Ceramic

Fabrication
Technology

Roy W. Rice
Alexandria, Virginia

MARCEL

EL MARCEL DEKKER, INC. NEW YORK • BASEL

Copyright © 2003 Marcel Dekker, Inc.

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 MATERIALS ENGINEERING

1. Modern Ceramic Engineering: Properties, Processing, and Use in De-

sign: Second Edition, Revised and Expanded, David W. Richer-son
2. Introduction to Engineering Materials: Behavior, Properties, and
Selection, G. T. Murray
3. Rapidly Solidified Alloys: Processes . Structures . Applications, edited
by Howard H. Liebermann
4. Fiber and Whisker Reinforced Ceramics for Structural Applications,
David Belitskus
5. Thermal Analysis of Materials, Robert F. Speyer
6. Friction and Wear of Ceramics, edited by Said Jahanmir
7. Mechanical Properties of Metallic Composites, edited by Shojiro
Ochiai
8. Chemical Processing of Ceramics, edited by Burtrand I. Lee and
Edward J. A. Pope
9. Handbook of Advanced Materials Testing, edited by Nicholas P.
Cheremisinoff and Paul N. Cheremisinoff
10. Ceramic Processing and Sintering, M. N. Rahaman
11. Composites Engineering Handbook, edited by P. K. Mallick
12. Porosity of Ceramics, Roy W. Rice
13. Intermetallic and Ceramic Coatings, edited by Narendra B. Dahotre
and T. S. Sudarshan
14. Adhesion Promotion Techniques: Technological Applications, edited
by K. L Mittal and A. Pizzi
15. Impurities in Engineering Materials: Impact, Reliability, and Control,
edited by Clyde L Briant
16. Ferroelectric Devices, Kenji Uchino
17. Mechanical Properties of Ceramics and Composites: Grain and Par-
ticle Effects, Roy W. Rice
18. Solid Lubrication Fundamentals and Applications, Kazuhisa Miyoshi
19. Modeling for Casting and Solidification Processing, edited by Kuang-
O (Oscar) Yu
20. Ceramic Fabrication Technology, Roy W. Rice

Additional Volumes in Preparation

Coatings for Polymers and Plastics, edited by Rose Ann Ryntz and Philip
V. Yaneff

Micromechatronics, Kenji Uchino and Jayne Giniewicz

Copyright © 2003 Marcel Dekker, Inc.

 Preface

There is a spectrum of needs for reference, overview, and instructional material

concerning the fabrication of ceramic and ceramic composite specimens and es-
pecially components. These needs range from, at one extreme, addressing basic
scientific principles and parameters of different processing and fabrication meth-
ods to, at the other extreme, basic engineering aspects, including costs and re-
lated operational factors. Scientific principles are most extensively treated in
various books that focus on individual, or a limited range of, established process-
ing methods, mostly those based exclusively on pressureless sintering. Such
books may address in a perfunctory manner, or not at all, important topics such
as pressure sintering processes, melt processing and fabrication, and chemical
reaction processes, especially the important subject of chemical vapor deposition
(CVD). Some engineering aspects of some processes are treated in some books,
but mostly in a limited way and often in older books. The counterpart of basic
scientific and basic engineering aspects are detailed operational factors that ad-
dress both cost and component performance trade-offs that are needed for a suc-
cessful manufacturing process. However, these are addressed very little or not at
all in the literature since they would be very extensive and generally proscribed
in their treatment by proprietary concerns.
The concept and goal of this book is to provide a link between basic sci-
ence and the ultimate, but nonexistent, detailed engineering/operational treat-

in

Copyright © 2003 Marcel Dekker, Inc.

 iv Preface

ment of the subject. It is intended to complement several very useful books em-
phasizing scientific aspects by providing a more pragmatic engineering-oriented
approach and a broader, more comprehensive perspective. The book includes in-
dustrially and technologically important topics such as pressure sintering, reac-
tion processing and fabrication, and various fusion processes, as well as
speciality processing/fabrication, e.g., for porous or composite bodies. This is
not at the expense of the more extensively used powder consolidation and pres-
sureless sintering, but some less used methods, such as electrophoretic deposi-
tion, and emerging ones, such as rapid prototyping/solid free-form fabrication,
are also treated. Instead, a balance has been sought by focusing on overall and
key engineering aspects, with more limited detailed discussion of processes that
are extensively treated in other books. Important engineering factors are often
addressed via summary descriptions of successful solutions to engineering chal-
lenges, e.g., at the extreme of processing parameters such as handling great
shrinkages in sintering large parts.
The practical engineering aspect of the book is provided in three fashions.
The first is the selection and balance of topics, as mentioned above, including
substantial discussion of costs and trade-offs. Such discussion is extended to
promising processes not yet used in production, to aid in their development and
evaluation for niche, and possibly more extensive, opportunities for production.
Examples of this broader, more pragmatic approach include substantial emphasis
on processing and fabrication by methods other than pressureless sintering, as
well as a chapter on densification with additives and one on use of additives in
powder preparation and other processing and fabrication methods. Another im-
portant example of the broader approach taken in this book is attention to the ca-
pabilities and limitations of various processing and fabrication methods in terms
of materials and microstructures, hence the effect on component performance, as
well as component character, e.g., size, shape, and costs.
The first of three additional factors to note about this book is the referenc-
ing. There is a huge and still rapidly growing literature on topics included in the
book, making a comprehensive presentation impossible. Literature searches of
data bases can help provide information on specific topics, and were used some,
but such searches cannot be effective as a means of assembling the bulk of the
information for preparation of a book. This author has instead followed nearly all
of the topics of this book, and in two companion books (Porosity of Ceramics
and Mechanical Properties of Ceramics and Composites: Grain and Particle Ef-
fects, both titles, Marcel Dekker, Inc.) continuously for over 30 years. Much of
this included obtaining and filing, on an ongoing basis, copies of the first, multi-
ple, or complete page(s) of papers or reports of interest. This organized collec-
tion, which fills over 10 full-sized file cabinets, was the primary basis for
references for this book (and the two companion ones), but the bulk of this infor-
mation was still too voluminous to include. Thus, pertinent files were reviewed

Copyright © 2003 Marcel Dekker, Inc.

 Preface v

to select material to be used and referenced, with the primary selection criteria
being the pertinence and importance of the results. The bulk of the references
came from the author's files, but still generally constitute a few to several per-
cent of his files. Other reviews and summaries along with earlier, especially
landmark, as well as more recent, work indicating newer directions, giving other
pertinent references, or both, have been included to the extent possible. Overall
the author's perspective from continuous interest, contacts, and activity in im-
proved fabrication and processing of advanced ceramics and ceramic composites
has been the basis of selecting the topics covered and the literature referenced.
The second additional feature of this book to note is its relation to the two
other books referenced above. The three books together summarize the linkage
between fabrication/processing and most important properties of ceramics. In
particular, this book notes the impact of fabrication and processing on mi-
crostructure and, to some extent, on properties, as a guide, while more detailed
property effects via impacts of microstructure can be found in the two books
noted above.
The third additional aspect to mention of this book is the evaluation of spe-
cific industrial practices, especially uses of specific processes. Such information
is generally limited, especially more recent changes in usage, due to proprietary
interests. Where such usage is not clearly documented or widely known, but is
known to the author with a reasonable degree of certainty, it is indicated with
qualifications such as probable, appears, or believed.
Many people have contributed in a variety of ways to the development of
this book, especially colleagues at my three places of employment: The Boeing
Co. (Seattle WA), the U.S. Naval Research Lab (Washington, DC), and W R.
Grace (Columbia, MD), particularly the following from Grace: Ken Anderson,
Jerry Block, Rasto Brezny, Craig Cameron, Jyoti Chakraverti, Jack Enloe, Av
Kerkar, and Tariq Quidir at W. R. Grace. Several people have aided by reading
drafts of chapters or sections of them (numbers shown in parenthesis), providing
comments, and sometimes additional references, as follows: Dave Lewis (U.S.
Naval Res. Lab.) and Bob Ruh (Air Force Materials Lab.) (1-8); Jack Sibold
(TDA Res. Inc.) (2); Ken Anderson (now with Zircoa), and Jyoti Chakraverti
(now with Ferro Corp.) (4); Jack Rubin (consultant) (5); John Locher
(Saphikon), Rich Palicka (Cercom Inc.), Ken Sandhage (Ohio State Univ.), and
Fred Schmid (Crystal Systems) (6), as well as Curt Scott (now deceased) for sev-
eral discussion and inputs. Finally, Drs. Steve Freiman and Sheldon Wiedrehorn
and Mr. George Quinn of NIST are thanked for making me a visiting scientist
there and hence giving me library access.
Roy W. Rice

Copyright © 2003 Marcel Dekker, Inc.

 Contents

Preface Hi
Abbreviations xi

1. BACKGROUND AND OVERVIEW 1

1.1 Introduction 1
1.2 Why Ceramics and Which Ones 3
1.3 Political and Economic Factors Impacting Development
and Application of Advanced Ceramics 8
1.4 Cost and Profit Factors 12
1.5 Overview of Ceramic Fabrication Technology 21
1.6 Summary and Conclusions 24
References 25

2. PREPARATION OF CERAMIC POWDERS 27

2.1 Introduction and Background 27
2.2 Processing Established Binary Oxide Powders via Conventional
Chemical Salt Precipitation and Calcination 29
2.3 Production of Other Single and Mixed-Oxide Powders via
Salt Precursor Decomposition 35

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 viii Contents

2.4 Direct Production of Oxide Powders 41

2.5 Processing of Nonoxide Powders 48
2.6 Powder Particle Coating and Characterization 57
2.7 Powder and Particle Characterization 60
2.8 Discussion, Summary, and Conclusions 62
References 63

3. USE OF ADDITIVES IN POWDER PREPARATION

AND OTHER RAW MATERIALS AND
NONDENSIFICATION USES 73
3.1 Introduction 73
3.2 Use of Additives in Preparing Ceramic Powders 74
3.3 Additive Effects on Crystallographic Phase Transformations 78
3.4 Use of Additives in the Growth of Ceramic and Related
Whiskers and Platelets 83
3.5 Use of Additives in Other Ceramic Processing, Especially
Melt Processing 85
3.6 Discussion, Summary, and Conclusions 90
References 91

4. FORMING AND PRESSURELESS SINTERING OF POWER-

DERIVED BODIES 99
4.1 Introduction 99
4.2 Powder Consolidation Under Pressure with Little Binder
and Plastic Flow 100
4.2.1 Die Pressing 100
4.2.2 Hydrostatic/isostatic pressing 110
4.3 Plastic Forming 113
4.3.1 Extrusion 113
4.3.2 Injection molding 118
4.4 Colloidal Processing 121
4.4.1 Slip, tape, and pressure casting 121
4.4.2 Electrophoretic deposition (EPD) 126
4.5 Miscellaneous Powder Consolidation Technologies 129
4.6 Binder Systems, Drying, Green Machining, Binder-Burnout,
and Bisque Firing/Machining 131
4.7 Sintering 135
4.8 Discussion and Summary 138
References 141

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 Contents ix

5. USE OF ADDITIVES TO AID DENSIFICATION 147

5.1 Introduction 147
5.2 Additives for Densification of Aluminum Oxide 149
5.3 Other Oxides 155
5.4 Mixed Oxides 166
5.4.1 Aluminates 166
5.4.2 Silicates 167
5.4.3 Ferrites 167
5.4.4 Electrical ceramics 169
5.5 Nonoxides 172
5.6 Ceramic Composites 181
5.7 Discussion and Conclusions 184
References 187

6. OTHER GENERAL DENSIFICATION AND FABRICATION

METHODS 205
6.1 Introduction 205
6.2 Hot Pressing 206
6.2.1 Practice and results 206
6.2.2 Extending practical capabilities of hot pressing 215
6.3 Press Forging and Other Deformation Forming
Processes 220
6.4 Hot Isostatic Pressing 225
6.5 Reaction Processing 228
6.6 Melt Processing 246
6.6.1 Glasses and polycrystalline bodies 246
6.6.2 Single crystals 251
6.6.3 Eutectic ceramics and directional crystallization
of glasses 257
6.7 Summary 259
References 261

7. SPECIAL FABRICATION METHODS 270

7.1 Introduction 270
7.2 Fabrication of Filaments, Fibers, and Related Entities for
Reinforcement and Other Applications 270
7.2.1 Introduction to miscellaneous and polymer-derived
ceramic fibers 270

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 x Contents

7.2.2 Preparation of ceramic fibers from ceramic powders

and by conversion of other fibers 275
7.2.3 CVD of ceramic filaments and melt-derived
fibers and filaments 278
7.2.4 Fiber and filament behavior, uses in composites,
and future directions 281
7.3 Fabrication of Porous Bodies 283
7.3.1 Introduction 283
7.3.2 Porous bodies via ceramic bead and balloon and
other fabrication methods 288
7.4 Rapid Prototyping/Solid Freeform Fabrication (SFF) 292
7.4.1 Introduction and methods 293
7.4.2 SFF applications, comparisons, and trends 297
7.5 Ceramic Fiber Composites 302
7.6 Coatings 306
7.7 Discussion and Summary 309
References 310

8. CROSSCUTTING, MANUFACTURING FACTORS, AND

FABRICATION 317
8.1 Introduction 317
8.2 Important Crosscutting Factors 317
8.2.1 Anion/gaseous impurities and outgassing prior to
or during densification 317
8.2.2 Effects of alternate heating methods 322
8.2.3 Fabrication of ceramic composites 325
8.3 Manufacturing Factors 329
8.3.1 Machining and surface finishing 329
8.3.2 Component inspection and nondestructive
evaluation (NDE) 333
8.3.3 Attachment and joining 335
8.4 Fabrication Overview and Opportunities to Improve
Manufacturing Processes 341
References 348

Index 353

Copyright © 2003 Marcel Dekker, Inc.

 Abbreviations

CVD chemical vapor deposition

CVI chemical vapor infiltration
EFG edge film-fed growth (of single crystals or eutectic systems)
HEM heat exchanger method (of single crystal growth and possibly
of eutectic or polycrystalline bodies)
PVD physical vapor deposition (e.g., evaporation or sputtering
processes)
RBSN or RSSN reaction bonded or sintered silicon nitride
RSSC reaction sintered SiC
SFF solid freeform fabrication, closely related to, and often
synonymous with, rapid prototyping
v/o volume percent
w/o weight percent

Copyright © 2003 Marcel Dekker, Inc.