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Modern Ceramic Engineering
Properties, Processing, and Use in Design
Fourth Edition
http://taylorandfrancis.com
Modern Ceramic Engineering
Properties, Processing, and Use in Design
Fourth Edition

David W. Richerson
William E. Lee
CRC Press
Taylor & Francis Group
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© 2018 by Taylor & Francis Group, LLC

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Contents
Preface.............................................................................................................................................xxi
Authors.......................................................................................................................................... xxiii

Part I Ceramics as Engineering Materials

Chapter 1 What Is a Ceramic?.......................................................................................................3

1.1 Definitions of Ceramics...................................................................................... 3
1.2 Material Types Generally Considered in the Ceramics Family.........................3
1.2.1 Polycrystalline Ceramics Fabricated by Sintering................................3
1.2.2 Glass......................................................................................................4
1.2.3 Glass Ceramics...................................................................................... 4
1.2.4 Single Crystals of Ceramic Compositions............................................4
1.2.5 Chemical Synthesis or Bonding............................................................ 5
1.2.6 Natural Ceramics.................................................................................. 5
1.3 So What Is a Ceramic?.......................................................................................5
Special Optional Assignment........................................................................................ 6
References..................................................................................................................... 7
Study Guide................................................................................................................... 7

Chapter 2 History of Ceramics...................................................................................................... 9

2.1 Ceramics in the Stone Age................................................................................. 9
2.1.1 Use of Natural Ceramics....................................................................... 9
2.1.2 Synthetic Stone: Clay Transformed by Fire........................................ 11
2.1.3 First Practical Use of Earthenware..................................................... 11
2.1.4 Other Neolithic Ceramic Innovations................................................. 12
2.2 Rise of Traditional Ceramic Industries............................................................ 13
2.2.1 Ceramic Innovations during the Chalcolithic Period.......................... 13
2.2.2 Ceramics and the Metal Ages............................................................. 15
2.2.3 Emergence of Glass............................................................................. 15
2.2.4 Ceramics in Building.......................................................................... 16
2.2.5 Ceramic Whitewares...........................................................................20
2.3 From Traditional to Modern Ceramics............................................................. 21
2.4 Summary.......................................................................................................... 23
References................................................................................................................... 23
Additional Recommended Reading on Technical Aspects of Traditional Ceramics....... 23
Study Guide................................................................................................................. 23

Chapter 3 Applications: Engineering with Ceramics..................................................................25

3.1 High-Temperature Applications.......................................................................25
3.1.1 Ceramics in Metal Processing.............................................................25
3.1.2 Glass Production................................................................................. 29
3.1.3 Industrial Processes............................................................................. 29
3.1.3.1 Furnace and Reaction Vessel Linings................................. 29

v
vi Contents

3.1.3.2 Heat Sources........................................................................ 30

3.1.3.3 Heat Exchangers.................................................................. 30
3.1.3.4 Heat Exchange for Chemical Processing............................. 33
3.1.4 Heat Engines.......................................................................................34
3.1.4.1 Gas Turbine Engines............................................................34
3.1.4.2 Internal Combustion Engines.............................................. 37
3.1.4.3 Aerospace............................................................................ 38
3.2 Wear and Corrosion Resistance Applications.................................................. 39
3.2.1 Seals.................................................................................................... 39
3.2.2 Valves.................................................................................................. 43
3.2.3 Pumps..................................................................................................46
3.2.4 Bearings..............................................................................................46
3.2.5 Thread Guides..................................................................................... 48
3.2.6 Ceramics in Papermaking................................................................... 49
3.3 Cutting and Grinding....................................................................................... 49
3.3.1 Ceramic Cutting Tool Inserts.............................................................. 50
3.3.2 Superhard Abrasives............................................................................ 53
3.3.3 Waterjet Cutting.................................................................................. 53
3.4 Electrical Applications of Ceramics................................................................. 54
3.4.1 Ceramic Electrical Insulators.............................................................. 54
3.4.2 Dielectric Ceramics............................................................................. 57
3.4.3 Semiconductors................................................................................... 58
3.4.4 Electrical Conductors..........................................................................60
3.4.5 Ceramic Superconductors................................................................... 63
3.5 Magnetic Ceramics...........................................................................................64
3.6 Optical Applications of Ceramics.................................................................... 65
3.6.1 Applications Based on Transparency..................................................66
3.6.1.1 Window Glass......................................................................66
3.6.1.2 Container Glass.................................................................... 68
3.6.1.3 Optical Glass Fibers............................................................. 68
3.6.1.4 Lenses.................................................................................. 68
3.6.2 Applications Based on Phosphorescence and Fluorescence............... 69
3.6.2.1 Fluorescent Light................................................................. 69
3.6.2.2 Television and Oscilloscopes............................................... 69
3.6.2.3 Electroluminescent Lamps.................................................. 70
3.6.2.4 Lasers................................................................................... 70
3.7 Composites....................................................................................................... 71
3.8 Medical Applications of Ceramics................................................................... 72
3.8.1 Replacement and Repair...................................................................... 72
3.8.1.1 Dental Ceramics.................................................................. 72
3.8.1.2 Hip Implants........................................................................ 74
3.8.1.3 Spine Repair........................................................................ 75
3.8.1.4 Middle-Ear Implants............................................................ 75
3.8.1.5 Eye Repairs.......................................................................... 75
3.8.1.6 Heart Valve Implants........................................................... 76
3.8.1.7 Prosthetic Devices............................................................... 76
3.8.2 Ceramics for Medical Diagnosis......................................................... 76
3.8.2.1 CT Scanner.......................................................................... 76
3.8.2.2 Endoscopy............................................................................ 77
3.8.2.3 Ultrasound Imaging............................................................. 78
3.8.3 Ceramics in Medical Treatment and Therapy..................................... 79
Contents vii

3.9 Energy Efficiency and Pollution Control.......................................................... 81

3.9.1 Energy Savings in the Home............................................................... 81
3.9.1.1 Fiberglass Insulation............................................................ 81
3.9.1.2 Efficient Light Sources........................................................ 82
3.9.1.3 Gas Appliances....................................................................84
3.9.2 Ceramics for Power Generation..........................................................84
3.9.3 Ceramics in the Transportation Sector................................................ 85
3.9.4 Other Uses of Ceramics for Energy Efficiency and Pollution Control..... 87
3.10 Military............................................................................................................. 87
3.11 Recreation......................................................................................................... 88
3.12 Ceramics Modeling and Simulation................................................................. 89
3.13 Summary..........................................................................................................92
References...................................................................................................................92
Study Guide................................................................................................................. 93

Part II Structures and Properties

Chapter 4 Atomic Bonding and Crystal Structure.......................................................................97

4.1 Electronic Configuration of Atoms..................................................................97
4.2 Bonding.......................................................................................................... 100
4.2.1 Metallic Bonding............................................................................... 102
4.2.2 Ionic Bonding.................................................................................... 102
4.2.3 Covalent Bonding.............................................................................. 107
4.2.4 Ionic and Covalent Bond Combinations............................................ 109
4.2.5 van der Waals Bonds......................................................................... 109
4.3 Polymorphic Forms and Transformations...................................................... 111
4.4 Noncrystalline Structures............................................................................... 113
4.4.1 Glasses............................................................................................... 113
4.4.2 Gels.................................................................................................... 115
4.4.3 Vapor Deposition............................................................................... 115
4.5 Molecular Structures...................................................................................... 115
4.5.1 Hydrocarbons.................................................................................... 115
4.5.2 Addition Polymerization................................................................... 116
4.5.3 Condensation Polymerization............................................................ 117
4.5.4 Polymer Crystallization..................................................................... 118
4.5.5 Cross-Linking and Branching........................................................... 118
References................................................................................................................. 120
Problems.................................................................................................................... 120
Study Guide............................................................................................................... 120

Chapter 5 Crystal Chemistry and Specific Crystal Structures.................................................. 123

5.1 Crystal Structure Notations............................................................................ 123
5.1.1 Crystal Systems and Bravais Lattices............................................... 123
5.1.2 Crystal Directions and Planes........................................................... 123
5.1.3 Structure, Composition, and Coordination Notations....................... 127
5.2 Crystal Chemistry of Ceramics...................................................................... 127
5.2.1 Crystal Chemistry Concepts............................................................. 128
5.2.1.1 Ionic Radius....................................................................... 128
viii Contents

5.2.1.2 Ionic Packing..................................................................... 128

5.2.1.3 Effect of Charge................................................................. 130
5.2.2 Crystal Chemical Substitutions......................................................... 131
5.2.3 Derivative Structures......................................................................... 132
5.2.3.1 Ordering............................................................................. 132
5.2.3.2 Nonstoichiometry.............................................................. 132
5.2.3.3 Stuffing.............................................................................. 132
5.2.3.4 Distortion........................................................................... 133
5.3 Metallic and Ceramic Crystal Structures....................................................... 133
5.3.1 Metallic Crystal Structures............................................................... 133
5.3.2 Ceramic Structures with a Single Element....................................... 134
5.3.3 Binary Ceramic Structures................................................................ 138
5.3.3.1 [Rock Salt] Structure A[6]X[6]............................................. 139
5.3.3.2 [Nickel Arsenide] Structure A[6]X[6].................................. 139
5.3.3.3 [Cesium Chloride] Structure A[8]X[8]................................. 139
5.3.3.4 [Zinc Blende] and [Wurtzite] Structures A[4]X[4]............... 139
5.3.3.5 [Fluorite] Structure A[8]X[4] 2 ................................................ 140
5.3.3.6 [Antifluorite] Structure A[4]X[8].......................................... 141
5.3.3.7 [Rutile] Structure A[6]X[3]................................................... 141
5.3.3.8 Silica Structures A[4]X[2] 2 ..................................................... 142
5.3.3.9 [Corundum] Structure A[6] [4]
2 X 3 ............................................ 144
5.3.4 Ternary Ceramic Structures.............................................................. 144
5.3.4.1 A2BX4 Structures............................................................... 145
5.3.4.2 ABX4 Structures................................................................ 148
5.3.4.3 ABX3 Structures................................................................ 148
5.3.4.4 Other Structures................................................................. 150
5.3.4.5 Carbide and Nitride Structures.......................................... 151
5.3.5 Crystal Defects and Stoichiometry................................................... 152
5.3.5.1 Zero-Dimensional (Point) Defects..................................... 152
5.3.5.2 One-Dimensional (Line) Defects....................................... 154
5.3.5.3 Two-Dimensional (Planar) Defects................................... 154
5.3.5.4 Three-Dimensional (Volume) Defects............................... 159
5.3.5.5 Accommodating Nonstoichiometry in Crystals................ 160
References................................................................................................................. 160
Additional Recommended Reading.......................................................................... 161
Problems.................................................................................................................... 161
Study Guide............................................................................................................... 162

Chapter 6 Phase Equilibria and Phase Equilibrium Diagrams.................................................. 163

6.1 Phase Equilibrium Diagrams......................................................................... 163
6.1.1 Concept of Phase Equilibria.............................................................. 164
6.1.2 Phase Rule......................................................................................... 164
6.1.3 One-Component Phase Diagrams..................................................... 165
6.1.4 Two-Component Systems.................................................................. 166
6.1.4.1 Binary Eutectic Systems.................................................... 168
6.1.5 Intermediate Compounds.................................................................. 169
6.1.5.1 Solid Solution..................................................................... 174
6.1.5.2 Liquid Immiscibility.......................................................... 174
Contents ix

6.1.5.3 Exsolution.......................................................................... 176

6.1.5.4 Polymorphism.................................................................... 176
6.1.6 Three-Component Systems............................................................... 177
6.1.6.1 Simple Eutectic Ternary Diagram..................................... 177
6.1.6.2 Ternary System with Congruently Melting Binary
Compound AB................................................................... 181
6.1.6.3 Ternary System with Incongruently Melting Binary
Compound AB................................................................... 182
6.1.6.4 Ternary Compounds.......................................................... 183
6.1.6.5 Polymorphic Transformations........................................... 183
6.1.6.6 Immiscible Liquids in Ternary Systems............................ 183
6.1.6.7 Solid Solution in Ternary Systems.................................... 185
6.1.6.8 Real Ternary Systems........................................................ 187
6.2 Phase Equilibrium Diagram Composition Calculations................................ 188
6.2.1 Composition Conversions.................................................................. 188
6.2.2 Binary Composition Calculations..................................................... 191
6.2.3 Ternary Composition Calculations.................................................... 192
6.3 Isoplethal Crystallization Paths...................................................................... 193
6.3.1 Binary Isoplethal Analysis................................................................ 193
6.3.2 Ternary System Isoplethal Analysis.................................................. 194
6.4 Nonequilibrium Behavior............................................................................... 196
6.4.1 Sluggish Kinetics............................................................................... 197
6.4.2 Rapid Heating or Cooling................................................................. 197
6.4.3 Nucleation Difficulty......................................................................... 198
6.4.4 Elastic Constraint of a Polymorphic Transformation........................ 198
6.4.5 Additional Information on Nonequilibrium...................................... 198
References................................................................................................................. 199
Problems.................................................................................................................... 199
Study Guide...............................................................................................................200

Chapter 7 Physical and Thermal Behavior................................................................................ 203

7.1 Physical Properties......................................................................................... 203
7.1.1 Density..............................................................................................203
7.1.1.1 Crystallographic Density...................................................203
7.1.1.2 Bulk Density......................................................................205
7.1.1.3 Theoretical Density...........................................................206
7.1.1.4 Specific Gravity.................................................................207
7.1.1.5 Open Porosity....................................................................207
7.1.1.6 Density Comparisons.........................................................209
7.1.2 Melting Behavior...............................................................................209
7.2 Thermal Properties......................................................................................... 212
7.2.1 Heat Capacity.................................................................................... 212
7.2.2 Thermal Conductivity....................................................................... 213
7.3 Thermal Expansion........................................................................................ 221
7.3.1 Factors Influencing Thermal Expansion........................................... 222
7.3.1.1 Thermal Expansion of Metals........................................... 222
7.3.1.2 Thermal Expansion of Ceramics....................................... 223
7.3.1.3 Thermal Expansion of Noncrystalline Solids.................... 228
7.3.1.4 Thermal Expansion of Organic Solids.............................. 228
x Contents

7.3.1.5 Importance of Thermal Expansion.................................... 228

7.3.1.6 Simulating Thermal Properties......................................... 229
7.3.1.7 Thermal Properties in the Future...................................... 230
References................................................................................................................. 230
Problems.................................................................................................................... 231
Study Guide............................................................................................................... 232

Chapter 8 Mechanical Behavior and Measurement................................................................... 235

8.1 Elasticity......................................................................................................... 235
8.1.1 Modulus of Elasticity........................................................................ 236
8.1.2 Elastic Modulus Measurement..........................................................240
8.1.3 Poisson’s Ratio...................................................................................240
8.2 Strength..........................................................................................................240
8.2.1 Theoretical Strength.......................................................................... 241
8.2.2 Effects of Flaw Size.......................................................................... 242
8.2.2.1 Pore Shape.........................................................................244
8.2.2.2 Pore–Crack Combinations.................................................244
8.2.2.3 Internal Pores.....................................................................244
8.2.2.4 Pore Clusters......................................................................246
8.2.2.5 Inclusions...........................................................................246
8.2.3 Strength Measurement......................................................................246
8.2.3.1 Tensile Strength.................................................................246
8.2.3.2 Compressive Strength........................................................248
8.2.3.3 Bend Strength.................................................................... 249
8.2.3.4 Biaxial Strength................................................................. 251
8.2.4 Strength Data for Ceramic Materials................................................ 252
8.3 Fracture Toughness......................................................................................... 254
8.4 Ductile versus Brittle Behavior...................................................................... 257
8.4.1 Mechanism of Plastic Deformation................................................... 257
8.4.2 Deformation Behavior of Metals....................................................... 258
8.4.3 Deformation Behavior in Ceramics...................................................260
8.4.3.1 Single Crystals...................................................................260
8.4.3.2 Polycrystalline Ceramics...................................................264
8.4.4 Ceramics Deformation Summary.....................................................264
8.5 Advanced Mechanical Testing Techniques and Modeling.............................264
References................................................................................................................. 265
Additional Recommended Reading..........................................................................266
Problems.................................................................................................................... 267
Study Guide............................................................................................................... 268

Chapter 9 Time, Temperature, and Environmental Effects on Properties................................ 269

9.1 Creep.............................................................................................................. 269
9.1.1 Effects of Temperature and Stress on Creep..................................... 270
9.1.2 Effects of Single-Crystal Structure on Creep................................... 271
9.1.3 Effects of Microstructure of Polycrystalline Ceramics on Creep..... 272
9.1.4 Creep in Noncrystalline Ceramics.................................................... 273
9.1.5 Effects of Composition, Stoichiometry, and Environment................ 274
9.1.6 Measurement of Creep...................................................................... 274
9.1.7 Creep Consideration for Component Design.................................... 277
Contents xi

9.2 Static Fatigue.................................................................................................. 278

9.3 Chemical Effects............................................................................................ 281
9.3.1 Gas–Solid Reactions......................................................................... 282
9.3.1.1 Oxidation........................................................................... 282
9.3.1.2 Reduction and Other Reactions......................................... 286
9.3.1.3 Thermodynamics............................................................... 287
9.3.1.4 Interactions with Water Vapor........................................... 288
9.3.1.5 Vaporization and Dissociation........................................... 289
9.3.2 Liquid–Solid Reactions..................................................................... 289
9.3.2.1 Ambient Temperature Corrosion.......................................290
9.3.2.2 High-Temperature Corrosion of Oxides............................ 290
9.3.2.3 Condensed-Phase Corrosion.............................................. 292
9.3.2.4 Corrosion in Coal Combustion Environments................... 295
9.3.3 Solid–Solid Reactions....................................................................... 297
9.4 Mechanically Induced Effects........................................................................ 297
9.4.1 Surface Flaw Formation.................................................................... 297
9.4.2 Removal of Surface Material............................................................ 301
9.5 Thermal Shock............................................................................................... 303
References................................................................................................................. 310
Problems.................................................................................................................... 312
Study Guide............................................................................................................... 313

Chapter 10 Electrical Behavior.................................................................................................... 315

10.1 Fundamentals and Definitions........................................................................ 315
10.2 Electronic Conductivity.................................................................................. 316
10.3 Ionic Conductivity.......................................................................................... 320
10.3.1 Mechanisms of Ionic Conductivity................................................... 320
10.3.2 Ceramic Materials Exhibiting Ionic Conductivity............................ 321
10.3.3 Applications of Zirconia Oxygen Ion Conductive Ceramics............ 323
10.3.3.1 Oxygen Sensors................................................................. 323
10.3.3.2 Oxygen Pumps................................................................... 325
10.3.3.3 Electrolysis and Thermolysis............................................. 326
10.3.3.4 SOx –NOx Decomposition.................................................. 326
10.3.3.5 Solid Oxide Fuel Cells....................................................... 326
10.3.3.6 Resistance Heating Elements............................................. 328
10.3.3.7 Galvanic Cells for Thermodynamic and Kinetic
Measurements.................................................................... 329
10.3.4 Alternative Oxygen Ion Conductors.................................................. 329
10.3.5 Sodium Ion Conductors and Applications......................................... 329
10.3.6 Lithium Ion Conduction and Applications........................................ 332
10.4 Conductive Polymers...................................................................................... 333
10.5 Electrical Insulators........................................................................................ 333
10.5.1 Applications of Electrical Insulators................................................. 335
10.5.1.1 Integrated Circuit Substrates and Packages....................... 336
10.5.1.2 Spark Plug Insulators......................................................... 338
10.5.1.3 Power Line Insulators........................................................ 338
10.6 Semiconductors.............................................................................................. 338
10.6.1 Mechanisms of Semiconduction....................................................... 338
10.6.2 Applications of Ceramic Semiconductors......................................... 341
10.6.3 Photovoltaic Semiconductors............................................................ 342
xii Contents

10.7 Superconductivity........................................................................................... 345

10.7.1 Mechanism of Superconductivity...................................................... 345
10.7.2 Characteristics of Superconductivity................................................ 347
10.7.3 Evolution of Superconductor Materials.............................................348
10.7.4 Structure of High-Tc Ceramic Superconductors................................ 349
10.7.5 Characteristics of the 1:2:3 Ceramic Superconductor....................... 349
10.7.6 Applications of Superconductors...................................................... 351
References................................................................................................................. 352
Additional Recommended Reading.......................................................................... 353
Problems.................................................................................................................... 353
Study Guide............................................................................................................... 354

Chapter 11 Dielectric, Magnetic, and Optical Behavior.............................................................. 355

11.1 Dielectric Properties....................................................................................... 355
11.1.1 Polarization....................................................................................... 355
11.1.2 Dielectric Constant............................................................................ 356
11.1.3 Dielectric Strength............................................................................ 358
11.1.4 Dielectric Loss.................................................................................. 358
11.1.5 Capacitance....................................................................................... 361
11.1.5.1 Functions of a Capacitor....................................................364
11.1.5.2 History of Capacitors.........................................................364
11.1.5.3 Mechanism of High Dielectric Constant...........................364
11.1.5.4 Types of Capacitors........................................................... 366
11.1.6 Piezoelectricity.................................................................................. 367
11.1.7 Pyroelectricity................................................................................... 369
11.1.8 Ferroelectricity.................................................................................. 369
11.1.8.1 Types of Ferroelectric Crystals.......................................... 372
11.1.8.2 Polycrystalline Ferroelectrics............................................ 372
11.2 Magnetic Behavior......................................................................................... 380
11.2.1 Source of Magnetism........................................................................ 380
11.2.2 Magnetic Terminology...................................................................... 384
11.2.3 Applications of Magnetic Ceramics.................................................. 385
11.3 Optical Behavior............................................................................................. 388
11.3.1 Absorption and Transparency........................................................... 388
11.3.2 Color.................................................................................................. 390
11.3.3 Phosphorescence............................................................................... 391
11.3.4 Lasers................................................................................................ 392
11.3.5 Index of Refraction............................................................................ 393
11.3.6 Electro-Optics and Integrated Optic Devices................................... 397
References................................................................................................................. 397
Problems.................................................................................................................... 398
Study Guide............................................................................................................... 399

Part III Processing of Ceramics

Chapter 12 Introduction to Ceramic Fabrication Approaches Including Powder Processing.....403

12.1 General Ceramic Processing Approaches......................................................403
12.1.1 Conventional Ceramic Processing by Compaction of Powders........403
Contents xiii

12.1.2 Refractory Processing.......................................................................405

12.1.3 Melting and Fusion Ceramic Processing...........................................406
12.1.4 Room- or Low-Temperature Processing............................................409
12.1.5 Other Ceramic Processing Options...................................................409
12.1.5.1 Coatings............................................................................. 410
12.1.5.2 Infiltration Processes......................................................... 410
12.1.5.3 Metal–Gas Reaction.......................................................... 411
12.1.5.4 Porous Ceramics................................................................ 412
12.1.5.5 Advanced and Emerging Processes................................... 412
12.2 Powder Processing.......................................................................................... 413
12.2.1 Raw Materials................................................................................... 414
12.2.1.1 Traditional Ceramics......................................................... 414
12.2.1.2 Modern Ceramics.............................................................. 414
12.2.2 Raw Material Selection Criteria........................................................ 416
12.2.2.1 Purity................................................................................. 416
12.2.2.2 Particle Size and Reactivity............................................... 417
12.3 Powder Preparation and Sizing...................................................................... 418
12.3.1 Mechanical Sizing............................................................................. 418
12.3.1.1 Screening........................................................................... 418
12.3.1.2 Air Classification............................................................... 420
12.3.1.3 Elutriation.......................................................................... 421
12.3.1.4 Ball Milling....................................................................... 422
12.3.1.5 Attrition Milling................................................................ 425
12.3.1.6 Vibratory Milling.............................................................. 426
12.3.1.7 Fluid Energy Milling......................................................... 428
12.3.1.8 Hammer Milling................................................................ 428
12.3.1.9 Roll Crushing..................................................................... 428
12.3.1.10 Miscellaneous Crushing.................................................... 429
12.3.2 Chemical Sizing................................................................................ 429
12.3.2.1 Precipitation....................................................................... 429
12.3.2.2 Freeze Drying.................................................................... 429
12.3.2.3 Hot Kerosene Drying......................................................... 430
12.3.2.4 Sol–Gel.............................................................................. 431
12.3.2.5 Liquid Mix Process............................................................ 432
12.3.2.6 Spray Roasting................................................................... 432
12.3.2.7 Decomposition................................................................... 433
12.3.2.8 Hydrothermal Synthesis.................................................... 433
12.3.2.9 Plasma Techniques............................................................. 435
12.3.2.10 Laser Techniques............................................................... 435
12.3.3 Miscellaneous Powder Synthesis/Sizing Techniques........................ 435
12.3.3.1 Calcining............................................................................ 435
12.3.3.2 Rotary Kiln........................................................................ 435
12.3.3.3 Fluidized Bed..................................................................... 436
12.3.3.4 Self-Propagating Combustion............................................ 436
12.3.3.5 Gas Condensation.............................................................. 436
12.4 Preconsolidation............................................................................................. 436
12.4.1 Additives............................................................................................ 437
12.4.2 Spray Drying..................................................................................... 439
12.4.3 Granulation........................................................................................440
12.5 Batch Determination...................................................................................... 441
xiv Contents

References................................................................................................................. 443
Additional Recommended Reading.......................................................................... 445
Problems.................................................................................................................... 445
Study Guide............................................................................................................... 445

Chapter 13 Shape-Forming Processes......................................................................................... 447

13.1 Pressing.......................................................................................................... 447
13.1.1 Steps in Pressing............................................................................... 447
13.1.2 Selection of Additives.......................................................................448
13.1.2.1 Binders and Plasticizers.....................................................448
13.1.2.2 Lubricants and Compaction Aids...................................... 453
13.1.2.3 Removal of Organic Additives.......................................... 454
13.1.3 Uniaxial Pressing: Presses and Tooling............................................ 455
13.1.3.1 Dry Pressing...................................................................... 457
13.1.3.2 Wet Pressing...................................................................... 457
13.1.3.3 Uniaxial Pressing Problems............................................... 457
13.1.4 Isostatic Pressing............................................................................... 461
13.1.4.1 Wet-Bag Isostatic Pressing................................................ 463
13.1.4.2 Dry-Bag Isostatic Pressing................................................464
13.1.5 Applications of Pressing....................................................................465
13.2 Casting............................................................................................................466
13.2.1 Slip Casting.......................................................................................466
13.2.1.1 Raw Materials....................................................................466
13.2.1.2 Powder Processing............................................................. 467
13.2.1.3 Slip Preparation and Rheology..........................................468
13.2.1.4 Particle Size and Shape Effects.........................................468
13.2.1.5 Particle Surface Effects..................................................... 470
13.2.1.6 Slip Preparation................................................................. 477
13.2.1.7 Mold Preparation............................................................... 478
13.2.1.8 Casting............................................................................... 479
13.2.1.9 Casting Process Control.................................................... 485
13.2.1.10 Drying................................................................................ 485
13.2.2 Tape Casting...................................................................................... 486
13.2.2.1 Doctor Blade Process......................................................... 486
13.2.2.2 Other Tape-Casting Processes........................................... 486
13.2.2.3 Preparation of Tape-Casting Slurries................................ 487
13.2.2.4 Applications of Tape Casting............................................. 488
13.3 Plastic Forming.............................................................................................. 489
13.3.1 Extrusion........................................................................................... 491
13.3.1.1 Extrusion Equipment......................................................... 491
13.3.1.2 Binders and Additives for Extrusion................................. 492
13.3.1.3 Extrusion Steps.................................................................. 495
13.3.1.4 Common Extrusion Defects............................................... 498
13.3.1.5 Applications of Extrusion.................................................. 499
13.3.2 Injection Molding..............................................................................500
13.3.2.1 Injection-Molding Parameters...........................................500
13.3.2.2 Injection-Molding Defects................................................. 505
13.3.2.3 Applications of Injection Molding..................................... 510
13.3.2.4 Nonthermoplastic Injection Molding................................. 511
13.3.3 Compression Molding....................................................................... 514
Contents xv

13.3.4 Roll Forming..................................................................................... 514

13.3.5 Jiggering............................................................................................ 515
13.4 Green Machining............................................................................................ 515
References................................................................................................................. 516
Additional Recommended Reading.......................................................................... 518
Problems.................................................................................................................... 518
Study Guide............................................................................................................... 520

Chapter 14 Densification.............................................................................................................. 523

14.1 Theory of Sintering........................................................................................ 523
14.1.1 Stages of Sintering............................................................................ 523
14.1.2 Mechanisms of Sintering.................................................................. 525
14.1.2.1 Vapor-Phase Sintering....................................................... 525
14.1.2.2 Solid-State Sintering.......................................................... 527
14.1.2.3 Liquid-Phase Sintering...................................................... 533
14.1.2.4 Reactive Liquid Sintering.................................................. 534
14.1.3 Control of Conventional Sintering.................................................... 536
14.1.3.1 Atmosphere........................................................................ 537
14.1.3.2 Time and Temperature Cycle............................................. 537
14.1.3.3 Design of the Furnace........................................................ 537
14.1.4 Sintering Problems............................................................................540
14.1.4.1 Warpage.............................................................................540
14.1.4.2 Overfiring.......................................................................... 541
14.1.4.3 Burn-Off of Binders.......................................................... 541
14.1.4.4 Decomposition Reactions.................................................. 541
14.1.4.5 Polymorphic Transformations........................................... 542
14.2 Modified Densification Processes.................................................................. 542
14.2.1 Modified Particulate Processes......................................................... 542
14.2.1.1 Overpressure Sintering...................................................... 542
14.2.2 Hot Pressing......................................................................................544
14.2.2.1 Unique Hot-Pressed Properties.......................................... 547
14.2.2.2 Hot-Pressing Limitations................................................... 548
14.2.3 Hot Isostatic Pressing........................................................................ 550
14.2.4 Field-Assisted Sintering Techniques................................................. 552
14.2.5 Chemical Processes........................................................................... 554
14.2.5.1 Chemical Reaction............................................................. 554
14.2.6 Cementitious Bonding....................................................................... 559
14.2.7 Pyrolysis............................................................................................ 560
14.2.8 Melt Processing................................................................................. 562
14.2.8.1 Casting, Drawing, and Blowing......................................... 562
14.2.8.2 Spraying............................................................................. 562
14.2.9 Crystallization................................................................................... 563
14.2.10 Vapor Processing............................................................................... 567
14.2.11 Infiltration.......................................................................................... 571
14.2.12 Metal–Gas Reaction.......................................................................... 571
References................................................................................................................. 572
Additional Recommended Reading.......................................................................... 574
Problems.................................................................................................................... 575
Study Guide............................................................................................................... 575
xvi Contents

Chapter 15 Final Machining........................................................................................................ 577

15.1 Mechanisms of Material Removal................................................................. 577
15.1.1 Mounted-Abrasive Machining.......................................................... 577
15.1.2 Free-Abrasive Machining.................................................................. 578
15.1.3 Impact Abrasive Machining.............................................................. 578
15.1.4 Chemical Machining......................................................................... 579
15.1.4.1 Photoetching...................................................................... 579
15.1.5 Electrical Discharge Machining........................................................ 579
15.1.6 Laser Machining............................................................................... 580
15.2 Effects on Strength......................................................................................... 581
15.2.1 Effect of Grinding Direction............................................................. 582
15.2.2 Effects of Microstructure.................................................................. 583
15.2.3 Effects of Grinding Parameters........................................................ 584
15.2.4 Optimization of Grinding................................................................. 586
15.2.4.1 Lapping.............................................................................. 588
15.2.4.2 Annealing.......................................................................... 590
15.2.4.3 Oxidation........................................................................... 590
15.2.4.4 Chemical Etching.............................................................. 590
15.2.4.5 Surface Compression......................................................... 590
15.2.4.6 Flame Polishing................................................................. 591
15.3 Additional Sources of Information................................................................. 592
References................................................................................................................. 592
Additional Recommended Reading.......................................................................... 593
Problems.................................................................................................................... 593
Study Guide............................................................................................................... 594

Chapter 16 Quality Assurance..................................................................................................... 595

16.1 In-Process QA................................................................................................ 595
16.2 Specification and Certification....................................................................... 596
16.3 Proof Testing.................................................................................................. 598
16.4 Nondestructive Inspection.............................................................................. 598
16.4.1 Penetrants.......................................................................................... 599
16.4.2 X-Ray Radiography........................................................................... 599
16.4.2.1 Conventional X-Ray Radiography..................................... 599
16.4.2.2 Microfocus X-Ray Radiography........................................ 601
16.4.2.3 Image Enhancement.......................................................... 601
16.4.3 Computed Tomography.....................................................................603
16.4.4 Ultrasonic NDI..................................................................................606
16.4.5 Other NDI Techniques......................................................................609
16.5 Quality Problem Solving and Improvement...................................................609
16.5.1 Nature of Variation in a Fabrication Process....................................609
16.5.2 SPC Tools and Techniques................................................................ 610
16.5.2.1 Flow Chart......................................................................... 610
16.5.2.2 Check Sheet....................................................................... 611
16.5.2.3 Pareto Chart....................................................................... 612
16.5.2.4 Brainstorming.................................................................... 612
16.5.2.5 Cause and Effect Diagram (Fishbone Diagram)............... 612
16.5.2.6 Five-Whys Diagram........................................................... 613
16.5.2.7 Run Charts and Control Charts......................................... 613
Contents xvii

16.5.3 Use of SPC Tools for Continuous Improvement............................... 615

16.5.4 QA Perspective of the End User........................................................ 616
16.6 Future Developments in QA........................................................................... 616
References................................................................................................................. 616
Additional Recommended Reading.......................................................................... 618
Problems.................................................................................................................... 618
Study Guide............................................................................................................... 618

Part IV Design with Ceramics

Chapter 17 Design Considerations............................................................................................... 623

17.1 Requirements of the Application.................................................................... 623
17.2 Property Limitations...................................................................................... 624
17.3 Fabrication Limitations.................................................................................. 626
17.4 Cost Considerations........................................................................................ 628
17.5 Reliability Requirements................................................................................ 628
17.6 Summary........................................................................................................ 629
References................................................................................................................. 629
Study Guide............................................................................................................... 629

Chapter 18 Design Approaches................................................................................................... 631

18.1 Empirical Design............................................................................................ 631
18.2 Deterministic Design...................................................................................... 631
18.3 Probabilistic Design....................................................................................... 634
18.3.1 Weibull Statistics............................................................................... 634
18.3.2 Use of the Weibull Distribution in Design........................................ 639
18.3.3 Advantages of Probabilistic Design.................................................. 639
18.3.4 Limitations of Probabilistic Design.................................................. 641
18.4 Linear Elastic Fracture Mechanics Approach................................................ 641
18.5 Combined Approaches................................................................................... 642
18.6 Computer-Assisted Design............................................................................. 642
References................................................................................................................. 643
Additional Recommended Reading.......................................................................... 643
Problems....................................................................................................................644
Study Guide............................................................................................................... 645

Chapter 19 Failure Analysis......................................................................................................... 647

19.1 Fractography................................................................................................... 647
19.1.1 Location of the Fracture Origin........................................................648
19.1.1.1 Fracture Mirror and Hackle...............................................649
19.1.1.2 Wallner Lines..................................................................... 651
19.1.1.3 Other Features................................................................... 651
19.1.2 Techniques of Fractography.............................................................. 653
19.1.3 Determining Failure Cause............................................................... 656
19.1.3.1 Material Flaws................................................................... 658
19.1.3.2 Machining Damage........................................................... 659
xviii Contents

19.1.3.3 Residual Stresses............................................................... 661

19.1.3.4 Thermal Shock................................................................... 662
19.1.3.5 Impact................................................................................ 665
19.1.3.6 Biaxial Contact.................................................................. 667
19.1.3.7 Oxidation–Corrosion......................................................... 669
19.1.3.8 Slow Crack Growth........................................................... 673
19.2 Summary........................................................................................................ 674
References................................................................................................................. 674
Additional Recommended Reading.......................................................................... 676
Study Guide............................................................................................................... 676

Chapter 20 Toughening of Ceramics........................................................................................... 677

20.1 Toughening Mechanisms................................................................................ 677
20.1.1 Modulus Transfer.............................................................................. 678
20.1.1.1 Effect of Elastic Modulus.................................................. 678
20.1.1.2 Effect of Volume Fraction and Architecture..................... 678
20.1.1.3 Effect of Fiber Length....................................................... 680
20.1.1.4 Effect of Interfacial Bond.................................................. 681
20.1.2 Prestressing....................................................................................... 681
20.1.3 Crack Deflection or Impediment....................................................... 682
20.1.4 Crack Bridging..................................................................................684
20.1.5 Pullout............................................................................................... 685
20.1.6 Crack Shielding................................................................................. 685
20.1.7 Energy Dissipation............................................................................ 688
20.2 Examples of Toughened Ceramics................................................................. 689
20.2.1 Self-Reinforced Ceramics................................................................. 689
20.2.1.1 Self-Reinforced Si3N4........................................................690
20.2.1.2 Self-Reinforced ZrC..........................................................690
20.2.1.3 Aluminate Platelet-Reinforced
Transformation- Toughened ZrO2......................................690
20.2.1.4 La β-Alumina-Reinforced Transformation-Toughened
ZrO2...................................................................................690
20.2.2 Transformation-Toughened Ceramics............................................... 693
20.2.2.1 Transformation-Toughened ZrO2....................................... 693
20.2.2.2 Other Transformation-Toughened Ceramics..................... 697
20.2.3 Particulate-Reinforced Ceramics...................................................... 698
20.2.4 Whisker-Reinforced Ceramics.......................................................... 698
20.2.5 Al2O3 Reinforced with SiC Whiskers............................................... 699
20.2.6 Si3N4 Reinforced with SiC and Si3N4 Whiskers................................ 704
20.2.7 MoSi2 and MoSi2–WSi2 Reinforced with SiC Whiskers................... 704
20.2.8 Fiber-Reinforced Ceramics............................................................... 704
20.2.8.1 Glass Fibers....................................................................... 704
20.2.8.2 Carbon Fibers.................................................................... 705
20.2.8.3 Oxide Fibers...................................................................... 707
20.2.8.4 Nonoxide Fibers................................................................. 709
20.2.9 Examples of Ceramic Matrix Composites Reinforced
with Ceramic Fibers.......................................................................... 712
20.2.9.1 Cement Matrix Composites............................................... 712
20.2.9.2 Glass Matrix Composites................................................... 712
20.2.9.3 Glass–Ceramic Matrix Composites.................................. 714
Contents xix

20.2.9.4 SiC Matrix Composites Fabricated by Chemical

Vapor Infiltration............................................................... 716
20.2.9.5 SiC Matrix Composites Fabricated by Si Melt
Infiltration....................................................................... 719
20.2.9.6 SiC Matrix Composites Fabricated by Preceramic
Polymer Infiltration............................................................ 720
20.2.9.7 Oxide Matrix Composites Fabricated by Infiltration........ 721
20.2.9.8 Si3N4 Matrix Composites................................................... 721
20.2.9.9 Other Fiber-Reinforced Ceramic Matrix Composites....... 724
20.2.10 Composites with Surface Compression............................................. 726
20.2.11 Fibrous Monolith............................................................................... 727
20.3 Summary........................................................................................................ 728
References................................................................................................................. 729
Problems.................................................................................................................... 734
Study Guide............................................................................................................... 734

Part V Applying Ceramics to Real-World Challenges

Chapter 21 Solving Past Challenges: Case Studies..................................................................... 739

21.1 Evolution of the Integrated Circuit................................................................. 739
21.1.1 Silicon Crystal Growth...................................................................... 741
21.1.2 Slicing, Grinding, and Polishing....................................................... 742
21.1.3 Doping to Achieve Semiconductor Behavior.................................... 742
21.1.4 Buildup of the Device Layers............................................................ 743
21.2 Evolution of the Flash Memory and the Digital Camera............................... 746
21.3 Challenges of the Digital Watch..................................................................... 747
21.4 Invention and Evolution of the Catalytic Converter....................................... 747
21.4.1 Ceramic Material Selection and Development.................................. 748
21.4.2 Design Selection and Fabrication Development................................ 748
21.4.3 Improvements in Catalytic Converters.............................................. 749
21.5 Bioglass and Bioceramics............................................................................... 750
21.6 Refractory Evolution....................................................................................... 750
21.6.1 Refractories Development................................................................. 750
21.6.2 In Situ Refractories............................................................................ 752
21.7 Ceramics in the Nuclear Industry................................................................... 754
21.7.1 Development of Nuclear Fuel............................................................ 755
21.7.2 Nuclear Wasteforms.......................................................................... 760
21.8 Silicon Nitride: Seeking Uses for a New Material......................................... 763
References................................................................................................................. 768

Chapter 22 Where Next for Ceramics? Future Trends and Challenges....................................... 771
22.1 Nanotechnology and Nanoprocessing............................................................ 771
22.1.1 Review of Importance of Particle Size and Arrangement................ 771
22.1.2 Further Nanoscale Manipulation....................................................... 773
22.1.2.1 Control of Chemistry for Self-Assembly
and Engineered Structures................................................. 773
22.1.2.2 Quantum Dots.................................................................... 775
xx Contents

22.1.2.3 Nanoscale Thin Film Deposition....................................... 776

22.1.2.4 Carbon Nanotubes............................................................. 776
22.2 Ceramics in Environmental Cleanup............................................................. 776
22.3 Raw Materials Challenges.............................................................................. 778
22.4 Modeling......................................................................................................... 778
22.5 Advances in Processing.................................................................................. 779
22.5.1 Additive Layer Manufacture............................................................. 779
22.5.2 Cold Sintering................................................................................... 781
22.6 Extreme Environment Challenges.................................................................. 782
22.6.1 Thermal and Environmental Barrier Coatings................................. 782
22.6.1.1 Using Coupled Modeling to Help Solve a Materials
Problem.............................................................................. 784
References................................................................................................................. 785

Appendix A: Glossary.................................................................................................................. 787

Appendix B: Effective Ionic Radii for Cations and Anions...................................................... 795
Appendix C: The Periodic Table of the Elements...................................................................... 801
Index............................................................................................................................................... 803
Preface
Modern Ceramic Engineering has evolved as has the whole field of materials engineering. The first
edition in 1982 was written as a reference or guide to primarily mechanical engineers at a time that
they were thrust into the challenge of designing ceramics into gas turbine engines. I was surprised
when the book was selected as a text, so a second edition was prepared that doubled the length and
added key content so it would be suitable as a comprehensive introductory text. This second edition
was published in 1992.
In 1991, I began teaching advanced composites and various ceramics courses at the University of
Utah. When one teaches in front of a live class, one learns what works and what does not work and
receives feedback from other instructors using the text. These lessons learned were incorporated
into the third edition, which was published in 2006 with the goal of improving student interest and
comprehension. To increase interest, chapters were added on the history of ceramics and on the
wide variety of applications of ceramics. The approach was to encourage the students to think about
material development and selection in the context of the property and design requirements of each
specific application. Thus, the third edition was divided into four parts:

• Part I: Ceramics as Engineering Materials

• Part II: Structure and Properties
• Part III: Processing of Ceramics
• Part IV: Design with Ceramics

So much has advanced in ceramics, glass, and composites since the first edition and even since
the third edition that I felt the book needed a major updating. I decided to add a coauthor. I chose
William (“Bill”) E. Lee from Imperial College in London. His career and specializations were
quite different from mine and have greatly added to the content of this fourth edition. In addition
to updates in almost every chapter, we have added Part V, including two new chapters, Chapters 21
and 22. Chapter 21 presents a variety of case histories that not only provide the students with excel-
lent examples of how scientists and engineers have tackled and solved challenges, but also give the
students clues about the many directions a career path might progress. This chapter concludes with
a brief review of the career paths of the coauthors. The final chapter discusses future challenges and
trends that might guide students in launching their careers.
Bill and I would like to thank all the individuals who have contributed to all four editions with
their reviews and suggestions. We also thank our students for their feedback during each course that
has helped us present the information in what we hope is perceived as both interesting and compre-
hensive. Dr. Michael Rushton from Bill’s research group is acknowledged for significant help with
improvements to many of the figures. Finally, I personally want to thank Bill for being willing to
coauthor the fourth edition. My first contact with Bill was even before the first edition was writ-
ten. I was preparing a home study course for the American Society for Metals (ASM) on structural
ceramics. Bill was one of the individuals who had been recruited by the ASM to review each lesson
as it was completed. My last lesson was planned to be a review of the many applications of ceram-
ics, but I was slow in providing it. Bill offered to help speed up the process by drafting a portion of
the lesson. So we have come full circle, and Bill is now rightfully the coauthor. Oddly enough, Bill
and I did not meet in person until he visited Salt Lake City in 2016 to be inducted as the president
of the American Ceramic Society.
Bill thanks the following for help with his input to the fourth edition: Doni Daniel, Eugenio
Zapata-Solvas, Nasrin Al Nasiri, Michael Rushton, Wirat Lerdprom, Bai Cui, Edoardo Giorgi,
Thomas Mellan, Mike Finnis, Finn Giuliani, Luc Vandeperre, Eduardo Saiz, Julian Jones, Derek
Sinclair, Dierk Raabe, Caizhi Zhou, Carlos Levi, and David Poerschke.

xxi
xxii Preface

As was the goal for previous editions, the first goal of the fourth edition is to continue to help
the reader understand the key concepts/technology of materials science and engineering with the
emphasis on ceramics and composites containing ceramics. Rather than just focusing on the aca-
demic technology, though, a second goal is to guide the reader on why and how to apply the con-
cepts and technology to “real” engineering. To aid in reaching this goal, Part V, “Applying Ceramics
to Real-World Challenges,” has been added to the fourth edition.
The “why” and “how” can take many paths. One is driven by a need to solve a specific problem
such as a component or system failure or a perceived need for an improved product. A failure in an
existing product requires an immediate and usually interdisciplinary intensive effort. The develop-
ment of an improved product is generally ongoing and can be long term. Another key aspect of
materials science and engineering involves discovering a new material or phenomenon, conducting
basic research to better understand and improve it, and working with other scientists and engineers
to apply the evolving phenomenon or material to useful products. In this fourth edition, we have
highlighted the increasing importance of modeling and simulation in contributing to our under-
standing of ceramics in engineering applications, a trend that will only become more important in
the future. Again, we acknowledge the help of Dr. Michael Rushton in providing input on this topic.
Many examples of the various paths are included in the fourth edition, and some are presented
as case histories. Being exposed to the challenges other materials scientists and engineers have
encountered and sometimes overcome (and sometimes failed to overcome) is an important and use-
ful aspect of effectively applying materials science and engineering to new challenges. Thus, in the
fourth edition, more description of key case histories is included. For example, how did the materi-
als and fabrication technology evolve from the starting point of a few thousand transistors with a
size resolution of 10,000 nm on an integrated circuit to a modern integrated circuit with 15 nm reso-
lution containing billions of transistors? Furthermore, how was this technology then used to achieve
our modern flash drives and digital cameras? Other case history examples are the development of
the catalytic converter for automobile pollution reduction; the evolution of semiconductor ceramics
for photovoltaic devices and light-emitting diodes; the development of polycrystalline piezoelec-
tric ceramics; and the evolution of advanced refractories, nuclear ceramics, ultrahigh-temperature
ceramics, and ceramic matrix composites.
Note that all these ceramic-based developments have dramatically affected every aspect of our
daily lives, but there are still key issues regarding efficient energy production, pollution reduction,
nuclear waste, and even availability of rare raw materials. These issues are discussed in various
chapters throughout the book and especially in the final chapter.

David W. Richerson
Authors
David W. Richerson earned degrees in ceramic science and engineering from The University of
Utah (1967) and The Pennsylvania State University (1969). He conducted research on boron carbide
armor, silicon nitride, and composites at Norton Company from 1969 to 1973; coordinated materials
efforts from 1973 to 1985 at Garrett Turbine Engine Company to integrate ceramic materials into
gas turbine engines; and conducted and managed a wide range of materials programs while direc-
tor of Research and Development and later vice president at Ceramatec, Inc., from 1985 to 1991.
From 1991 to the present, Richerson has worked as a consultant, taught at The University of Utah,
and planned and conducted volunteer science outreach projects in schools and in the community.
Richerson has authored or coauthored 5 books, 13 book chapters, 21 government program final
reports, 5 patents, and 59 technical publications. He has edited or coedited four additional books,
made numerous technical and educational presentations, and presented two-day to four-day short
courses worldwide. Richerson is a fellow and past board member of the American Ceramic Society,
a member of the National Institute of Ceramic Engineers and the Ceramic Education Council, and
a past member of ASM International.

William E. Lee earned a BSc in physical metallurgy from Aston University in the United Kingdom
(1980) and a DPhil from Oxford University (1983) on radiation damage in sapphire. After postdoc-
toral research at Case Western Reserve University, he became an assistant professor at The Ohio
State University, United States, before returning to a lectureship at Sheffield University in the United
Kingdom in 1989 and becoming professor there in 1998. He moved to be the head of the Materials
Department at Imperial College London in 2006. His research has covered structure–property–
processing relations in a range of ceramics including electroceramics, glasses and glass ceramics,
nuclear ceramics, refractories, ultrahigh temperature ceramics, and whitewares. He has supervised
61 students to completion of their PhDs and authored and coauthored more than 400 articles, includ-
ing 5 books, 7 edited proceedings or journal special issues, 6 invited book/encyclopedia chapters,
and 14 invited review papers. Professor Lee is a fellow of the United Kingdom’s Royal Academy of
Engineering, the City and Guilds Institute, the Institute of Materials, Minerals and Mining, and the
American Ceramic Society, for which he was president in 2016/2017.

xxiii
http://taylorandfrancis.com
Part I
Ceramics as Engineering Materials

The objective of Part I is to introduce the reader to ceramics as key engineering materials. Chapter 1
strives to define the field of ceramics and where ceramics fit into the overall field of materials.
Chapter 2 reviews the history of ceramics and how they have expanded in scope from the invention
of earthenware in ancient times to the slow evolution of traditional ceramic industries to an explo-
sion during the last 75 years of high-technology modern applications. Part I concludes with Chapter 3,
which introduces examples of the wide range of applications of modern ceramics. The focus is on
comparison of the engineering requirements of each application with the unique characteristics of
the ceramic material best suited for that application.
http://taylorandfrancis.com
 1 What Is a Ceramic?

Individuals who have not previously studied ceramics typically ask, “What is a ceramic?” That is a
good question, especially since this book is written to be used in an introductory course in ceramic
engineering. Unfortunately, it is a difficult question. Do we categorize ceramics and other materials
according to their behavior and properties or does another approach work better such as examining
their chemical makeup or the nature of their atomic bonding? Or are materials categorized based
on some historical perspective? This chapter provides a brief review of prior definitions of ceram-
ics, discusses some problems with these definitions, identifies types of materials that should clearly
be categorized as ceramics, and concludes with an explanation of the approach that will be used
throughout the remainder of this book.

1.1 DEFINITIONS OF CERAMICS
The word ceramic was initially derived from the Greek word keramos, which means roughly “burnt
stuff.”1 Webster defines ceramics as “of or having to do with pottery.”2 Both of these definitions go
back to the earliest origins of ceramics when early peoples dug earthy clay, mixed in some water to
achieve the consistency of potter’s clay, crafted a shape, dried it in the sun, and placed it in a fire.
The resulting hard, brittle material was our first ceramic that we now refer to as “earthenware.”
However, over the subsequent millennia, many additional materials were invented that we also
think of as ceramics. The definition broadened to “the art and science of making and using solid
articles formed by the action of heat on earthy raw materials.”1
By the latter half of the twentieth century, scientists and engineers had learned to synthesize
many new ceramics, sometimes by chemical and room temperature methods that did not quite fit
the older definitions. In addition, where do cements (made at room temperature) fit? Many mod-
ern cements are now used in high-temperature, refractory, applications. W. David Kingery, often
regarded as the father of modern ceramic engineering, suggested in his classic text Introduction
to Ceramics1 a new definition: “the art and science of making and using solid articles which have
as their essential component, and are composed in large part of, inorganic nonmetallic materials.”
This definition essentially says that a ceramic is anything that is not an organic material or a metal.
It suggests three basic categories of materials: ceramics, organics, and metals. However, it still gives
no information about how to distinguish between the three categories, so we are right back where
we started. Also, it does not give us any hints about where salts, semiconductors, intermetallics, and
metalloids fit into the scheme of materials.
Since we are not likely to come up with a precise or all-encompassing definition that really dis-
tinguishes ceramics from other materials, perhaps we can try a different approach. Let us look at
some examples that are considered by most materials engineers to be in the category of ceramics.

1.2 MATERIAL TYPES GENERALLY CONSIDERED IN THE CERAMICS FAMILY

1.2.1 Polycrystalline Ceramics Fabricated by Sintering
The first earthenware pottery and most ceramics that we use today are fabricated starting with
a powder. The powder is mixed with water or other materials (such as a polymer and a solvent)
and formed to the desired shape by processes such as pressing, slip casting, extrusion, and injec-
tion molding. This “greenware” is then dried, any organic materials removed, and the remaining
particulate compact fired (sintered) at a high temperature such that the particles bond together to

3
4 Modern Ceramic Engineering

form a solid polycrystalline (made of many small crystals or grains) ceramic. This type of material
certainly fits into the prior definitions and represents the majority of the discussion in this book.

1.2.2 Glass
Glass typically starts out with powdered or crushed raw materials, but instead of sintering the
powders to form a solid, the raw materials are heated to a high enough temperature that they melt
to form a homogeneous liquid. The liquid, which is usually quite viscous (ranging from the consis-
tency of hot taffy to thick maple syrup depending on the chemical composition and temperature),
is formed into the desired shape and then cooled in such a way that no crystals or grains form. The
resulting glass material can have the same chemical composition as a polycrystalline ceramic, but
with very different properties. The difference between the polycrystalline ceramic and the glass is
the arrangement of the atoms.
In the case of the polycrystalline ceramic (as well as a single crystal ceramic), the atoms are
arranged in a repeatable three-dimensional pattern. For example, SiO2 (silicon dioxide or “silica”)
is composed of units of one silicon atom bonded to four oxygen atoms. Each unit is shaped like a
tetrahedron and bonds to four adjacent SiO 4−
4 tetrahedra to form a network structure that has both
short-range and long-range repeatability (order) throughout the material. Silica glass involves the
same SiO 4− 4 units bonded to adjacent units, but not organized into as repeatable a structure. The
glass is said to have short-range order but not long-range order. Should the SiO2 glass and other
glasses of typical ceramic chemical compositions be included in the broad materials category of
“ceramics”? Our vote is yes.
Some metals can also be processed by extremely rapid cooling from a melt to result in a glassy
structure. These are also sometimes described in the literature as “glass,” but obviously would not
fall into the category of ceramics.

1.2.3 Glass Ceramics
The atomic arrangement of glass is stable at high temperature, but not at room temperature. The
atoms want to rearrange into a crystalline structure, but do not have enough mobility at room tem-
perature. However, the glass can be induced to crystallize by adding a “nucleating agent” when
the glass is initially formed and then by heat treating at a suitable temperature below the melting
temperature. Enough energy is present at this temperature to allow the atoms to move (diffuse).
The atoms in the glass rearrange around the atoms of the nucleating agent to form a polycrystalline
ceramic called a glass ceramic. This also fits the prior definitions of a ceramic.

1.2.4 Single Crystals of Ceramic Compositions

Single crystals of natural minerals such as quartz, ruby, and diamond are occasionally found in nature.
They have special characteristics compared to polycrystalline forms of the same minerals, but are
much rarer. At first thought, single crystals may seem to us to be too exotic to be considered for large-
scale use. On the contrary, we have learned to synthesize single crystals of a wide variety of ceramic
compositions and have established uses ranging from synthetic diamonds to ruby laser rods to cubic
zirconia jewelry. For example, more than 900 t of synthetic diamond crystals were produced in 2014.
Most single crystals are produced at high temperature from ceramic powders and clearly fit into
the existing definitions as ceramics. However, some single crystals are produced at essentially room
temperature by growth from a supersaturated solution. An example is sodium chloride. Is this a
ceramic? NaCl certainly is not organic or metallic, but many people have trouble perceiving it as a
ceramic, especially because it is soluble in water. But NaCl and other ionically bonded salts are best
categorized as ceramics because of their mode of atomic bonding and crystal structures, as will be
discussed in later chapters.
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