 12.5 Protein Crystals 160 12.6 Energetic Crystals (Explosives) 161 12.7 Commentary 161 13 Polymers 163 13.1 Introduction 163 13.2 Thermosetting Resins (Phenolic and Epoxide) 164 13.3 Thermoplastic Polymers 165 13.4 Mechanisms of Inelastic Plasticity 166 13.5 "Natural" Polymers (Plants) 166 13.6 "Natural" Polymers (Animals) 168 14 Glasses 171 14.1 Introduction 171 14.2 Inorganic Glasses 172 14.3 Metallic Glasses 176 14.3.1 Hardness Shear Modulus Relationship 177 14.3.2 Stable Compositions 180 15 Hot Hardness 183 15.1 Introduction 183 15.2 Nickel Aluminide versus Oxides 184 15.3 Other Hard Compounds 184 15.4 Metals 185 15.5 Intermetallic Compounds 187 16 Chemical Hardness 189 16.1 Introduction 189 16.2 Defi nition of Chemical Hardness 190 16.3 Physical (Mechanical) Hardness 192 16.4 Hardness and Electronic Stability 193 16.5 Chemical and Elastic Hardness (Stiffness) 194 16.6 Band Gap Density and Polarizability 194 16.7 Compression Induced Structure Changes 195 16.8 Summary 196 17 "Superhard" Materials 197 17.1 Introduction 197 17.2 Principles for High Hardness 197 17.3 Friction at High Loads 198 17.4 Superhard Materials 199 References 200 Index 203

About the Author

John J. Gilman, PhD, is Research Professor in the Department of Materials Science and Engineering at UCLA. He has been contributing to the scientific literature of mechanical hardness for almost fifty years. Dr. Gilman is the author of three other books and 325 technical papers, and the owner of six patents. He has been an editor for various books and magazines.

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