Ceramic Materials - Science and Engineering Carter and Norton PDF

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Contents Preface ................................................ vii PART I HISTORY AND INTRODUCTION 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.1 Definitions 3 1.2 General Properties 4 1.3 Types of Ceramic and their Applications...

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Contents

Preface PART I 1

Contents

MAT_PR.indd xi

HISTORY AND INTRODUCTION 3

1.1 1.2 1.3 1.4 1.5 1.6

3 4 5 6 7

Definitions General Properties Types of Ceramic and their Applications Market Critical Issues for the Future Relationship between Microstructure, Processing and Properties Safety Ceramics on the Internet On Units

8 9 10 10

Some History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

15

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13

15 17 19 19 20 21 22 24 25 26 28 29 29

PART II 3

vii

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.7 1.8 1.9 2

................................................

Earliest Ceramics: The Stone Age Ceramics in Ancient Civilizations Clay Types of Pottery Glazes Development of a Ceramics Industry Plaster and Cement Brief History of Glass Brief History of Refractories Major Landmarks of the Twentieth Century Museums Societies Ceramic Education MATERIALS

Background You Need to Know . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

35

3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9

35 36 37 37 39 42 44 45 47

The Atom Energy Levels Electron Waves Quantum Numbers Assigning Quantum Numbers Ions Electronegativity Thermodynamics: The Driving Force for Change Kinetics: The Speed of Change

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4

5

6

7

Bonds and Energy Bands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

51

4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8

51 51 53 58 63 64 64 66

Types of Interatomic Bond Young’s Modulus Ionic Bonding Covalent Bonding Metallic Bonding in Ceramics Mixed Bonding Secondary Bonding Electron Energy Bands in Ceramics

Models, Crystals, and Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

71

5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11

71 74 75 76 76 79 81 81 82 83 83

Terms and Definitions Symmetry and Crystallography Lattice Points, Directions, and Planes The Importance of Crystallography Pauling’s Rules Close-Packed Arrangements: Interstitial Sites Notation for Crystal Structures Structure, Composition, and Temperature Crystals, Glass, Solids, and Liquid Defects Computer Modeling

Binary Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

87

6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 6.13

87 88 88 89 90 91 92 93 93 93 94 95 96

Background CsCl NaCl (MgO, TiC, PbS) GaAs (β-SiC) AlN (BeO, ZnO) CaF2 FeS2 Cu2O CuO TiO2 Al2O3 MoS2 and CdI2 Polymorphs, Polytypes, and Polytypoids

Complex Crystal and Glass Structures . . . . . . . . . . . . . . . . . . . . . . . .

100

7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15

100 101 102 104 105 106 107 107 108 109 109 110 111 111 111

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Introduction Spinel Perovskite The Silicates and Structures Based on SiO4 Silica Olivine Garnets Ring Silicates Micas and Other Layer Materials Clay Minerals Pyroxene β-Aluminas and Related Materials Calcium Aluminate and Related Materials Mullite Monazite

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7.16 7.17 7.18 7.19 7.20 7.21 8

YBa2Cu3O7 and Related High-Temperature Superconductors (HTSCs) Si3N4, SiAlONs, and Related Materials Fullerenes and Nanotubes Zeolites and Microporous Compounds Zachariasen’s Rules for the Structure of Glass Revisiting Glass Structures

112 113 113 114 115 117

Equilibrium Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

120

8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 8.11

120 121 124 124 125 126 128 130 132 132 133

What’s Special about Ceramics? Determining Phase Diagrams Phase Diagrams for Ceramists: The Books Gibbs Phase Rule One Component (C = 1) Two Components (C = 2) Three and More Components Composition with Variable Oxygen Partial Pressure Quaternary Diagrams and Temperature Congruent and Incongruent Melting Miscibility Gaps in Glass

PART III TOOLS 9

Furnaces 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 9.13

10

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The Need for High Temperatures Types of Furnace Combustion Furnaces Electrically Heated Furnaces Batch or Continuous Operation Indirect Heating Heating Elements Refractories Furniture, Tubes, and Crucibles Firing Process Heat Transfer Measuring Temperature Safety

139 139 139 140 141 141 143 144 146 147 148 148 149 151

Characterizing Structure, Defects, and Chemistry . . . . . . . . . . . . . .

154

10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 10.10 10.11 10.12 10.13 10.14 10.15

154 155 157 158 159 161 162 163 163 165 166 168 168 169 171

Characterizing Ceramics Imaging Using Visible-Light, IR, and UV Imaging Using X-rays and CT Scans Imaging in the SEM Imaging in the TEM Scanning-Probe Microscopy Scattering and Diffraction Techniques Photon Scattering Raman and IR Spectroscopy NMR Spectroscopy and Spectrometry Mössbauer Spectroscopy and Spectrometry Diffraction in the EM Ion Scattering (RBS) X-ray Diffraction and Databases Neutron Scattering

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10.16 10.17 10.18 10.19 10.20

Mass Spectrometry Spectrometry in the EM Electron Spectroscopy Neutron Activation Analysis (NAA) Thermal Analysis

172 172 174 175 175

PART IV DEFECTS 11

12

13

Point Defects, Charge, and Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . .

181

11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 11.10 11.11 11.12 11.13 11.14 11.15 11.16

181 182 183 184 184 186 187 189 190 191 192 192 193 197 197 199

Are Defects in Ceramics Different? Types of Point Defects What Is Special for Ceramics? What Type of Defects Form? Equilibrium Defect Concentrations Writing Equations for Point Defects Solid Solutions Association of Point Defects Color Centers Creation of Point Defects in Ceramics Experimental Studies of Point Defects Diffusion Diffusion in Impure, or Doped, Ceramics Movement of Defects Diffusion and Ionic Conductivity Computing

Are Dislocations Unimportant? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

201

12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 12.10 12.11 12.12 12.13 12.14

202 206 206 208 208 211 214 215 216 216 217 219 219 220

A Quick Review of Dislocations Summary of Dislocation Properties Observation of Dislocations Dislocations in Ceramics Structure of the Core Detailed Geometry Defects on Dislocations Dislocations and Diffusion Movement of Dislocations Multiplication of Dislocations Dislocation Interactions At the Surface Indentation, Scratching, and Cracks Dislocations with Different Cores

Surfaces, Nanoparticles, and Foams . . . . . . . . . . . . . . . . . . . . . . . . . . .

224

13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 13.10 13.11 13.12

224 225 225 227 230 230 231 232 233 233 234 235

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Background to Surfaces Ceramic Surfaces Surface Energy Surface Structure Curved Surfaces and Pressure Capillarity Wetting and Dewetting Foams Epitaxy and Film Growth Film Growth in 2D: Nucleation Film Growth in 2D: Mechanisms Characterizing Surfaces

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13.13 13.14 13.15 13.16 13.17 14

15

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239 240 241 241 242

Interfaces in Polycrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

246

14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10 14.11 14.12 14.13 14.14

246 248 249 251 254 255 258 259 262 263 264 265 265 265

What Are Grain Boundaries? For Ceramics GB Energy Low-Angle GBs High-Angle GBs Twin Boundaries General Boundaries GB Films Triple Junctions and GB Grooves Characterizing GBs GBs in Thin Films Space Charge and Charged Boundaries Modeling Some Properties

Phase Boundaries, Particles, and Pores . . . . . . . . . . . . . . . . . . . . . . . .

269

15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 15.9 15.10 15.11 15.12 15.13 15.14 15.15

269 269 270 270 271 272 276 276 277 278 279 280 281 282 283

PART V 16

Steps In Situ Surfaces and Nanoparticles Computer Modeling Introduction to Properties

The Importance Different Types Compared to Other Materials Energy The Structure of PBs Particles Use of Particles Nucleation and Growth of Particles Pores Measuring Porosity Porous Ceramics Glass/Crystal Phase Boundaries Eutectics Metal/Ceramic PBs Forming PBs by Joining MECHANICAL STRENGTH AND WEAKNESS

Mechanical Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

289

16.1 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 16.10 16.11 16.12 16.13

289 291 292 294 295 296 296 297 298 299 300 301 301

Philosophy Types of Testing Elastic Constants and Other “Constants” Effect of Microstructure on Elastic Moduli Test Temperature Test Environment Testing in Compression and Tension Three- and Four-Point Bending K Ic from Bend Test Indentation Fracture Toughness from Indentation Nanoindentation Ultrasonic Testing

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17

18

16.14 Design and Statistics 16.15 SPT Diagrams

302 305

Deforming: Plasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

309

17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 17.9 17.10 17.11 17.12 17.13 17.14

309 310 312 313 314 315 317 317 318 318 319 321 321 322

Plastic Deformation Dislocation Glide Slip in Alumina Plastic Deformation in Single Crystals Plastic Deformation in Polycrystals Dislocation Velocity and Pinning Creep Dislocation Creep Diffusion-Controlled Creep Grain-Boundary Sliding Tertiary Creep and Cavitation Creep Deformation Maps Viscous Flow Superplasticity

Fracturing: Brittleness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

325

18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 18.9 18.10 18.11 18.12

325 326 327 329 329 330 331 332 335 338 338 339

The Importance of Brittleness Theoretical Strength: The Orowan Equation The Effect of Flaws: The Griffith Equation The Crack Tip: The Inglis Equation Stress Intensity Factor R Curves Fatigue and Stress Corrosion Cracking Failure and Fractography Toughening and Ceramic Matrix Composites Machinable Glass-Ceramics Wear Grinding and Polishing

PART VI PROCESSING 19

20

Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

345

19.1 19.2 19.3 19.4 19.5 19.6 19.7 19.8

345 345 347 347 348 348 351 354

Geology, Minerals, and Ores Mineral Formation Beneficiation Weights and Measures Silica Silicates Oxides Nonoxides

Powders, Fibers, Platelets, and Composites . . . . . . . . . . . . . . . . . . . . .

359

20.1 20.2 20.3 20.4 20.5 20.6 20.7 20.8 20.9

359 360 360 362 363 363 364 365 365

Making Powders Types of Powders Mechanical Milling Spray Drying Powders by Sol-Gel Processing Powders by Precipitation Chemical Routes to Nonoxide Powders Platelets Nanopowders by Vapor-Phase Reactions

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20.10 20.11 20.12 20.13 20.14 20.15 20.16 20.17 20.18 20.19 20.20 20.21 20.22 20.23 20.24 20.25 20.26 20.27 21

22

23

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MAT_PR.indd xvii

Characterizing Powders Characterizing Powders by Microscopy Sieving Sedimentation The Coulter Counter Characterizing Powders by Light Scattering Characterizing Powders by X-ray Diffraction Measuring Surface Area (the BET Method) Determining Particle Composition and Purity Making Fibers and Whiskers Oxide Fibers Whiskers Glass Fibers Coating Fibers Making Ceramic–Matrix Composites Ceramic–Matrix Composites from Powders and Slurries Ceramic–Matrix Composites by Infiltration In Situ Processes

366 366 366 367 368 368 369 369 370 370 371 372 372 373 374 374 375 375

Glass and Glass-Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

379

21.1 21.2 21.3 21.4 21.5 21.6 21.7 21.8 21.9 21.10 21.11 21.12 21.13 21.14 21.15 21.16

379 380 383 385 386 386 386 386 388 388 388 390 392 393 394 396

Definitions History Viscosity, η Glass: A Summary of Its Properties, or Not Defects in Glass Heterogeneous Glass Yttrium–Aluminum Glass Coloring Glass Glass Laser Precipitates in Glass Crystallizing Glass Glass as Glaze and Enamel Corrosion of Glass and Glaze Types of Ceramic Glasses Natural Glass The Physics of Glass

Sols, Gels, and Organic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . .

400

22.1 22.2 22.3 22.4 22.5 22.6

400 401 402 403 406 407

Sol-Gel Processing Structure and Synthesis of Alkoxides Properties of Alkoxides The Sol-Gel Process Using Metal Alkoxides Characterization of the Sol-Gel Process Powders, Coatings, Fibers, Crystalline, or Glass

Shaping and Forming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

412

23.1 23.2 23.3 23.4 23.5 23.6 23.7 23.8 23.9

412 413 413 414 414 415 416 417 418

The Words Binders and Plasticizers Slip and Slurry Dry Pressing Hot Pressing Cold Isostatic Pressing Hot Isostatic Pressing Slip Casting Extrusion

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23.10 23.11 23.12 23.13 23.14 23.15 23.16 23.17 24

25

26

Injection Molding Rapid Prototyping Green Machining Binder Burnout Final Machining Making Porous Ceramics Shaping Pottery Shaping Glass

419 420 420 421 421 422 422 423

Sintering and Grain Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

427

24.1 24.2 24.3 24.4 24.5 24.6 24.7 24.8 24.9 24.10 24.11 24.12 24.13 24.14 24.15 24.16 24.17 24.18

427 429 429 429 431 431 433 433 434 435 436 437 438 439 439 440 441 441

The Sintering Process The Terminology of Sintering Capillary Forces and Surface Forces Sintering Spheres and Wires Grain Growth Sintering and Diffusion Liquid-Phase Sintering Hot Pressing Pinning Grain Boundaries More Grain Growth Grain Boundaries, Surfaces, and Sintering Exaggerated Grain Growth Fabricating Complex Shapes Pottery Pores and Porous Ceramics Sintering with Two and Three Phases Examples of Sintering in Action Computer Modeling

Solid-State Phase Transformations and Reactions . . . . . . . . . . . . . . .

444

25.1 25.2 25.3 25.4 25.5 25.6 25.7 25.8 25.9 25.10 25.11 25.12 25.13 25.14 25.15 25.16 25.17 25.18 25.19 25.20

444 445 445 447 448 449 450 451 451 452 453 454 454 455 457 458 459 459 460 461

Transformations and Reactions: The Link The Terminology Technology Phase Transformations without Changing Chemistry Phase Transformations Changing Chemistry Methods for Studying Kinetics Diffusion through a Layer: Slip Casting Diffusion through a Layer: Solid-State Reactions The Spinel-Forming Reaction Inert Markers and Reaction Barriers Simplified Darken Equation The Incubation Period Particle Growth and the Effect of Misfit Thin-Film Reactions Reactions in an Electric Field Phase Transformations Involving Glass Pottery Cement Reactions Involving a Gas Phase Curved Interfaces

Processing Glass and Glass-Ceramics . . . . . . . . . . . . . . . . . . . . . . . . .

463

26.1 26.2 26.3

463 463 467

The Market for Glass and Glass Products Processing Bulk Glasses Bubbles

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26.4 26.5 26.6 26.7 26.8 26.9 26.10 26.11 26.12 26.13 26.14 26.15 27

28

481

27.1 27.2 27.3 27.4 27.5 27.6 27.7

481 481 484 484 485 486 488

Defining Thick Film Tape Casting Dip Coating Spin Coating Spraying Electrophoretic Deposition Thick-Film Circuits

Thin Films and Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

494

28.1 28.2 28.3 28.4 28.5 28.6

494 494 495 495 497

The Difference between Thin Films and Thick Films Acronyms, Adjectives, and Hyphens Requirements for Thin Ceramic Films Chemical Vapor Deposition Thermodynamics of Chemical Vapor Deposition Chemical Vapor Deposition of Ceramic Films for Semiconductor Devices Types of Chemical Vapor Deposition Chemical Vapor Deposition Safety Evaporation Sputtering Molecular-Beam Epitaxy Pulsed-Laser Deposition Ion-Beam-Assisted Deposition Substrates

MAT_PR.indd xix

498 499 500 500 501 502 503 504 504

Growing Single Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

507

29.1 29.2 29.3 29.4 29.5 29.6 29.7 29.8 29.9 29.10 29.11 29.12

507 507 508 509 511 511 514 515 516 516 517

Why Single Crystals? A Brief History of Growing Ceramic Single Crystals Methods for Growing Single Crystals of Ceramics Melt Technique: Verneuil (Flame-Fusion) Melt Technique: Arc-Image Growth Melt Technique: Czochralski Melt Technique: Skull Melting Melt Technique: Bridgman–Stockbarger Melt Technique: Heat-Exchange Method Applying Phase Diagrams to Single-Crystal Growth Solution Technique: Hydrothermal Solution Technique: Hydrothermal Growth at...