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Ceramic
Processing
Ceramic
Processing

Mohamed N. Rahaman
University of Missouri-Rolla, USA

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Library of Congress Cataloging-in-Publication Data

Rahaman, M. N. 1950-
Ceramic processing / Mohamed Rahaman.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-7285-2 (acid-free paper)
1. Ceramics. 2. Ceramic engineering. 3. Polycrystals. 4. Sintering. I. Title.

TP807.R278 2006
666--dc22 2006043889

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7285_book.fm Page xi Friday, June 9, 2006 10:28 AM

Contents
Chapter 1 Ceramic Fabrication Processes: An Introductory Overview .......................................1
1.1 Introduction...............................................................................................................................1
1.2 Ceramic Fabrication Processes.................................................................................................2
1.2.1 Gas-Phase Reactions ....................................................................................................2
1.2.1.1 Chemical Vapor Deposition ..........................................................................4
1.2.1.2 Directed Metal Oxidation .............................................................................7
1.2.1.3 Reaction Bonding..........................................................................................8
1.2.1.4 Silicon Nitride ...............................................................................................9
1.2.1.5 Oxides..........................................................................................................10
1.2.1.6 Silicon Carbide............................................................................................11
1.2.2 Liquid Precursor Methods..........................................................................................12
1.2.2.1 Sol–Gel Processing .....................................................................................12
1.2.2.2 Polymer Pyrolysis .......................................................................................15
1.2.2.3 Silicon Carbide............................................................................................15
1.2.2.4 Silicon Nitride .............................................................................................17
1.2.2.5 Boron Nitride and Boron Carbide ..............................................................18
1.2.3 Fabrication from Powders ..........................................................................................19
1.2.3.1 Melt Casting ................................................................................................19
1.2.3.2 Sintering of Compacted Powders ...............................................................20
1.3 Production of Polycrystalline Ceramics from Powders: An Overview.................................21
1.3.1 Powder Synthesis and Powder Characterization........................................................21
1.3.2 Powder Consolidation ................................................................................................22
1.3.3 The Sintering Process.................................................................................................22
1.3.4 Ceramic Microstructures ............................................................................................25
1.4 Case Study in Processing: Fabrication of TiO2 from Powders .............................................28
1.5 Concluding Remarks ..............................................................................................................30
Problems...........................................................................................................................................30
References ........................................................................................................................................32

Chapter 2 Synthesis of Powders .................................................................................................37

2.1 Introduction.............................................................................................................................37
2.2 Powder Characteristics ...........................................................................................................37
2.3 Powder Synthesis Methods ....................................................................................................38
2.4 Powder Preparation by Mechanical Methods ........................................................................39
2.4.1 Comminution ..............................................................................................................39
2.4.1.1 High Compression Roller Mills..................................................................40
2.4.1.2 Jet Mills.......................................................................................................41
2.4.1.3 Ball Mills.....................................................................................................41
2.4.2 Mechanochemical Synthesis ......................................................................................45
2.5 Powder Synthesis by Chemical Methods...............................................................................46
2.5.1 Solid-State Reactions..................................................................................................46
2.5.1.1 Decomposition.............................................................................................47
2.5.1.2 Chemical Reaction between Solids ............................................................53
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2.5.1.3 Reduction ....................................................................................................57

2.5.2Liquid Solutions .........................................................................................................58
2.5.2.1 Precipitation from Solution.........................................................................58
2.5.2.2 Evaporation of the Liquid...........................................................................74
2.5.2.3 Gel Route ....................................................................................................79
2.5.2.4 Nonaqueous Liquid Reaction......................................................................81
2.5.3 Vapor-Phase Reactions ...............................................................................................81
2.5.3.1 Gas–Solid Reaction.....................................................................................82
2.5.3.2 Reaction between a Liquid and a Gas........................................................84
2.5.3.3 Reaction between Gases .............................................................................84
2.6 Special Topic: Synthesis of Nanoscale Ceramic Powders.....................................................87
2.6.1 Liquid Solution Techniques .......................................................................................87
2.6.2 Vapor-Phase Techniques.............................................................................................88
2.7 Concluding Remarks ..............................................................................................................89
Problems...........................................................................................................................................89
References ........................................................................................................................................91

Chapter 3 Powder Characterization.............................................................................................97

3.1 Introduction.............................................................................................................................97
3.2 Physical Characterization .......................................................................................................97
3.2.1 Types of Particles .......................................................................................................98
3.2.1.1 Primary Particles .........................................................................................98
3.2.1.2 Agglomerates...............................................................................................98
3.2.1.3 Particles .......................................................................................................98
3.2.1.4 Granules.......................................................................................................99
3.2.1.5 Flocs ............................................................................................................99
3.2.1.6 Colloids .......................................................................................................99
3.2.1.7 Aggregates...................................................................................................99
3.2.2 Particle Size and Particle Size Distribution ...............................................................99
3.2.2.1 Definition of Particle Size.........................................................................100
3.2.2.2 Average Particle Size ................................................................................101
3.2.2.3 Representation of Particle Size Data ........................................................102
3.2.3 Particle Shape ...........................................................................................................106
3.2.4 Measurement of Particle Size and Size Distribution...............................................106
3.2.4.1 Microscopy................................................................................................106
3.2.4.2 Sieving.......................................................................................................107
3.2.4.3 Sedimentation............................................................................................109
3.2.4.4 Electrical Sensing Zone Techniques (the Coulter Counter).....................110
3.2.4.5 Light Scattering.........................................................................................111
3.2.4.6 X-Ray Line Broadening............................................................................113
3.2.5 Surface Area .............................................................................................................113
3.2.6 Porosity of Particles .................................................................................................116
3.2.6.1 Gas Adsorption..........................................................................................116
3.2.6.2 Mercury Porosimetry ................................................................................119
3.2.6.3 Pycnometry................................................................................................121
3.3 Chemical Composition .........................................................................................................122
3.3.1 Optical Atomic Spectroscopy: Atomic Absorption and Atomic Emission..............122
3.3.2 X-Ray Fluorescence Spectroscopy...........................................................................124
3.4 Crystal Structure and Phase Composition ...........................................................................125
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3.5 Surface Characterization ......................................................................................................127

3.5.1 Surface Structure ......................................................................................................129
3.5.2 Surface Chemistry ....................................................................................................130
3.5.2.1 Auger Electron Spectroscopy (AES) ........................................................130
3.5.2.2 X-Ray Photoelectron Spectroscopy (XPS)...............................................132
3.5.2.3 Secondary Ion Mass Spectrometry (SIMS)..............................................133
3.6 Concluding Remarks ............................................................................................................136
Problems.........................................................................................................................................136
References ......................................................................................................................................138

Chapter 4 Science of Colloidal Processing...............................................................................141

4.1 Introduction...........................................................................................................................141
4.2 Types of Colloids .................................................................................................................142
4.3 Attractive Surface Forces .....................................................................................................142
4.3.1 van der Waals Forces between Atoms and Molecules ............................................142
4.3.2 van der Waals Forces between Macroscopic Bodies...............................................144
4.3.3 The Hamaker Constant.............................................................................................146
4.3.4 Effect of the Intervening Medium ...........................................................................148
4.4 Stabilization of Colloidal Suspensions ................................................................................148
4.5 Electrostatic Stabilization.....................................................................................................149
4.5.1 The Development of Charges on Oxide Particles in Water ....................................149
4.5.1.1 Isomorphic Substitution ............................................................................150
4.5.1.2 Adsorption of Ions from Solution ............................................................150
4.5.2 Origins of the Electrical Double Layer ...................................................................153
4.5.3 Isolated Double Layer ..............................................................................................154
4.5.4 Surface Charge .........................................................................................................157
4.5.5 Repulsion between Two Double Layers ..................................................................158
4.5.6 Stability of Electrostatically Stabilized Colloids.....................................................160
4.5.7 Kinetics of Flocculation ...........................................................................................161
4.5.8 Electrokinetic Phenomena ........................................................................................162
4.5.8.1 Microelectrophoretic Technique ...............................................................163
4.5.8.2 Significance of the ζ Potential..................................................................164
4.6 Steric Stabilization................................................................................................................164
4.6.1 Adsorption of Polymers from Solution....................................................................165
4.6.2 Origins of Steric Stabilization..................................................................................167
4.6.3 Effects of Solvent and Temperature.........................................................................168
4.6.4 Stability of Sterically Stabilized Suspensions .........................................................170
4.6.5 Stabilization by Polymers in Free Solution .............................................................171
4.7 Electrosteric Stabilization.....................................................................................................172
4.7.1 Dissociation of Polyelectrolytes in Solution............................................................172
4.7.2 Adsorption of Polyelectrolytes from Solution.........................................................174
4.7.3 Stability of Electrosterically Stabilized Suspensions ..............................................175
4.8 Structure of Consolidated Colloids......................................................................................176
4.9 Rheology of Colloidal Suspensions .....................................................................................178
4.9.1 Rheological Properties..............................................................................................178
4.9.2 Factors Influencing the Rheology of Colloidal Suspensions ..................................180
4.9.2.1 Influence of Interparticle Forces...............................................................180
4.9.2.2 Influence of Particle Interactions on the Viscosity...................................183
4.9.2.3 Influence of Particle Characteristics .........................................................185
4.10 Concluding Remarks ............................................................................................................187
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Problems.........................................................................................................................................187
References ......................................................................................................................................189

Chapter 5 Sol–Gel Processing...................................................................................................193

5.1 Introduction...........................................................................................................................193
5.2 Types of Gels........................................................................................................................194
5.2.1 Particulate Gels.........................................................................................................194
5.2.2 Polymeric Gels .........................................................................................................195
5.3 Sol–Gel Processing of Aqueous Silicates ............................................................................197
5.3.1 Effect of pH ..............................................................................................................198
5.3.1.1 Polymerization in the pH range of 2 to 7 ................................................198
5.3.1.2 Polymerization above pH ≈ 7 ...................................................................200
5.3.1.3 Polymerization below pH ≈ 2...................................................................200
5.4 Metal Alkoxides....................................................................................................................201
5.4.1 Preparation of Metal Alkoxides ...............................................................................201
5.4.1.1 Reactions between Metals and Alcohols ..................................................201
5.4.1.2 Reactions Involving Metal Chlorides .......................................................202
5.4.1.3 Miscellaneous Methods.............................................................................202
5.4.2 Basic Properties ........................................................................................................204
5.4.2.1 Physical Properties ....................................................................................204
5.4.2.2 Chemical Properties ..................................................................................205
5.5 Sol–Gel Processing of Silicon Alkoxides ............................................................................206
5.5.1 Precursors .................................................................................................................206
5.5.2 Hydrolysis and Condensation ..................................................................................207
5.5.2.1 Acid-Catalyzed Conditions .......................................................................208
5.5.2.2 Base-Catalyzed Conditions .......................................................................209
5.5.3 Polymer Growth .......................................................................................................209
5.5.3.1 Polymer Growth Models...........................................................................210
5.5.3.2 Structural Evolution of Sol–Gel Silicates ................................................212
5.5.3.3 Rheological Measurements .......................................................................212
5.5.4 Gelation.....................................................................................................................215
5.5.5 Aging of Gels ...........................................................................................................216
5.5.6 Drying of Gels..........................................................................................................216
5.5.6.1 Conventional Drying .................................................................................217
5.5.6.2 Supercritical Drying ..................................................................................227
5.5.6.3 Structural Changes during Drying............................................................229
5.5.7 Gel Densification during Sintering ..........................................................................230
5.6 Sol–Gel Preparation Techniques ..........................................................................................234
5.6.1 Preparation of Particulate Gels ................................................................................234
5.6.1.1 Single-Component Gels ............................................................................234
5.6.1.2 Multicomponent Gels................................................................................236
5.6.2 Preparation of Polymeric Gels .................................................................................237
5.6.2.1 Use of Double Alkoxides..........................................................................237
5.6.2.2 Partial Hydrolysis of the Slowest Reacting Alkoxide..............................238
5.6.2.3 Use of a Mixture of Alkoxides and Metal Salts ......................................239
5.6.2.4 Slow Addition of Small Amounts of Water..............................................240
5.6.2.5 Matched Hydrolysis Rates ........................................................................241
5.7 Applications of Sol–Gel Processing ....................................................................................241
5.7.1 Thin Films and Coatings..........................................................................................242
5.7.1.1 Dip Coating ...............................................................................................242
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5.7.1.2 Spin Coating..............................................................................................244

5.7.1.3 Structural Evolution in Films ...................................................................245
5.7.1.4 Applications of Films................................................................................245
5.7.2 Fibers ........................................................................................................................245
5.7.3 Monoliths..................................................................................................................246
5.7.4 Porous Materials.......................................................................................................247
5.8 Concluding Remarks ............................................................................................................247
Problems.........................................................................................................................................247
References ......................................................................................................................................249

Chapter 6 Mixing and Packing of Powders ..............................................................................253

6.1 Introduction...........................................................................................................................253
6.2 Mixing of Particulate Solids ................................................................................................254
6.2.1 Types of Mixtures.....................................................................................................254
6.2.2 Mixing and Segregation Mechanisms......................................................................254
6.2.3 Mixture Composition and Quality ...........................................................................257
6.2.3.1 Statistical Methods ....................................................................................257
6.2.3.2 Measurement Techniques..........................................................................259
6.2.4 Mixing Technology...................................................................................................260
6.3 Packing of Particles ..............................................................................................................262
6.3.1 Regular Packing of Monosized Spheres ..................................................................263
6.3.2 Random Packing of Particles ...................................................................................264
6.3.2.1 Monosized Particles ..................................................................................265
6.3.2.2 Bimodal Mixtures of Spheres ...................................................................266
6.3.2.3 Binary Mixtures of Nonspherical Particles ..............................................269
6.3.2.4 Ternary and Multiple Mixtures.................................................................270
6.3.2.5 Continuous Particle Size Distributions.....................................................271
6.4 Concluding Remarks ............................................................................................................274
Problems.........................................................................................................................................274
References ......................................................................................................................................276

Chapter 7 Forming of Ceramics................................................................................................279

7.1 Introduction...........................................................................................................................279
7.2 Additives in Ceramic Forming.............................................................................................280
7.2.1 Solvents.....................................................................................................................280
7.2.2 Dispersants................................................................................................................282
7.2.2.1 Inorganic Acid Salts..................................................................................283
7.2.2.2 Surfactants .................................................................................................284
7.2.2.3 Low- to Medium-Molecular-Weight Polymers ........................................286
7.2.3 Binders......................................................................................................................287
7.2.4 Plasticizers ................................................................................................................290
7.2.5 Other Additives.........................................................................................................292
7.3 Forming of Ceramics............................................................................................................292
7.3.1 Dry and Semidry Pressing .......................................................................................292
7.3.1.1 Die Compaction ........................................................................................292
7.3.1.2 Isostatic Compaction.................................................................................301
7.3.2 Casting Methods.......................................................................................................302
7.3.2.1 Slip Casting ...............................................................................................302
7.3.2.2 Pressure Casting ........................................................................................306
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7.3.2.3 Tape Casting..............................................................................................308

7.3.2.4 Gelcasting..................................................................................................311
7.3.2.5 Electrophoretic Deposition .......................................................................313
7.3.3 Plastic-Forming Methods .........................................................................................316
7.3.3.1 Extrusion ...................................................................................................317
7.3.3.2 Coextrusion ...............................................................................................320
7.3.3.3 Injection Molding......................................................................................320
7.4 Solid Freeform Fabrication ..................................................................................................323
7.4.1 Particle-Filled Polymer Methods .............................................................................324
7.4.1.1 Fused Deposition Modeling......................................................................324
7.4.1.2 Laminated Object Manufacturing .............................................................325
7.4.2 Powder Methods .......................................................................................................325
7.4.2.1 Selective Laser Sintering ..........................................................................325
7.4.2.2 Three-Dimensional Printing......................................................................326
7.4.3 Suspension Methods.................................................................................................326
7.4.3.1 Stereolithography ......................................................................................326
7.4.3.2 Direct Ceramic Ink-Jet Printing................................................................327
7.4.3.3 Robocasting ...............................................................................................328
7.4.3.4 Freeze Casting...........................................................................................328
7.5 Concluding Remarks ............................................................................................................330
Problems.........................................................................................................................................330
References ......................................................................................................................................333

Chapter 8 Drying, Debinding, and Microstructural Characterization of Green Bodies...........337

8.1 Introduction...........................................................................................................................337
8.2 Drying of Granular Ceramics...............................................................................................338
8.2.1 Drying of Granular Layers.......................................................................................338
8.2.2 Drying of Granular Solids........................................................................................340
8.2.2.1 Driving Forces for Shrinkage and Moisture Movement ..........................341
8.2.2.2 Stages of Drying .......................................................................................341
8.2.2.3 Moisture Distribution and Movement.......................................................347
8.2.2.4 Drying Stresses .........................................................................................348
8.2.2.5 Warping and Cracking ..............................................................................349
8.2.2.6 Drying Technology....................................................................................351
8.3 Binder Removal (Debinding) ...............................................................................................352
8.3.1 Extraction by Capillary Flow...................................................................................352
8.3.2 Solvent Extraction ....................................................................................................352
8.3.3 Thermal Debinding...................................................................................................353
8.3.3.1 Stages and Mechanisms of Thermal Debinding.......................................353
8.3.3.2 Models for Thermal Debinding ................................................................354
8.3.3.3 Thermal Debinding in Practice.................................................................357
8.4 Green Microstructures and Their Characterizations............................................................358
8.5 Concluding Remarks ............................................................................................................361
Problems.........................................................................................................................................361
References ......................................................................................................................................362

Chapter 9 Sintering and Microstructure Development .............................................................365

9.1 Introduction...........................................................................................................................365
9.2 Solid-State Sintering.............................................................................................................366
7285_book.fm Page xvii Friday, June 9, 2006 10:28 AM

9.2.1 Driving Force for Sintering......................................................................................367

9.2.2 Effects of Surface Curvature ....................................................................................369
9.2.2.1 Stress on the Atoms under a Curved Surface...........................................369
9.2.2.2 Chemical Potential of the Atoms under a Curved Surface ......................370
9.2.2.3 Vacancy Concentration under a Curved Surface......................................371
9.2.2.4 Vapor Pressure over a Curved Surface .....................................................372
9.2.3 Grain Boundary Effects............................................................................................373
9.2.4 Mechanisms of Sintering..........................................................................................375
9.2.5 Stages of Sintering ...................................................................................................377
9.2.6 Sintering Models and Their Predictions ..................................................................379
9.2.6.1 Analytical Models .....................................................................................379
9.2.6.2 Predictions of the Analytical Models .......................................................385
9.2.6.3 Effect of Applied Pressure ........................................................................387
9.2.6.4 Numerical Simulations of Sintering .........................................................387
9.3 Grain Growth and Coarsening .............................................................................................387
9.3.1 Normal Grain Growth ..............................................................................................389
9.3.2 Abnormal Grain Growth ..........................................................................................394
9.3.3 Ostwald Ripening .....................................................................................................395
9.3.4 Control of Grain Growth..........................................................................................398
9.3.4.1 Effect of Dopants: Solute Drag ................................................................398
9.3.4.2 Effect of Fine, Inert Second-Phase Particles............................................401
9.3.5 Grain Growth and Pore Evolution in Porous Compacts .........................................403
9.3.6 Interactions between Pores and Grain Boundaries..................................................406
9.3.6.1 Pore Mobility ............................................................................................406
9.3.6.2 Kinetics of Pore–Boundary Interactions...................................................409
9.3.6.3 Microstructural Maps ................................................................................410
9.4 Liquid-Phase Sintering .........................................................................................................412
9.4.1 Stages of Liquid-Phase Sintering.............................................................................414
9.4.2 Kinetic and Thermodynamic Factors .......................................................................416
9.4.2.1 Contact Angle............................................................................................416
9.4.2.2 Dihedral Angle ..........................................................................................418
9.4.2.3 Effects of Gravity......................................................................................418
9.4.2.4 Grain Boundary Films ..............................................................................419
9.4.2.5 Volume Fraction of Liquid Phase .............................................................420
9.4.3 Phase Diagrams in Liquid-Phase Sintering .............................................................420
9.5 Sintering Practice..................................................................................................................421
9.5.1 Heating Schedules ....................................................................................................422
9.5.1.1 Isothermal Sintering ..................................................................................422
9.5.1.2 Constant Heating–Rate Sintering..............................................................423
9.5.1.3 Multistage Sintering ..................................................................................423
9.5.1.4 Rate-Controlled Sintering .........................................................................424
9.5.1.5 Fast Firing .................................................................................................425
9.5.1.6 Microwave Sintering .................................................................................426
9.5.1.7 Plasma-Assisted Sintering.........................................................................427
9.5.2 Pressure-Assisted Sintering ......................................................................................428
9.5.2.1 Hot Pressing ..............................................................................................428
9.5.2.2 Sinter Forging............................................................................................430
9.5.2.3 Hot Isostatic Pressing (HIPing) ................................................................430
9.5.3 Particle and Green Compact Characteristics ...........................................................430
9.5.3.1 Particle Size...............................................................................................430
9.5.3.2 Particle Size Distribution ..........................................................................431
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9.5.3.3 Particle Shape and Particle Structure .......................................................432

9.5.3.4 Particle Packing.........................................................................................432
9.5.3.5 Effect of Green Density ............................................................................434
9.5.4 Chemistry Considerations ........................................................................................435
9.5.4.1 Gases in Pores...........................................................................................435
9.5.4.2 Vapor Transport.........................................................................................437
9.5.4.3 Volatilization and Decomposition.............................................................437
9.5.4.4 Oxidation State..........................................................................................438
9.5.4.5 Defect Chemistry and Stoichiometry .......................................................439
9.6 Concluding Remarks ............................................................................................................440
Problems.........................................................................................................................................441
References ......................................................................................................................................446

Appendix A: Physical Constants ..................................................................................................453

Appendix B: SI Units — Names and Symbols ...........................................................................455

Appendix C: Conversion of Units................................................................................................457

Appendix D: Aperture Size of U.S. Standard Wire Mesh Sieves (ASTM E 11:87) ..................459

Appendix E: Densities and Melting Points of Some Elements, Ceramics, and Minerals..........461

Index ..............................................................................................................................................465
7285_book.fm Page v Friday, June 9, 2006 10:28 AM

Dedicated to Vashanti, Lennard, and Ronald

7285_book.fm Page vii Friday, June 9, 2006 10:28 AM

Preface
The production and application of ceramics are among the oldest technological skills. The field of
ceramic materials has its roots in the more traditional aspects of the subject such as clay-based
ceramics and glasses. During the past few decades, new developments in the use of ceramics in
more advanced technological applications have attracted considerable attention. The discovery of
ceramic superconductors, as well as the use of ceramics for heat-resistant tiles in the space shuttle,
optical fibers, components in high temperature engines, and the electrolyte in solid oxide fuel cells,
has generated considerable interest in the field.
The increasing use of ceramics in more advanced technological applications has resulted in a
heightened demand for improvements in properties and reliability. In recent years, there has been
the realization that such improvements can be achieved only through careful attention to the
fabrication process. The engineering properties of polycrystalline ceramics are controlled by the
microstructure, which, in turn, depends on the processing method used to fabricate the body.
Therefore, the fabrication process governs the production of microstructures with the desired
properties. It is often stated that materials science is a field at the interface between the physical
sciences (physics, chemistry, and mathematics) and engineering (such as electrical, mechanical,
and civil). In this view, the approach to ceramic processing is concerned with the understanding
of fundamentals and the application of the knowledge to the production of microstructures with
useful properties.
This book is concerned primarily with the processing of polycrystalline ceramics. Because of
its importance and widespread use, the fabrication of ceramics by the consolidation and sintering
of powders forms the focus of this book. A brief treatment of the production of ceramics (and
glasses) by the less conventional sol–gel route is also included. The approach is to outline the
fundamental issues of each process and to show how they are applied to the practical fabrication
of ceramics. Each fabrication route involves a number of processing steps, and each step has the
potential for producing microstructural flaws that degrade the properties of the fabricated material.
An important feature of this treatment is the attempt to show the importance of each step as well
as the interconnection between the various steps in the overall fabrication route. Chapter 1 provides
an introductory overview of the various methods that can be used for the production of ceramic
materials. The overview also forms a basis for the more detailed treatment of powder processing
and sol–gel processing, which is discussed later in the book. Chapter 2 to Chapter 9 form a logical
development from the start of the fabrication process to the final fabricated microstructure.
My intention has been to prepare a textbook that is suitable for a one-semester (or two-quarter)
course in ceramic processing at the upper undergraduate level or the introductory graduate level.
A background in the concepts and processing of traditional ceramics, typically obtained in lower-
level undergraduate courses, is assumed. It is hoped that the book will also be useful to researchers
in industry who are involved in the production of ceramics or who would wish to develop a
background in the processing of ceramics.
I wish to thank the many authors and publishers who have allowed me permission to reproduce
their figures in this book. Last but not least, I wish to thank my wife, Vashanti, for her encouragement
and support when I was preoccupied with the completion of this book.
7285_C001.fm Page 10 Thursday, June 22, 2006 12:34 PM

10 Ceramic Processing

pressing). On the other hand, RBSN bodies with a high degree of dimensional accuracy and with
complex shapes can be prepared fairly readily without the need for expensive machining after
firing.

1.2.1.5 Oxides

A reaction bonding route involving both gas–solid and gas–liquid reactions is the reaction-bonded
aluminum oxide (RBAO) process developed by Claussen and coworkers [23–27]. The RBAO
process utilizes the oxidation of powder mixtures containing a substantial amount of Al (30 to 65
vol%). A mixture of Al (particle size ∼20 μm), α-Al2O3 (0.5 to 1.0 μm), and ZrO2 (∼0.5 μm) is
milled vigorously in an attrition mill, dried and compacted to produce a green article (porosity ≈
30 to 40%). During heat treatment in an oxidizing atmosphere (commonly air), the Al oxidizes to
nanometer-sized γ-Al2O3 crystals below ∼900°C that undergo a phase transformation to α-Al2O3
at temperatures up to ∼11~00°C. The volume expansion (28 vol%) associated with the oxidation
of Al to α-Al2O3 is used to partially compensate for the shrinkage due to sintering, so that dense
RBAO ceramics can be achieved with lower shrinkage than conventionally sintered Al2O3 ceramics.
Figure 1.7 shows a micrograph of a reaction-bonded Al2O3/ZrO2 ceramic produced from a starting
mixture of 45 vol% Al, 35 vol% Al2O3, and 20 vol% ZrO2. Successful application of the RBAO
process depends on several variables, such as the characteristics of the starting powders (e.g.,
particle size and volume fraction of the Al), the milling parameters, the green density of the
compacted mixture, and the heating (oxidation) schedule. ZrO2 is known to aid the microstructure
development during sintering, but its role is not clear. In addition to Al2O3, the RBAO process has
been applied to the fabrication of mullite ceramics [28] and composites [29].
A gas–solid reaction involving the oxidation of a combination of an alkaline earth metal and
another metal has been used recently to produce ceramics containing an alkaline earth element
[30–35]. An unusual feature of most alkaline earth metals is the reduction in solid volume
accompanying oxidation. For example, the molar volume of MgO is 19% smaller than that of
Mg. In contrast, most other metals tend to expand during oxidation. The reduction in volume due
to the oxidation of an alkaline earth metal can be used to offset the volume expansion of
accompanying the oxidation of another metal. In this way, dense ceramics containing an alkaline
earth element can be produced with little change in external dimensions from dense preforms of
metal-bearing precursors.

1 μm

FIGURE 1.7 Scanning electron micrograph showing the microstructure of a reaction-bonded aluminum oxide
(RBAO) sample. The white phase is ZrO2 (∼20 vol%) and the dark phase is Al2O3. (Courtesy of M.P. Harmer.)
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