CARBIDE, NITRIDE

AND BORIDE
MATERIALS
SYNTHESIS AND
PROCESSING
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CARBIDE, NITRIDE
AND BORIDE
MATERIALS
SYNTHESIS AND
PROCESSING
Edited by

Alan W. Weimer
Professor of Chemical Engineering
University of Colorado
Boulder
USA
Published by Chapman & Hall, 2~ Boundary Row, London SEl 8HN, UK

Chapman & Hall, 2~ Boundary Row, London SE1 8HN, UK

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First edition 1997

1997 Chapman & Hall
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Typeset in 10/12 pt Palatino by Academic & Technical Typesetting, Bristol
ISBN-13 :978-94-01 0-6521-4 e-ISBN-13 :978-94-009-0071-4
DOl: 10.1007/978-94-009-0071-4

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CONTENTS

List of contributors xiii

Foreword xvii

Preface xix

Acknowledgments xxi

List of symbols xxiii

PART ONE INTRODUCTION 1

Overview 1
Safety issues 2
1 Non-oxide materials: applications and engineering 3
Makuteswara Srinivasan and William Rafaniello
Introduction 3
Advanced ceramics - origin, current status, trends 4
Applications engineering 18
References 38
2 Critical powder characteristics 43
William Rafaniello
Introduction 43
Tungsten carbide (WC) 43
Silicon carbide (SiC) 47
Silicon nitride (Si3 N 4 ) 53
Aluminum nitride (AIN) 58
Summary 67
References 68

PART TWO CARBOTHERMAL REDUCTION SYNTHESIS PROCESSES 75

Overall process 75
Safety issues 76
3 Thermochemistry and kinetics 79
Alan W. Weimer
Introduction 79
Thermochemistry 79
vi Contents
Kinetics 81
Importance of the gas phase 88
Synthesis of carbide and nitride powders 89
References 110
4 Acheson process 115
Philip J. Guichelaar
Introduction, history 115
Basic silicon carbide process description 116
Manufacturing cost factors 126
Summary 127
References 128
5 Electric arc furnace processes 131
William S. Wilson and Philip J. Guichelaar
Introduction 131
Boron carbide manufacturing 131
Other non-oxide ceramics 135
References 135
6 Tube/pusher/moving bed furnace processes 137
William E. Hollar Jr and Jonathan J. Kim
Introduction 137
Fundamental physio-chemical considerations 146
System design considerations 153
Process scale-up considerations 154
Conclusions 156
Acknowledgments 157
References 157
7 Rotary tube reactor processes 159
Peter T.B. Shaffer
Introduction 159
Rotary furnace design configurations 160
Process considerations 162
Operating difficulties 164
Applications to non-oxide powder synthesis 165
References 168
8 Fluidized bed reactor processes 169
Alan W. Weimer
Background 169
Application to carbothermal reduction processes 170
References 179

PART THREE COMBUSTION SYNTHESIS PROCESSES 181

Overall process 181
Safety issues 182
 Contents vii
9 Thermochemistry and kinetics 183
Jan A. Puszynski
Principles of combustion synthesis 183
Thermodynamics and thermochemistry 187
Ignition of condensed reacting systems 190
Combustion front structure and stability analysis 192
Gasless combustion 199
Gas-solid combustion 208
Synthesis of complex composites and solid solutions 221
References 224
10 Processes 229
Stephen D. Dunmead
Introduction 229
Solid-solid reactions 229
Gas-solid reactions 244
Summary 269
References 269

PART FOUR GAS PHASE SYNTHESIS PROCESSES 273

Overall process 273
Safety issues 273
References 274
11 Thermochemistry and kinetics 275
Richard C. Flagan
Introduction 275
Thermodynamics of gas phase synthesis 276
Reaction kinetics 278
Aerosol dynamics 281
Reaction routes for vapor phase ceramic synthesis 293
Summary 302
References 303
12 Thermal aerosol processes 307
M. Kamal Akhtar and Sotiris E. Pratsinis
Overview 307
Fundamentals 308
Design and operation 315
Applications 317
Summary 337
References 338
13 Laser processes 343
Arne K. Knudsen
Introduction 343
Laser synthesis of powders 343
viii Contents
Applications 351
References 357
14 Plasma processes 359
Peter C. Kong and Emil Pfender
Introduction 359
Plasma generation 361
Plasma reactors 362
Powder synthesis 365
References 383

PART FIVE LIQUID PHASE SYNTHESIS PROCESSES 389

Overall process 389
Safety issues 389
Reference 390
15 Liquid phase reaction processes 391
Gary M. Crosbie
Introduction 391
Silicon nitride powder processes: imide intermediate routes 392
Silicon nitride powder processes: silazane intermediate routes 401
Boron nitride and aluminum nitride processes 403
Carbides and borides 405
References 405

PART SIX SYNTHESIS OF WHISKERS, PLATELETS AND FIBERS 409

Safety issues 410
References 410
16 Whisker and platelet synthesis processes 411
Terry N. Tiegs and Sam C. Weaver
Introduction 411
Non-oxide whisker growth mechanisms 412
Silicon carbide whisker growth processes 413
Silicon carbide whisker characterization 419
Platelet synthesis 426
Acknowledgments 430
References 430
17 Fiber synthesis processes 433
Jonathan Lipowitz
Introduction 433
Process 434
Composition and structure 438
Properties 446
Applications 452
 Contents ix
Future developments 452
References 453

PART SEVEN PRE-fPOST-SYNTHESIS PROCESSING 457

Safety issues 457

18 Size reduction 459

Leonard G. Austin and Peter T. Luckie
Introduction 459
Some general definitions and principles 459
Comminution and fracture mechanics 462
Very fine and ultrafine grinding 467
Criteria to be considered in selection of equipment 475
References 476

19 Chemical purifica tion 479

Kevin J. Nilsen and Alan W. Weimer
Effect of chemistry on processing and properties 479
Origin of chemical impurities 480
Removal of carbon 483
Removal of oxygen and metal impurities 492
Summary 500
References 500

20 Solids dispersion in liquids 505

Andrew G. Haerle and Kevin J. Nilsen
Introduction 505
Dispersion 505
Colloid stability 508
Non-aqueous media 509
Steric stabilization 510
Ceramic systems 513
Rheology of non-oxide slips 516
Spray drying 519
References 521

21 Spray drying 525

Fred V. Shaw and Michael H. Andrews
Introduction 525
Basic process - open systems 526
Closed cycle systems 534
Process control 536
Capital investment 538
Operating cost 539
Experience with non-oxide systems 540
References 542
x Contents
PART EIGHT COATINGS, FILMS AND INFILTRATION PROCESSES 545
Overall process 545
Safety issues 545
22 Chemical vapor deposition (CVD) and infiltration (CVI) 547
Theodore M. Besmann, David P. Stinton, Richard A. Lowden and Woo Y. Lee
Introduction 547
Chemical vapor deposition (CVD) 547
Chemical vapor infiltration (CVI) 563
References 573
23 Plasma-enhanced chemical vapor deposition (PECVD) 579
Steven R. Droes, Toivo T. Kodas and Mark f. Hampden-Smith
Introduction 579
Glow discharge plasmas 580
Plasma characterization 581
Effect of plasma process parameters on film properties 584
Film deposition 586
Advantages and limitations of PECVD-prepared coatings 599
References 600

PART NINE HIGH TEMPERATURE FURNACE ENGINEERING 605

Types of high temperature furnaces 605
Safety issues 607
24 Design considerations for high temperature furnaces 609
Ellis W. Delahoy
Introduction 609
Process and product considerations 609
Furnace configurations 610
High temperature heat sources 618
High temperature insulation 621
Design package 621
References 629
25 Rotary tube calciners 631
David W. Dahlstrom
Introduction 631
General equipment description 632
Materials of construction 635
Equipment selection 635

APPENDICES SELECTED PROPERTY DATA 637

A Crystallographic properties 639
B Thermodynamic and thermal properties 641
 Contents xi
C Mechanical properties at 293 K 649
D Electrical and magnetic properties at 293 K 653
E Chemical properties 655
Index 665
CONTRIBUTORS

M. KAMAL AKHTAR STEVEN R. DROES

Department of Chemical Engineering, Department of Chemical Engineering,
Center for Aerosol Processes, University of New Mexico,
University of Cincinnati, Albuquerque, NM,
Cincinnati, OH, USA
USA
STEPHEN D. DUNMEAD
MICHAEL H. ANDREWS
Department of Chemical Engineering,
Niro, Inc., Ceramics & Advanced Materials,
Columbia, MD, The Dow Chemical Company,
USA Midland, MI,
LEONARD G. AUSTIN USA
Department of Mineral Engineering,
Mineral Processing Section, RICHARD C. FLAGAN
The Pennsylvania State University, California Institute of Technology,
University Park, PA, Pasadena, CA,
USA USA

THEODORE M. BESMANN PHILIP J. GUICHELAAR

Metals and Ceramics Division, Department of Mechanical and Aeronautical
Oak Ridge National Laboratory, Engineering,
Oak Ridge, TN, Western Michigan University,
USA Kalamazoo, MI,
USA
GARY M. CROSBIE
Ford Motor Company,
ANDREW G. HAERLE
Dearborn, MI,
Ceramics & Advanced Materials,
USA
The Dow Chemical Company,
DAVID W. DAHLSTROM Midland, MI,
ABB Raymond, USA
Lisle,IL,
USA MARK J. HAMPDEN-SMITH
Department of Chemistry and
ELLIS W. DELAHOY Center for Micro-engineered Materials,
Harper International Corporation, University of New Mexico,
Lancaster, NY, Albuquerque, NM,
USA USA
xiv Contributors
WILLIAM E. HOLLAR, JR PETER T. LUCKIE
The Carborundum Company, Department of Mineral Engineering,
Technology Division, Mineral Processing Section,
Niagara Falls, NY, The Pennsylvania State University,
USA University Park, P A,
USA
JONATHAN J. KIM
The Carborundum Company, KEVIN J. NILSEN
Technology Division, Ceramics & Advanced Materials,
Niagara Falls, NY, The Dow Chemical Company,
USA Midland, MI,
USA
ARNE K. KNUDSEN
Ceramics & Advanced Materials, EMIL PFENDER
The Dow Chemical Company, Department of Mechanical Engineering,
Midland, MI, University of Minnesota,
USA Minneapolis, MN,
USA
TOIVO T. KODAS
Department of Chemical Engineering and SOTIRIS E. PRATSINIS
Center for Micro-engineered Materials, Department of Chemical Engineering,
University of New Mexico, Center for Aerosol Processes,
Albuquerque, NM, University of Cincinnati,
USA Cincinnati, OH,
USA
PETER C. KONG
Idaho National Engineering Laboratory, JAN PUSZYNSKI
Lockheed Idaho Technologies Company, Chemistry and Chemical Engineering,
Idaho Falls, 10, South Dakota School of Mines and
USA Technology,
Rapid City, SO,
WOO Y. LEE USA
Metals and Ceramics Division,
Oak Ridge National Laboratory, WILLIAM RAFANIELLO
Oak Ridge, TN, Ceramics & Advanced Materials,
USA The Dow Chemical Company,
Midland, MI,
JONATHAN LIPOWITZ USA
Advanced Ceramics Program,
Dow Corning Corporation, PETER T.B. SHAFFER
Midland, MI, Consultant,
USA Cumming, GA,
USA
RICHARD A. LOWDEN
Metals and Ceramics Division, FRED V. SHAW
Oak Ridge National Laboratory, Niro, Inc.,
Oak Ridge, TN, Columbia, MD,
USA USA
 Contributors xv
MAKUTESWARA SRINIVASAN SAM C. WEAVER
Materials Solutions International, Inc., Third Millennium Technologies, Inc.,
Grand Island, NY, Knoxville, TN,
USA USA

DAVID P. STINTON
ALAN W. WEIMER
Metals and Ceramics Division,
Ceramics & Advanced Materials,
Oak Ridge National Laboratory,
The Dow Chemical Company,
Oak Ridge, TN,
Midland, MI,
USA
USA
TERRY N. TIEGS
Metals and Ceramics Division, WILLIAM S. WILSON
Oak Ridge National Laboratory, Consultant,
Oak Ridge, TN, Grand Island, NY,
USA USA
Foreword
The potential as materials of some of the large
group of man-made, non-oxide substances -
encompassing carbides, nitrides and borides
- has been recognized for a long time but
their use has been very slow in coming. Fifty
years passed before silicon carbide heaters
and tungsten carbide metal cutting bits, the
two early successes, were followed by other
significant industrial applications of more
materials from this family. The reasons for
this lull are well understood. As they are
man-made, these substances were (with the
exception of SiC) not available or only in
small amounts and in forms unsuitable for
powder processing into materials. Secondly,
techniques for their consolidation into
strong, dense bodies were not yet worked
out and later proved very expensive to
develop. Finally, the thermochemical or ther-
momechanical limits of other, more common
materials have not been reached. It was the
recognition that the design of new advanced
heat engines was running out of material
capabilities, which gave this field in the early
1970s a push and the necessary governmental
support. It generated interest in advanced
ceramics among mechanical engineers,
brought about exciting new challenges for
ceramicists and material engineers and even-
tually spawned the inventions and develop-
ments which made it possible to fabricate
components of extreme complexity and unbe-
lievable tolerances from the most intractable
substances. This was the 'golden age' of the
new ceramic materials.
The advent of non-oxide, covalently bonded
ceramics, substantially expanded the spec-
trum of properties that can be achieved in
materials. They now make possible new appli-
cations and may sometime generate entirely
new technologies. The materials that are the
hardest, most creep resistant, strongest at
high temperatures, most erosion resistant,
and with the highest chemical resistance and
thermal and electrical conductivity are found
among covalently bonded carbides, borides
and nitrides. Polycrystalline silicon carbide,
for instance, exhibits an excellent load-bearing
capacity at 2000 C and is helium tight at
1600C. No other known material comes
close. The use of these materials will certainly
grow; however, the growth will be relatively
slow and evolutionary in nature, because
most of the applications will serve new
developing technologies. Advanced ceramic
compounds turned out generally to be expen-
sive, which reduced their possible role as
substitutes for other more conventional
materials. The outcome of projects that tested
internal combustion engines with silicon
nitride parts demonstrated that costs were a
serious limitation.
Government and company sponsorship of
the field of new ceramics in the past 25 years
was driven by anticipated high-tech military
applications and made possible great strides
in science and technology. The information
that was generated was vast but, unfortu-
nately, much of it was locked up in govern-
ment or proprietary reports that are difficult
or impossible to obtain, making a comprehen-
sive review of the field very much in demand.
It is therefore very fortunate and timely that
Alan Weimer and his co-authors undertook
the difficult task of sorting out the large
amount of information about carbide, nitride
XVlll Foreword
and boride materials and are presenting us
with a monograph, the first one in this field.
The following 25 chapters and appendices
give different perspectives of the subject
discussing physical properties, bonding, ther-
mochemistry, reaction kinetics, synthesis of
powders, films, fibers, platelets, and whiskers
and post-processing, all reflecting the exper-
tise of the authors. For some time to come,
this book will be a great resource for anyone
interested in advanced ceramic materials.
Svante Prochazka
Ballston Lake, NY, 1996
Preface
Many of the advanced ceramics being devel-
oped today are carbide, nitride and boride
materials. These are targeted for applications
in both electronic and structural markets. For
example, materials such as aluminum nitride
(AlN) are targeted for use as a high thermal
conductivity substrate for hybrid and power
circuits and multichip modules, and as a
packaging material for integrated circuits.
Materials, like silicon nitride (Si3 N 4 ), are envi-
sioned for structural applications such as in
automobile and heavy duty truck engines
and in small gas turbine engines for auxiliary
power units. In both cases, the unique proper-
ties of these ceramics (the combination of high
thermal conductivity and electrical insulation
for the case of AIN and the combination of
high temperature oxidation resistance and
strength for Si3 N 4 ) are seen to provide
improved cost/performance advantages over
traditional materials. Other materials, such as
tungsten carbide, are widely used materials in
existing industries. Tungsten carbide (WC)
has superior wear resistance without chipping
and has found widespread usage in the
machinery industry as a hard metal (WC-
Co) for metal cutting and drilling. There is
substantial interest in the development of
finer grained WC materials for more demand-
ing applications such as microdrilling of
printed circuit boards. There is growing inter-
est in other materials such as B4 C, SiC, TiC
and TiB2 as well.
Although there is substantial interest in non-
oxides, no single text has been written specifi-
cally to address methods for the synthesis of
these materials. The need for such a text is
apparent. Carbide, Nitride and Boride Materials
Synthesis and Processing has been written to
fulfill this need. Each chapter has been written
by an expert practicing in the particular subject
area. In attempting to provide as complete a
text as possible, the editor first formulated
the Table of Contents for the text and then
went about the task of finding key contributors
to write the various chapters. Contributors are
affiliated with industry, academia and govern-
ment research facilities, thus providing a
broad perspective of information for the
reader. This text is intended as an overview
of the subject and is suitable for practitioners
in the industry as well as those looking for an
introduction to the field. It will be of interest to
chemical, mechanical and ceramic engineers,
materials scientists and chemists in both uni-
versity and industrial environments working
on or with refractory carbides, nitrides and
borides. The subject matter ranges from
introductory materials properties and appli-
cations to various methods of synthesis
including pre- and post-synthesis processing.
Although most of the text is concerned with
the synthesis of powders, chapters are
included for other materials including whis-
kers, platelets, fibers and coatings. Specific
safety considerations are discussed for each
part of the text.
This book is written in nine parts. Part One
provides an introduction to the carbide, nitride
and boride materials including a review of
their properties and applications (Chapter 1)
and some critical powder characteristics
(Chapter 2) impacting performance. Carbo-
thermal reduction synthesis is reviewed in
Part Two. Initially, a review of the thermo-
chemistry and kinetics (Chapter 3) for these
xx Preface
reactions is given. This is followed by a review
of traditional reactors, including the Acheson
process (Chapter 4) for producing SiC and
electric arc furnace processing (Chapter 5) for
B4 C and other materials. Developmental reac-
tor configurations including moving bed
(Chapter 6), rotary tube (Chapter 7) and fluid-
ized bed (Chapter 8) reactors are reviewed in
additional chapters. Part Three provides a
review of the thermochemistry and kinetics
(Chapter 9) of combustion synthesis reactions
and describes various direct nitridation and
self-propagating high temperature synthesis
(SHS) processes (Chapter 10). Gas phase
synthesis processes are contained in Part
Four. Following a review of the thermochem-
istry and kinetics (Chapter 11) for gas phase
reactions, the text includes chapters on ther-
mal aerosol (Chapter 12), laser (Chapter 13)
and plasma (Chapter 14) driven processes.
Liquid phase reaction processes (Chapter 15)
are reviewed in Part Five. The synthesis of
whiskers and platelets (Chapter 16) and
fibers (Chapter 17) is included as Part Six. Peri-
pheral processing (pre- and post-synthesis) is
the focus of Part Seven. Considerations include
size reduction (Chapter 18), chemical purifica-
tion (Chapter 19) and solids dispersion in
liquids (Chapter 20) for spray drying (Chapter
21). Coatings, films and infiltration processes
are the focus of Part Eight. Chemical vapor
deposition (CYD) with infiltration (CYI)
(Chapter 22) and plasma enhanced chemical
vapor deposition (PECYD) (Chapter 23) are
included. Finally, Part Nine reviews some of
the engineering considerations for high tem-
perature furnace reactors that use SiC, MoSi2 ,
Mo, W or graphite heating elements (Chapter
24). Large scale rotary tube calciners are con-
sidered in Chapter 25. The text also includes
appendices comprising selected property
data for crystallographic, thermodynamic,
thermal, mechanical, electrical, magnetic and
chemical properties of some carbide, nitride
and boride materials.
Alan W. Weimer
Boulder, Colorado
September 1996
E-mail: alan.weimer@colorado.edu
Acknowledgments
I would like to thank those who have sup-
ported me in many ways. My greatest thanks
go to my wife and children, Carol, Michael and
Lauren, who have supported the long hours
and stress associated with this task. I would
also like to thank The Dow Chemical Company
management of Dr Bruce Peters, Dr Robert
Nowak and Mr Alan Hart who understood
the soft issues associated with approving the
concept of this text. A particularly special
thanks goes to Mr Alan Hart who had a
profound impact on the content and timing!
I would like to thank the many reviewers of
chapters. Their comments were well received
and useful for making revisions as work
progressed. Chief among these were Glenn
Eisman, John Henley, Joe Repman, Dan
Howard, Mani Shabrang and Kevin Howard.
Finally, I would like to thank the contri-
butors who had the patience to see it through
and the willingness to revise chapters as
many as three times prior to final acceptance.
Surely, if not for them, there would be no
text.
Alan W. Weimer
Symbols

The more commonly used symbols are v Velocity (m/s)

defined below, shown with their 51 units. x Distance (m)
Other notations are defined within individual X Conversion
chapters.
DoG Gibbs free energy change (J I mol)
a Particle radius (m) DoH Enthalpy change (J/mol)
c Concentration (moUm 3 ) () Diffraction angle, dimensionless
Cp Heat capacity (J Ikg . K) temperature
d Particle diameter (m) Viscosity (kg/m . s)
M
D Diffusion coefficient (m2Is) p Density (kg/m3)
E Elastic (Young's) modulus (GPa)
Ea Activation energy (J I mol)
Vickers hardness (GPa) SUBSCRIPTS
Hv
kB Boltzmann's constant (1.38 x 10-23 JIK) ad Adiabatic
ko Arrhenius pre-exponential factor (s-l) e Effective
KIc Fracture toughness (MPa' m 1/ 2) f Formation
I Length (m) Species index
p Partial pressure (Pa) p Particle
p Pressure (Pa) R Reaction
Re Reynolds number 0 Initial
Rg Ideal gas law constant (8.314 JImol K)
t Time (s)
SUPERSCRIPTS
T Temperature (K)
u Combustion wave front velocity (ml s) 0 Standard conditions
PART ONE
INTRODUCTION
OVERVIEW
Many of the carbide, nitride and boride
materials are of considerable interest for struc-
tural and electronics applications due to their
unique properties including wear resistance
(e.g. WC), high temperature oxidation resis-
tance (e.g. SiC and Si3 N 4 ), high hardness
(e.g. B4 C), high toughness for a ceramic (e.g.
Si3 N 4 ), resistance to attack by molten metals
and glasses (e.g. TiB 2 , BN and AlN) and
unique combinations of properties such as
high thermal conductivity with electrical insu-
lation (e.g. AlN). Their structural applications
have included heat engine components, wear
components, armor, corrosion resistant cruci-
bles and high temperature burners, among
others. Their electronic applications have
included semiconductor processing and
applications for substrates or packaging.
The growth of advanced non-oxide ceramics
can be directly traced to the availability of high
quality powders. High quality is directly
related to the ability to consistently and easily
densify powders into fabricated parts which
exhibit desirable properties approaching the
theoretical limits of the materials. Important
quality characteristics of powders are particle
size and chemical and phase purity which
drastically impact the cost of densification
and the final part properties.
Increased commercial markets for the non-
oxide ceramic materials will be impacted
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
most significantly by improvements in cost/
performance over conventional materials. In
many cases, the competition for advanced
non-oxide ceramics is metallic superalloys or,
in the case of electronic applications, modifica-
tions in architecture (e.g. heat transfer fins or
the addition of fans for convective cooling
instead of changes to more thermally conduc-
tive substrate or packaging materials). Some
market applications are driven solely by the
need for a material which can operate under
extreme conditions where other materials
cannot, thus extending the range of applic-
ability.
Part One begins (Chapter 1) with a short
review of the origins, current status and
market trends for carbide, nitride and boride
materials. The properties which make certain
carbides, nitrides and borides useful are
reviewed relative to their applications. The
standard methods for part fabrication are
included. This is followed by a review of
critical powder characteristics (Chapter 2) for
some of the primary non-oxides of consider-
able interest: tungsten carbide (WC), silicon
carbide (SiC), silicon nitride (Si3 N 4 ) and alu-
minum nitride (AIN). Specifics here include
particle size distribution and phase and
chemical purity for each of these ceramics.
Also included is the development of sintering
technology, such as sintering additives for
achieving theoretical densification by pres-
sureless sintering.
2 Introduction
SAFETY ISSUES
Information contained in available Materials
Safety Data Sheets (MSDS) needs to be read,
understood and followed prior to production
or handling of a particular material. In the
United States, MSDS are packaged with all
products and are readily available from sup-
pliers. They contain information regarding
proper handling, reactivity, toxicity, how to
clean up spills or respond to emergency situa-
tions, and methods of disposal.
Ultrafine non-oxide ceramic powders have
the potential of being respirable. The guide-
lines recommended in the MSDS should be
followed, including the recommended type
of personal dust filters. Some powders may
be potentially more harmful than others and
need to be handled as such, possibly including
the use of the more expensive personal HEPA
(high efficiency particulate air filters) car-
tridge filters which are suitable for radioactive
nuclides. The allowable concentrations of the
dusts in air need to be noted and appropriate
measures taken to protect personnel in the
handling of these fine powders.
Some fine powders can be pyrophoric if
they are processed in inert environments and
then exposed to air during handling. In parti-
cular, the handling of ultrafine WC, especially
any milling operations which expose fresh
surfaces, may be potentially hazardous due
to the pyrophoric nature of this material.
Similar considerations need to be made for
fine titanium carbide (TiC) powders, among
others. Any processing of a pyrophoric
powder in a flammable solvent, such as the
processing of fine WC in acetone, cyclohexane
or other flammable organic solvent requires
special attention to prevent oxidation of
exposed powder surfaces.
Some fine powders, such as AlN, are water
reactive and will hydrolyze, releasing large
volumes of gas. In the particular case of fine
AIN powders, large volumes of NH3 will be
released. The AIN-H 20 reaction is highly pH
sensitive and may take many hours to achieve
a point after which the reaction proceeds
rapidly. Special precautions need to be taken
relative to waste disposal and machining. For
example, the saw blades used to cut an AIN tile
should never be cooled with a water spray.
Such practice will result in a boiling water
reservoir with NH3 release. Instead, a non-
reactive compatible heat transfer medium,
not water, needs to be used.
Each non-oxide powder will need to be con-
sidered separately. They will have unique
safety considerations regarding toxicity or
reactivity. Special safety issues for non-oxide
whiskers and fibers are discussed in Part Six.
Additional safety issues regarding methods
of synthesis are included in the appropriate
parts of the text.
NON-OXIDE MATERIALS:
APPLICATIONS AND ENGINEERING
Makuteswara Srinivasan and William Rafaniello
INTRODUCTION
The advanced ceramics of yesteryear, speci-
fically the non-oxide materials, have become
fully commercialized in several applications
where long life, improved performance,
unique design capability and cost advantages
have been explicitly utilized. Exploiting the
advantages of their unique properties com-
bined with the availability of complex
shapes, several industries such as mining
and metallurgical, paper and pulp, com-
modity and specialty chemicals, mechanical
machinery, food processing, electronics, semi-
conductor processing, aerospace, defense and
medical device manufacturing have dis-
covered the unique benefits of these technical
ceramics (RCG/Hagler, Bailly, Inc., 1990;
Schwartz, 1992). The promise of advanced
ceramics had been limited by the availability
of high quality, cost-effective powders, the
lack of reliable manufacturing technology
and the inability of engineers to design with
brittle materials. While progress is being
made on reducing actual and projected costs
for non-oxide ceramics, the latter two issues
have been satisfactorily overcome and
should no longer be impediments to the use
of advanced ceramics.
While overviews of the art and science of
advanced ceramics have been written
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
1
(Schwartz, 1992; ASM International, 1991),
specific details with respect to manufacturing
technologies remain sparse in the open
literature. Despite this vacuum of information,
substantial progress is still very much appar-
ent. The global nature of this competitive
business has helped spur the advancement
in manufacturing technologies. Equipment
manufacturers have specialized in building
equipment using advanced microprocessor-
based control technology in grinding mills,
blenders and mixers, spray dryers, compac-
tion presses, dryers and solvent removal
equipment, and special high temperature
controlled atmosphere furnaces including
very high temperature isostatic pressing.
Associated with this technology, novel in-
process quality assurance equipment has
been created utilizing the general principles
of x-ray radiography, ultrasonics, nuclear
magnetic resonance imaging and thermal
wave imaging. Post-fired materials can be pre-
cision machined to high tolerances using CNC
lathes and surface grinders. High quality
inspection machinery and well-established
procedures are also currently available.
For the users of advanced ceramics, a
detailed knowledge base is now available
with respect to the perennial question of
their brittle behavior. Thanks to the con-
tributions of many investigators, questions
4 Non-oxide materials: applications and engineering
regarding the reliability of ceramics can now
be handled with greater certainty using prob-
abilistic design methodology and advanced
fracture mechanics considerations which can
predict the useful life of components that are
subjected to crack growth under operational
conditions.
In this chapter, the non-oxide advanced
ceramics will be considered by their type,
chemical nature and functionality. Some
general manufacturing considerations will
also be described. Some of the technology
advancements that have led directly to early
commercialization of specific engineered
components will also be discussed. It is
recognized that selected oxide ceramics such
as partially stabilized zirconia and high per-
formance alumina and magnesia can also be
considered in the family of advanced
ceramics. However, these will be discussed
only as necessary for comparative purposes.
Of the non-oxide ceramics, only the predomi-
nant borides, carbides and nitrides will be
discussed.
ADVANCED CERAMICS - ORIGIN,
CURRENT STATUS, TRENDS
In order to better understand advanced
ceramics in terms of their competitive position
and utilization, we need to understand their
ongm. Advanced ceramics compete with
metals and alloys in applications involving
highly hostile environments that require
corrosion and high temperature resistance,
Le. in excess of 1173 K (900C). Additionally,
because of their high hardness and relatively
high elastic modulus, they also find utility in
high wear applications.
The useful life of metallic alloys can be
extended through the use of refractory coat-
ings. These ceramic coatings can be applied
using one of several techniques such as
simple flame spraying, plasma spraying,
high pressure jet coating, physical vapor
deposition and chemical vapor deposition.
Other surface modification technologies that
extend the life of the metallic surfaces
exposed to friction and wear, with or without
corrosion, include various ion beam surface
modification techniques in which suitable
ions are implanted on the metallic surfaces
thereby changing the surface chemistry and
the associated mechanical properties. How-
ever, in many situations, coatings offer only
a temporary resolution to the problem at
hand. The most single disadvantage with
the various coatings is their lack of adherence
to the substrate materiaL During service, the
coatings generally get degraded with the for-
mation of pinholes through which various
reaction components in the application can
diffuse and cause degradation of the sub-
strate. Also, the coatings tend to peel off
locally, limiting the eventual useful life of
the component. Another consideration,
depending on the application, is the repeated
exposure to thermal gradients which also
contributes to the thermal shock failure of
the coatings. While coatings offer measurable
benefits above the baseline, higher perform-
ing materials are needed.
ORIGINS OF ADVANCED CERAMICS
The definition of advanced ceramics has been
vague for many years. Confusing the issue
are the additional terms such as 'engineered'
ceramics, 'technical' ceramics and 'fine'
ceramics. Some are even called 'functional'
ceramics. A simple way to distinguish them
is to remind ourselves of what are considered
'classical' ceramics. The classical ceramics, in
general, are the clay-based ceramics which
have found more common use as electrical
insulators, whitewares used for plumbing
and china. Aluminum oxide and the other
specialty oxide ceramics such as the titanates
and the ferrites should also be considered as
advanced ceramics and the forerunners of the
newer non-oxide base materials.
The oxide ceramics mentioned above can be
manufactured with relatively inexpensive raw
materials leading to their widespread usage.
 Advanced ceramics - origin, current status, trends
The knowledge gained in making components
from them, such as setting specifications for
raw materials, their storage and handling,
powder granulation methods, compaction
and sintering technology, machining and
packing is very useful in setting the trend for
judicious investigation of these important
variables in the manufacture of the current
advanced ceramics.
RECENT STATUS
From a commercialization viewpoint, the
state of advanced ceramics is very much
application dependent. Traditional wear and
corrosion resistant applications are part of
mature businesses, while heat engine compo-
nents are at various stages of emergence.
These ceramics have been very selectively
introduced, primarily in Japan, into auto-
mobiles and heavy duty trucks. Their use, on
a regular basis, in extremely severe appli-
cations such as gas turbine engines is still
under development. Inevitably, practical use
limits are reached for existing materials and
innovation is required to meet more demand-
ing applications.
There are several classifications of advanced
ceramics, depending on their type, chemical
constituents and usage (functionality). In
terms of their chemical nature, they can be
classified broadly into oxides and non-
oxides. The most popular oxide ceramics
such as alumina and zirconia compete with
non-oxides in many applications. At present,
alumina captures the largest market share in
wear resistant applications. Because of their
unique characteristics and broad commercial
potential, the non-oxides such as the carbides,
nitrides and borides have been and continue
to be the most researched ceramic materials
since 1970.
In terms of their functionality, they can be
classified broadly into electronic ceramics
and structural ceramics. Until now, the elec-
tronics ceramics market has grown at a
much faster rate than the structural ceramics
5
market. However, many market forecasts
have and continue to predict a substantial
growth rate for structural ceramics. However,
these projections have yet to be realized and
electronic ceramics continue to dominate
advanced ceramic markets. Except for some
isolated cases that will be addressed later,
non-oxide ceramics are being primarily con-
sidered for structural applications due to
their wear characteristics, corrosion resistance
and high temperature properties.
MONOLITHIC CERAMICS
The term monolithic ceramics is applied to
those ceramics that are not, in general, compo-
sites. However, this definition is not entirely
accurate. Composites are materials containing
more than two constituents (phases), each
with appreciable amounts (for example,
greater about 5-10vol.%). Many of the so-
called monolithic ceramics have substantial
amounts of additives to help them achieve
full density during fabrication. Silicon nitrides
(Si3 N 4 ), for example, can have 15-20% total
additives in the finished ceramic. However,
in monolithic ceramics, the interface chemis-
try as well as the nature of mechanical and
chemical bonding established between the
two phases can be quite different from that
obtained in ceramic composites.
As mentioned before, there are a variety
of non-oxide advanced ceramics that are
broadly classified into carbides, borides and
nitrides. Many of the materials that are
commercially available in each of these
categories will be considered separately. This
description will be by no means inclusive.
Many materials are still under development
at various laboratories and cannot be con-
sidered here. Typical properties of the most
common non-oxide ceramics are summarized
in Table 1.1. The values shown in this table are
for the most part representative of high
density relatively pure materials. For a more
complete material and property listing see
the Appendices.
Table 1.1 Properties of common non-oxide ceramics

Physical Thermal Electrical and magnetic Mechanical

Specific Melting or Linear Conduc- Electrical Magnetic Elastic Poisson's Micro- Bend Compressive Fracture
gravity Pth dissociation expansion tivity k resistivity P suscepti- modulus ratio hardness strength strength toughness
(kg/rrf x 10-3 ) (d) tempera- coefficient (W/mK) (xl08 0 hmom) bility E(CPa) v at iN rItrs ac K 1c
ture (K) (300-1300 K) (xl0 6 ) load (MPa) (CPa) (MPa.m 1 / 2 )
a (10- 6 /K) x (1/mol) Hv (CPa)

AlN 3.26 2572(d) 5.0 180.0 >1019 320 0.25 15.3 320 3.8 2.8
B4C 2.52 2743 5.54 28.0 1000.0 427 0.19 31.5 340 6.6 3.2
BN 2.28 2600(d) 2.0 15.0 1.7 x 10 19 60 0.1 20 0.3 16.0
SiC 3.21 3103(d) 5.12 41.0 4 x 105 408 0.14 30.0 350 6.3 3.9
Si3N4 3.18 2151(d) 2.6 29.5 >1019 315 0.27 15.0 800 4.4 6.0
TiB2 4.52 3193 4.6 24.0 9.0 31.3 541 0.11 25.5 450 5.7 6.4
TiC 4.92 3290 7.95 17.2 200.0 5.0 494 0.19 30.0 500 1.4 2.0
TiN 5.44 3223 8.7 28.9 40.0 37.0 390 19.9 260 1.3
WC 15.8 3073(d) 5.76 29.3 19.2 9.8 737 0.24 30.0 530 4.3 6.0
 Advanced ceramics - origin, current status, trends 7
The nitrides Having the wurtzite structure and being
made up of relatively light elements, it was
The nitrides are the earliest of the current
predicted and experimentally verified that
advanced materials. Hot-pressed boron nitride
AIN should have a high thermal conductivity
(BN) has been well known and widely used for
value. The combination of high thermal con-
electrical applications as well as for crucibles
ductivity, high electrical resistivity, good
for molten metals etc. However, silicon nitride
dielectric properties and a linear thermal
(Si3N 4) has attracted the most attention as a
expansion coefficient that closely matches
structural ceramic, making inroads into auto-
silicon makes AlN an exciting ceramic
motive applications. Recent innovations have
material for electronic applications (Disson
focused on aluminum nitride (AlN) ceramics
and Bachelard, 1991). To achieve high sintered
as an electronic substrate material as well as a
densities and the desired electrical and
substitution for beryllia in thermal manage-
thermal characteristics, sintering additives
ment applications. Titanium nitride (TiN), as
selected from rare and alkaline earth com-
a physical vapor deposition (PVD) coating, is
pounds are necessary. For example, yttria,
very useful in providing improved tool perfor-
calcium oxide, yttrium fluoride and calcium
mance. It offers a higher hardness surface that
fluoride are often used (Sheppard, 1990).
is abrasion resistant and has a lower coefficient
Another unique characteristic of AlN
of friction. It also offers excellent resistance to
relative to other non-oxide ceramics is its
most common industrial acids and alkali.
elastic-perfectly plastic behavior under high
Like the other non-oxide materials, the
pressure loading conditions. This property
nitrides are predominantly covalent solids.
led to significant exploration of AlN as a
However, one distinction is that they tend to
high performance armor material. The refrac-
dissociate at elevated temperatures to nitro-
toriness of AlN provides additional opportu-
gen gas and the respective metal. For the
nities in structural applications. Since AIN is
common nitrides, the equilibrium dissociation
wet but is not eroded away by molten alumi-
temperature increases from Si3N4 to AlN to
num and is also largely unaffected by molten
BN. As expected, these temperatures can be
ferrous alloys, it is an excellent crucible and
increased with modest increases in nitrogen
gate material for molten metals.
pressure for closed systems. This behavior
has important ramifications in the synthesis
and densification of this important class of Boron nitride (BN)
non-oxide materials.
Boron nitride (BN) is isostructural with carbon
and exists in several crystallographic orien-
tations. Similar to carbon, the three most
Aluminum nitride (A IN)
common forms are amorphous, hexagonal
Aluminum nitride (AlN) is the most recent (graphite-like) and cubic (diamond-like). The
entrant into the advanced ceramics arena. cubic BN is a unique material with hardness
Relative to most of the other commercially close to that of diamond. It resists oxidation
important non-oxides, AlN's wurtzite struc- and does not react with iron and its alloys at
ture has significantly greater ionic bond char- temperatures of 1373-1573 K (1100-1300 DC). It
acter. This feature provides both benefits and is thus suitable for grinding high speed steel,
limitations. The weaker atomic bonding or cast iron or nickel or cobalt-based alloys
allows for higher diffusion rates and hence that cannot be ground by diamond. Also, the
better sinterability. However, from a mechan- cubic BN has thermal conductivity higher
ical property perspective, AlN has only mod- than that of copper and therefore can be
erate hardness and modulus values. used as a heatsink in electrical and electronic
8 Non-oxide materials: applications and engineering
applications. The cubic BN is usually made by At ordinary pressures, Si3N4 has no melting
processing hexagonal BN at super high pres- point, but dissociates into its elements at
sures and temperatures with a catalyst pre- fairly modest temperatures, about 1773 K
sent. The typical catalysts are alkaline metal, (1500C). Despite this relative instability, its
alkaline earth metal and their nitrides. As an diffusion coefficients are very low. Because
example, magnesium BN has been used to of these intrinsic characteristics, sintering
make a sintered cubic BN at pressures to Si3N4 is extremely difficult. Several processes
5 GPa (7.25 x 105 psi) and a temperature of have been developed to manufacture Si3N4
1523 K (1250C). A hardness of 60 to 65 GPa ceramics. Since these manufacturing methods
(8.7-9.4 x 106 psi) and a thermal conductivity strongly influence the properties of the fin-
of up to 600 W / m . K have been reported ished ceramic, it is important that these
(Ota, Sumiya and Yazu, 1987). Due to the pro- products be distinguished. In addition, each
cessing extremes needed for preparing cubic / research group has developed specific sinter-
BN, commercial opportunities are limited. ing formulations and schedules that also have
Boron nitride (BN), in the graphitic form, a profound influence on the performance
except for its high electrical resistivity, has a envelope for Si3N4 ceramics. There are, as
property envelope that is very similar to gra- yet, no standards in place that would simplify
phite. Because of this, it finds application as the engineering materials selection process.
a high temperature insulator and a solid The range of mechanical properties available
lubricant, and in containment. Several grades with Si3N4 ceramics is shown in Table 1.2.
of solid BN exist, including a high density, The version of Si3N4 that has probably
pyrolytic form that is used as boats and received the most attention was made by hot
crucibles in the semiconductor industry. It is pressing Si3N4 powders with MgO additions.
particularly valuable in those metal and This material was produced throughout most
ceramic processing situations where reducing of the 1970s and 1980s by Norton Company
environments from carbon furnacing would under the designation NC-132. It is a fully
be detrimental. Because of its stability in dense material that found tremendous accept-
molten glass and metal environments, BN is ance as a high temperature bearing material.
highly effective as a refractory coating as Typically, in industrial manufacture, ex-Si3N4
well. powders with additives such as MgO, Y20 3,
Zr02, Ce02 and SiBeN2 to promote densifi-
cation are used. The powder mixtures are
hot pressed at temperatures in excess of
Silicon nitride (Si3N 4) is a strongly covalent 2023 K (1750C) with applied pressures of
solid that exists in two hexagonal crystallo- 20-30 MPa (3000-5000 psi) for times up to 2 h.
graphic orientations. Both structures are Pressureless sintering of Si3N4 is possible
close packed arrays with tetrahedral coordina- because of the formation of a liquid phase by
tion that differ only by their stacking the additives used in the formulation. Numer-
sequence. The alpha (ex) or low temperature ous additives have been found for Si3N4 that
form has large openings that can accommo- allow full densification. Much effort was
date cations and allow for substantial alloying. directed to the modification of the chemistry
Beta (3) Si3N4 is the high temperature form and the volume of the liquid phase so that
and allows only limited solubility of other sintering can be achieved at moderate tem-
elements. Understanding and controlling the peratures while at the same time retaining
Si3N4 phase chemistry is critical to achieving desirable elevated-temperature mechanical
the desired microstructures and properties of strength and creep resistance. A notable out-
the finished ceramic. come of these research efforts is the discovery
Table 1.2 Reported properties for several silicon nitride ceramics

Densification methoda Density Porosity Flexure strength (MPa) Weibull Elastic Poisson's Toughness Coefficient of Thermal
(kg/m3 ) (vol.%) modulus modulus ratio at (KIc ) thermal conductivity
at293K 293K 1273K 1673K at 293 K (E) (CPa) 293K (MPa.m 1/ 2 ) expansion (W/mK)
at293K at 293K (10-6/K) at 293-
at 293- 1273K
1273K

HPSN,b 1%MgO 3190 <0.1 725 600 290 11 315 0.26 6.5 3.0 35 15
HPSN,b 13% Y203 3420 <0.1 735 770 605 10 310 0.26 6.5 3.2 30 10
RBSNb 2600 18.0 265 265 320 15 220 0.27 2.0 2.8 6 3
SSN,b 8% Y20 3,
l%MgO 3260 2.0 600 550 130 9.3 280 0.25 5.0 3.2 30 10
GPSN,c 9% Y20 3,
3% Al20 3 0.9 1400 900 19 300 9.0 2.4 26 10
HIPSN,d with MgO 3160 <0.1 800 320 5.0 2.9 29.3
GPSN,ewith MgO,
Y20 3,AlN 3200 1600 1100 20 320 6.2 2.7 52
HPSN/ with Y20 3,
MgO,CaO 3250 1100 890 270 14 314 0.27 8.5 31

a HPSN, hot-pressed silicon nitride; RBSN, reaction-bonded silicon nitride; HIPSN, hot-isostatically pressed silicon nitride; SSN, pressureless-sintered silicon
nitride; GPS, gas-pressure-sintered silicon nitride.
b Gellner, Schwetz and Lipp (1983).
C Riedel and Kruner (1993).

d Norton Product literature, NBD 200.

e Nishioka et al. (1992); Yamamoto et al. (1992).
f Pyzik, Carroll and Hwang (1992).
10 Non-oxide materials: applications and engineering
of a new range of materials in which the Si3N4
was alloyed with Al and 0 from additives,
known generically as 'sialons' (Oyama and
Kamigaito, 1971; Jack and Wilson, 1972).
Although termed 'pressureless' sintering, a
slight over-pressure of nitrogen is commonly
used in manufacturing to prevent the decom-
position of Si3N4 during sintering. Recent
advances using gas pressure sintering tech-
niques (GPS) have yielded superior Si3N4
test coupons (Erauw, Gilissen and Sleurs,
1994) as well as turbochargers for automobiles
(Katayamam, Watanabe and Matoba, 1986).
Virtually pore-free silicon nitride components
with very high reliability (Weibull modulus
greater than 40) have been produced by this
method.
Silicon nitrides have been developed with
unique microstructures containing needle-
like grains dispersed in a matrix comprising
equiaxed grains. The objective is to provide a
mechanism for dispersing the crack propa-
gation energy of an advancing crack to either
arrest, deflect or channel the crack direction
away from the main front (perpendicular to
the axis of the applied stress) so that brittle
fracture is postponed. The application of
such techniques to increase fracture tough-
ness, though not uncommon, requires careful
control of the microstructure development
through a rather narrow processing window,
especially for complex-shaped objects.
A novel method reported by Sullivan (1990)
used supercritical temperatures and pressures
to produce net-shape Si3N4 components for use
in the automotive industry. The process uses
ceramic compounds from a liquid (organome-
tallic precursors) rather than a powder by com-
bining silicon, carbon, hydrogen and chlorine
and allowing the solution to react with nitro-
gen. The ceramic parts are injection molded at
a maximum temperature of 973 K (700C).
They are then heat treated at 1483-1773K
(1200-1500C) for 10min. It has been claimed
that the process can produce automotive com-
ponents made of Si3N4 at costs comparable to
metal assemblies (Brooks, 1990).
Reaction-bonded Si3N4 (RBSN) utilizes a
chemical reaction during forming. Metallic
silicon (SO powders are first green compacted
with binders and additives, and then sub-
sequently nitrided. Because the nitriding
reaction is exothermic, controlled nitridation
was developed by Mangels (1981) in which
the nitriding reaction starts around 1273 K
(1000C) and is completed at about 1573 K
(1300C). The nitrogen demand depends
upon furnace load and the kinetics of the nitri-
dation reaction. Success was demonstrated by
devising a nitrogen demand cycle system
incorporating the furnace variables. In this
process, the reactants were allowed to control
the reaction rate through a rate-controlled
nitriding process.
The carbides
The carbides of tungsten, boron, silicon,
titanium and tantalum have been used for a
variety of applications over the years. In
general, they are very hard and possess
excellent wear resistance as well as oxidation
resistance. Powder green forming technolo-
gies are usually employed in manufacturing
engineered products of these materials.
Tungsten carbide (We)
Tungsten carbide (WC) is perhaps the earliest
of the non-oxide ceramic materials that found
widespread usage, primarily in the machinery
industry as a hard metal for metal cutting
and drilling (Prakash, 1995). While WC is
extremely hard and for a ceramic, relatively
tough, most of the WC-based products are
actually metal-ceramic composites. These are
prepared using powder metallurgy methods.
Typically, finely divided hard carbide
particles are sintered with one or more
metals of the iron group (Fe, Ni or Co), usually
cobalt. The carbides are present as individual
grains, and also as a finely dispersed network
resulting from the precipitation during
cooling, of carbide dissolved in cobalt during
 , 'n , current status, trends
Advanced cera mics - ongl 11
8

ti 5
Il.
~
.s:::.
0,

-
c:
....Q)
en

Transverse Rupture, <JTRS

15 20 25 30
10CObait (weight %)

20 25

.:::::In!nU!in

. n:miWii'iiiiii!iiiiii!)/

--~~,~
!i!!i!J"

L..
o "-----'--"-..........
hard metal ~~~"""""~~~~~"r'IT
- - compo sitions showmg
'
0
enormous range
available to

Figu 1.1 7=~:"'. comm~dal. of

(Adapted from B
~k"" 1992.)
h:~e iversal benefits lo~
engI:~';;a~ o~i
he measured
hard metal

m~ta
d",ignen;an . I 1%1). There ar.. e':es, the applications has
M Internaltona, I compo"- p P itions lor sp

numerous c~:.:b~
sintering (AS mercia! hard of these
1992). properhescontrolling
~Tnder ~~~onal I~r
compos ensive.

~dde
been uses th:
we hard metals
blades, r~lls
~or
n
lions. (Broo tailored largel; phase. . bearings, dl"':, hear
tools. The supe,:,or
g nd
matenals
ram hSIzec: , the amount
Figure 1.1,0 the 'drange 01
How- mc
and ingtance
g, and extru",:
witho chipping dunng
As s own m'1 ble is ex!rem ely WI e,do not we
Properties ava~ a tructural changes ar reSIS
' e mIcros
ever, Sinc
12 Non-oxide materials: applications and engineering

Figure 1.2 Typical products manufactured from hard metals. (Photo courtesy of Kennametal Inc.,
Latrobe, P A.)

application combined with long life has made Boron carbide (B 4 C)

this important material a workhorse material
in industry. Although used in the chemical
processing industry as a sealing material, the
corrosion resistance in selected applications
needs improvement since the cobalt phase in
the carbide reacts with several chemicals and
gets washed away, leaving the brittle skeleton
of WC particles to be eroded away during
service. Many of the types of hard metal
products are shown in Figure 1.2.
Boron carbide ranks next to diamond in its
hardness. Its properties typify the strongly
covalent non-oxide ceramics. While the B/C
ratio can range to significantly higher values,
B4 C is the compound normally considered
when referring to boron carbide. The B-C
phase system is shown in Figure 1.3. The crys-
tal structure for B4C (B 12 C3 ) is still somewhat
controversial, since there is not a general
 Advanced ceramics - origin, current status, trends 13

2800

-
2600
Q'

-...
~
::l
CIl
Q)
Co
I
I
I

E I
{Eo
2400

2200

o 6 12 18 24 30 36
B Atomic % C ......
Figure 1.3 Boron-carbon phase system. (Beauvy, J., 'System B-C, solid state phase equilibria,' f. Less-
Common Metals, 90(2), 169-75, 1983. Reprinted by kind permission from Elsevier Science SA, Lausanne,
Switzerland.)

acceptance for the location of the three carbon
atoms that make up the unit cell. The B atoms
are arranged in two dodecahedron cages that
are connected by three atoms. Carbon is
thought to make up at least two of the three
connecting atoms. However, the location of
the third C atom is still uncertain. From lattice
parameter measurements, it is known that C
can be reduced continuously until the B13 C2
stoichiometry is reached, without changing
the crystal structure. As shown in Figure 1.4,
controlling the B/C ratio is important for
achieving the maximum benefit with boron
carbide ceramics. Hardness is maximized at
the stoichiometric ratio of 4, while higher B
materials are preferred when EMF (electro-
motive force) is the property of interest. In
addition to performance considerations, pro-
cessability must also be addressed when
specifying the B/C ratio of the starting
powders.
Unlike most of the other non-oxide ceramics
being considered, B4 C can be densified with-
out the use of sintering additives. It can be
manufactured to full densities by either
pressureless sintering or hot pressing. The
14 Non-oxide materials: applications and engineering

50

";'
D.
~ 45
>
J:
iii
III
CII
c:
'EIII 40
:I:
...CII
III

.!IO:
0
:> 35

Boron/Carbon Ratio
Figure 1.4 The effect of B/C ratio on the hardness of boron carbide ceramics. (Niihara, K., Nakahira, A.
and Hirai, T., 'The effect of stoichiometry on mechanical properties of boron carbide,' J. Am. Ceram. Soc.,
67(1), C13-14, 1984. Reprinted by permission of the American Ceramic Society, Westerville, OH.)

sintering is usually carried out at tempera-
tures below 2473-2523 K (2200-2250C)
above which peritectic decomposition occurs
with the formation of boron and a liquid
phase rich in carbon (Kuzenkova et al., 1980).
For successful pressureless sintering, usually
the addition of carbon is required. Schwetz
and Vogt (1980) have sintered B4 C with 0.1
to 8.0 wt% of free carbon in the form of
graphite.
The combination of high hardness and low
specific gravity has made B4 C an ideal can-
didate for lightweight armor. The natural pre-
sence of the lOB isotope makes it valuable as a
neutron absorber in nuclear reactors. Boron
carbide has been studied for space power
generation, due to its ability to generate an
electromotive force (EMF) with the presence
of thermal gradients (Koumoto, 1994). Since
this effect increases with temperature, B4 C
has also been used as a high temperature
thermocouple. Its exceptional wear resistance,
particularly in erosion, has led to a number of
industrial applications.
Silicon carbide (SiC)
Among the various non-oxide ceramics that
have found commercial applications, silicon
carbide (SiC) is the leader. The attractive
properties - such as good specific strength
and Young's modulus as a function of tem-
perature, the specific stiffness, relatively low
weight, corrosion and erosion resistance and,
most of all, easy availability in complex engi-
neering shapes - have made SiC an attractive
alternative to the hard metal compositions.
Compared to Si3 N 4 , the raw materials to
make SiC are relatively inexpensive and there-
fore the final products are cost-competitive,
besides offering technical performance advan-
tage. While the opportunities for SiC ceramics
 Advanced ceramics - origin, current status, trends
are significant, its use as an abrasive grit is the
commercial driving force.
Depending on the synthesis temperature,
SiC can be prepared with several crystallo-
graphic orientations. Low temperature reac-
tions usually lead to the formation of ,B-SiC
This has a cubic or zincblende crystal struc-
ture. Higher temperature processes, which
are more prevalent, form one or more hexago-
nal modifications. These modifications, which
differ only by the position of the atomic layers,
are referred to as a-SiC
The fabrication of SiC via hot pressing at
temperatures greater than 2273 K (2000C) has
been practiced for a long time in the ceramic
industry, primarily using aluminum and simi-
lar elements as hot pressing aids. However, the
earliest use of shapes was in the form of a
silicon-SiC composite made by the reaction-
sintering or reaction-bonding process (RBSC).
Typically, the SiC grains are mixed with carbon
in various forms and the mixture heated in
contact with molten silicon. The term reaction
sintering arises from the reaction between car-
bon and silicon to form SiC The carbon used in
the process is converted to new SiC which
bonds to the original SiC particles.
The widespread use of SiC for structural
applications became a reality when pressure-
less densification methodology was discov-
ered in the early 1970s. Both ,B (Prochazka,
1974) and a (Coppola and McMurtry, 1976)
forms could be sintered to very high densities
by using boron and carbon additions in var-
ious forms. The fact that aluminum and its
compounds can also be used for densification
was demonstrated in Europe (Boecker, Land-
fermann and Hausner, 1979; Schwetz and
Lipp, 1979). In the 1980s, more discoveries
were made in using transition elements and
compounds to help pressureless sintering of
SiCs, primarily in Japan.
The borides
The borides of titanium and zirconium are
useful mostly as additives to carbides to
15
enhance their fracture resistance. Hot pressed
titanium diboride (TiB 2 ) has been used for
many years for a variety of applications
involving molten metals such as metallization
boats for evaporative loading of aluminum.
CERAMIC COMPOSITES
Ceramic matrix composites are being devel-
oped with the primary objective to overcome
the brittle fracture of monolithic ceramics.
Depending upon the nature of the reinforce-
ments, they are variously classified as particu-
late-, whisker-, platelet-, chopped-fiber- and
continuous-fiber-reinforced composites. The
actual manufacture and commercialization of
these materials are at varying stages depend-
ing upon the particular system(s).
One of the earliest developments to use SiC
continuous fibers in an SiC matrix resulted in
significant improvement in fracture resistance
(Lamicq et ai., 1986). Limitations to the
development of these high performance non-
oxide composites for commercial applications
have been (1) the lack of suitable high tem-
perature fibers and (2) the fabrication tech-
nology. With the development of fibrous SiC,
aluminum borosilicate, alumina, Si3 N 4 , carbon
and mullite, continuous-fiber reinforcement of
ceramic matrices can now be realized (Karnitz,
Craig and Richlen, 1991).
MANUFACTURING
Next, in a very general fashion, manufacturing
considerations involving non-oxide ceramics
will be addressed. Since the densification of
these materials is often difficult and extraordin-
ary measures are commonly applied, it is
important that the reader has an understand-
ing of some of these methods. The critical
aspects of the raw material powder manufac-
ture are elegantly detailed in the various
chapters of this text and will not be considered
here. It has been assumed that one begins with
highly characterized and well qualified raw
material powders and processing aids.
16 Non-oxide materials: applications and engineering
Green forming of monolithic ceramics temperatures in excess of 1873 K (1600C).
Typically, controlled atmosphere furnaces
The monolithic ceramics are most commonly
without any oxygen are used. The prevailing
manufac.t~red in the green (pre-fired) state by
gases may be inert, such as argon or helium
the tradItIonal dry-pressing and slip-casting
or. nitrogen. They have been highly purified
methods. However, because of the very
WIthout any traces of oxygen. The furnace
demanding products of complex shapes,
walls .typically would consist of high purity
?ther methods such as 'cold' isostatic press-
graphIte; the heating is generally accom-
mg, extrusion, injection molding, transfer
pl~shed us~ng electrical resistance heating
molding and gel casting can also be chosen.
WIth graphIte heating elements (Chapter 24).
To ac~ieve g~~ater homogeneity, uniformity
In addition to the prevention of oxidation of
and smterabIhty to full density the raw
the ceramic during sintering which retards
material powder constituents, in general,
densification, the graphite furniture on which
have well-controlled chemistry and geome-
the furnace ware is loaded as well as the
try. They usually have average particle size
heating elements and the furnace wall need
of less than 1 /-Lm and surface areas in excess
to be p:otected from any trace of oxygen.
of 5-15 m 2 / g. The surface chemistry of the
~ependmg upon furnace loading and the
granules, their shape and size distribution,
SIze of the furnace, heating, hold and cooling
and the type and the amount of binder
cycles are carefully established to obtain com-
used, are very influential in obtaining maxi-
po.nents of high density. Because of the pro-
mum green density under typical green pro-
pnet~ry nature of additives used and green
cessing conditions.
formmg methods and the variations in com-
Methods that utilize very little organic
ponent shapes, amounts, loading sequence
binders are preferable to those that use
etc. the furnacing techniques established are
larger quantities of binders. This is due to
highly local; generalities are usually not
the requirement of careful binder removal
useful.
te~hnique~ . that will insure crack-free parts
To achieve optimum properties, some
pno~ to fmng. Additionally, larger amounts
materials, especially the nitrides, require
of. bmders lead to higher shrinkage in firing
pressure to assist densification. This is
WIth resultant warpage requiring a high
because of the evaporation of the constituent
degree of control in sintering. It should be
materials at high temperatures. In such
realized, however, that certain parts, due to
cases, multi-stage densification has been
their sh~pe cha~acteristics, can be made only
invented that consists of densification at
~y plastIc-formmg techniques such as injec-
some moderate nitrogen over-pressures,
tIon molding requiring larger amounts of
~O MPa (145 psi) at two different temperatures
organics in the mix. The manufacturing tech-
m sequence.
nology is quite advanced and complex parts
are being made with greater dimensional
accuracy with higher yields using injection Pressure densification techniques
molding.
The c?mplete densification or sintering of
ceramICS that are hard to densify in a pressure-
less mode can be achieved by the application
Low or pressureless densification
of pressure simultaneous with high tempera-
techniques
tures. Usually this method yields better suc-
The firing of non-oxide monolithic ceramics cess t~an the pressureless sintering technique
is usually performed either in periodic or and IS the method employed for initial
continuous furnacing kilns (Chapter 24) at exploration in new materials development.
 Advanced ceramics - origin, current status, trends
Several variations of this method are com-
monly practiced in industry.
Hot pressing
A relatively simple method to manufacture
simple-shaped non-oxide ceramics to net
shape or near net shape is by hot pressing.
This method has been used traditionally and
profitably for decades and yields highly dense
and relatively more homogeneous products at
lower temperatures. A variation of this tech-
nique uses the concept of superplastic forging
to produce flaw-free ceramics. For example,
Panda, Seydel and Raj (1988) have described
a technique for making Si3N4 ceramics,
which uses isothermal pressing simulta-
neously with a suitable combination of strain
rate and temperature that will utilize the
superplasticity existing in this material under
these conditions. The use of partially densified
net-shape preforms is preferable because the
flow of material during processing can be
controlled to enhance product uniformity.
The unique feature of this process results in a
reduction of flaw sizes including the possi-
bility of their complete elimination that results
in enhanced strength (Venkatachari and Raj,
1987).
Hot isostatic pressing (HIPing)
Recently, considerable progress has been
made using very high temperature hot
isostatic pressing (HIPing) (Sheppard,
1992). Silicon nitrides (Si3N 4) have been hot
isostatically pressed to fully dense materials
of high strength and reliability. Although
glass-canned HIPing has been successfully
accomplished in the case of boron carbide
and SiC ceramics (Larker, Hermansson and
Adlerborn, 1988), it is not highly prevalent in
manufacturing complex-shaped components
of these materials. While progress, particu-
larly in glass canning of complex shapes
(Larker, Adlerborn and Karlsson, 1993), has
been made to reduce the inherent high cost
17
of this process, reproducibility in properties
and further reductions in processing costs
need to be demonstrated.
The glass-encapsulated HIP is a powerful
densification technique that can be used to
densify various single-phase and composite
ceramics that would not densify otherwise.
Usually the pressure is applied throughout
the densification process from the loose
powder to the fully dense ceramic part. The
glass enclosure helps prevent the dissociation
of Si3N4 even at high temperatures. Compared
to hot pressing in which only relatively simple
shapes can be made without further machin-
ing, glass-encapsulated HIP can be used to
make complex-shaped parts such as turbine
rotors and stators. In addition, improved
high temperature strength and resistance
towards slow crack growth were also
observed (Adlerborn et al., 1989).
The components that have been manu-
factured using this technology include gas
turbine rotors and stator rings, high speed
ball bearings, turbochargers, piston caps,
exhaust valves and seals, cutting tools, pre-
cision nozzles, high temperature crucibles,
thread guides, drawing dies and plugs, ther-
mal protection parts and heat exchangers
(ABB Autoclave Systems Inc., 1991).
Finishing of monolithic ceramics
These fired components, if planned well, can
be of close tolerance requiring very little, if
any, machining. The surface grinding requires
diamond machining. Final lapping and pol-
ishing is similarly accomplished using dia-
mond paste. In many instances, an annealing
treatment consisting of re-firing the finished
components under controlled atmosphere at
temperatures about 75% of the final densi-
fication temperature is necessary in order to
eliminate or homogenize the undesirable
tensile residual stresses. This treatment is
especially preferable for closed components
such as large rings etc. to avoid brittle fracture
on subsequent handling.
18 Non-oxide materials: applications and engineering
APPLICATIONS ENGINEERING
The engineered applications for these
advanced non-oxide ceramics are emerging
continuously due to their superior properties
compared to alternate metallic and other
non-metallic candidate materials. Specific
properties will depend upon the manu-
facturer, forming and finishing methods and
the status of the material, that is whether it is
in the development stage or in the production
stage. New opportunities will continually
evolve as more reliable processes and
materials are discovered and costs comparable
with existing materials are achieved. An
overview of current and potential markets for
the advanced non-oxide ceramics will be
given.
THE MARKET
The rather large world-wide effort in the
advanced non-oxide ceramics, in spite of all
the difficulties related to lack of adequate frac-
ture resistance, consistency and reproducibility
of reliable products etc. is due to the expecta-
tions of a relatively large future market (MIT!
Research Association, 1990). In the case of
advanced ceramics, the major portion (greater
than 70%) is expected to be in the area of elec-
tronic applications. However, several practical
applications have been identified for machinery
and structural use (Yamamoto and Kimura,
1987). The classification below is in terms of cur-
rently commercialized components, expected
to be commercialized within the next few
years, and longer-term commercialization.
These include the following:
Presently commercialized parts: mechani-
cal seals, abrasive wear-resistant nozzles,
bearings, grinding media for fine grinding
of ceramic powders, cutting tools, tools
and die components, heat exchangers,
valves, igniters, pump components used in
molten metal handling, furnace components
in semiconductor manufacturing and laser
mirrors.
Presently under commercialization: high
temperature heat exchangers, recuperators,
burners, turbocharger rotors, turbine rotors,
miscellaneous static components such as
burners, shrouds, vanes, piston caps, valve
seats and pre-combustion chambers. The
use of AlN as a substrate and heatsink
material is expected to be widespread.
Longer-term commercialization possibili-
ties: gas turbine components, MHD power
generation parts, Stirling engine parts.
For high temperature, low stress structural
applications, monolithic ceramics containing
Si3N4 and SiC are likely to remain the major
contenders well into the year 2000 (Lewis
and Leng-Ward, 1991).
WEAR COMPONENTS
Wear components such as cutting tools, dies,
guide rollers and nozzles have been prepared
by pressureless sintering TiB2 with small
amounts of additives (Nippon Kokan, 1987).
Sand-blasting experiments using aluminum
oxide grit showed very high erosion resistance
at 30 and 0 impingement angles. Boron
carbide is superior in its wear resistance and
has been used for extra-long-Iife blast nozzles,
crush dressing rolls, mold liners, crucibles,
bearings, gages, anvils, seals, mortars, sanding
templates, nuclear shields and controls
(Norton Company Advanced Ceramics,
1989). Silicon nitride (Si3N 4) cutting tools
are presently available commercially from
many sources.
SiC and Si3N4 tools, gages and dies are
commercially available from several sources
(VEPA Ceramic Processing Ltd., 1991) .
Thread guides
High volume production of thread guides for
the textile industry has been successfully accom-
plished by ABB Cerama AB using glass encap-
sulation HIP that requires no finish machining.
In 1990, one part made of Si3N4 with a

Figure 1.5 Typical silicon nitride sliding and rolling elements. (Photo courtesy of Saint Gobain/Norton,
Worcester, MA.)
maximum length of about 60 mm was produced
by this process at a rate of 700 pieces per week.
As early as 1980, sintered SiC had been commer-
cialized as guide ring material for fishing rods
(Lew Childre & Sons, 1980).
Bearings
Silicon nitride (Si3N 4) has been used in bear-
ings at high temperatures because of its inert-
ness and low friction coefficient without any
external lubricant (Sibley, 1982). Precision
bearings made of Si3N4 are now commercially
available from many vendors. A recent intro-
duction is by Enceratec consisting of both
monolithic bearing (ceramic balls and races)
and hybrid bearing (ceramic balls and steel
race). It has been claimed (Enceratec, Inc.,
1993) that hybrid bearings enable rotating
machine systems to attain significantly
higher speeds, even in lubrication starved
Applications engineering 19
environments. Typical sliding and rolling
elements are shown in Figure 1.5.
Pump seals
Perhaps the largest use of sintered SiC in the
wear market is in fluid sealing as mechanical
shaft seals. Lashway (1981) has described the
various manufacturing and performance
issues relating to the various forms of SiC in
chemical processing applications, especially
in abrasive, corrosive and high temperature
service. In terms of cost advantage, he
looked at one high volume application (auto-
motive seal faces) and one low volume
application (chemical process industry). For
high volume, water pump seal applications
(OD=22mm, quantity of 100000 pieces),
sintered SiC is used even though it is more
expensive than aluminum oxide. This is due
to its superior performance (Figure 1.6). The
20 Non-oxide materials: applications and engineering
SIC + 10%SI
High Volume
Automotive Seal Faces
'iii
0
()
CIl
.::
;;
Oi
a:
Figure 1.6 Relative cost for high volume automo-
tive seal faces. (Adapted from Lashway, 1981.)
relative costs for a typical low volume applica-
tion (00 = 60 mm, quantity of 25-50 pieces)
are shown in Figure 1.7. The increased
demand for SiC as seals in chemical process-
ing is due to its superior performance over
the metal-bonded hard metals. Whereas
sintered SiC can be used in virtually all chemi-
cal environments, the use of hard metals is
limited by its metallic binder, usually cobalt
or nickel. Additionally, SiC offers a higher
PV (pressure-shaft speed) capability than
hard metals when used with carbon-graphite,
the sacrificial face in a typical sealing
device.
Silicon carbide (SiC) has also found a
unique application in the automotive market.
The use of coolant formulations containing
high concentrations of silicates and nitrates
have a significant impact on water pump
seal performance. These additives act as corro-
sion inhibitors and are needed because of the
increased use of aluminum components in
modern engines. Premature seal failures
often result from the formation of a silicate
gel and build-up and smearing of crystalline
Low Volume
Chemical Process
Seal Faces
we
(6% eo)
'iii
8
CIl
.::;;
Qj
a:
Figure 1.7 Relative cost for low volume chemical
process seal faces. (Adapted from Lashway, 1981.)
deposits on the sealing faces, commonly
referred to as 'face-filming'. This can create
paths for leakage. This face-filming problem
and the need for extended service life has
created a niche-market for improved seal
face materials such as sintered a-SiC (Mac-
Beth, 1992). It was reported that Carborun-
dum has supplied over one million SiC seal
rings to European automotive manufacturers,
meeting their stringent quality standards
(Sheppard, 1988). The SiC water pump seals
are shown in Figure 1.8.
Abrasive waterjet cutting
While there have been many examples already
discussed that substantiate the benefits of non-
oxide ceramics in demanding engineering
applications, very few can match the impact
that ROCTEC* 100, a fine-grained, reaction-
bonded, WC-based composite, has had on an
industry. This metal- and void-free nozzle
material, lasting 20 to 25 times longer than
* Trademark of The Dow Chemical Company.

Figure 1.8 Silicon carbide automotive pump seals. (Photo courtesy of Carborundum Company, Niagara
Falls, NY.)
WC/Co products, has effectively revolution-
ized abrasive waterjet cutting (Dubensky
et al., 1992) (Figure 1.9). The severe abrasive
environment that the mixing tube must with-
stand is shown schematically in Figure 1.10.
Typical process conditions include water pres-
sures of 250-350MPa (36000-51 000 psi), and
garnet abrasive flow rates of 0.12kg/l!min
(lIb / gal! min). The dramatic improvement
observed in field tests mimics laboratory
results (Doty, Groves and Mort, 1989). These
results are summarized in Figure 1.11.
ROCTEC 100 is a reactive product of WC
and Mo that belongs to a family of reactive
compositions (Dubensky and Timm, 1990)
that follows the general scheme shown below:
AX + B --4 AX + (A, B)X (1.1)
where A and B are metals, and X is B, C, N
or Si.
Applications engineering 21
The WC composite was prepared using the
ROC (rapid omnidirectional compaction)
process. This unique combination of short
times, moderate temperatures and high form-
ing pressures results in a material having an
average grain size of ,...,0.25 J.Lm. The time-
pressure profile for the ROC process is
compared with some other pressure-assisted
densification methods (Figure 1.12). This fine
microstructure, shown in Figure loB, results
in a material with high hardness (,...,26GPa,
3.8 x 106 psi) and for a ceramic, high toughness
(,...,6 MPa . m 1/2, 5.5 ksi . in1/2) that is engineered
for wet abrasive wear applications like waterjet
cutting. The wear mechanism for the bore
diameter has been shown to be ductile
grooving in this application and related to
the abrasive particle/mixing tube hardness
ratio (Ness et al., 1994). This study also
showed that the use of a harder abrasive,
22 Non-oxide materials: applications and engineering

Figure 1.9 Abrasive waterjet cutting apparatus. (Photo courtesy of Boride Products Company, Traverse
City, MI.)

Al20 3, requires a harder nozzle material to
achieve acceptable wear life. Efficiencies and
range of cutting applications could be
expanded if an ultrahard abrasive particle
could be used.
CERAMIC ARMOR
Ceramics are attractive as the facing material
in an armor system. This is due to their
historically high hardness, high compressive
strength and low specific gravity. The
development of ceramic-faced armor was
accelerated rapidly in the mid-1960s by the
conflict in Southeast Asia. This battleground
marked the emergence of the helicopter as
the new workhorse for the infantry as well
as a powerful offensive weapon. However,
its vulnerability to light arms fire was pain-
fully apparent. A solution was needed that

High Pressure
Water Inlet
(25C 350 MPa)
JI~~~~~~~ Abrasive
MIXlng';;;-~~~~Ih~~~k:m:~"'i~r~-lnlel
Chamber
Mixing Tube
Abrasive Jet Mixing Head
Figure 1.10 Schematic of mixing tube arrangement
in abrasive waterjet cutting. (Photo courtesy of
Boride Products Company, Traverse City, MI.)
was effective, lightweight and economically
feasible. Protection for the crew and the
critical components of the hovering craft was
the incentive that led to the birth and rapid
deployment of B4 C armor. The evolution
from densifying small tiles in the laboratory
to full production of curved full body com-
posite vests remarkably took less than two
years to occur (Alliegro, 1967). The one-piece
B4 C facia is shown in Figure 1.14. Eventually,
crash-worthy helicopter seats (Figure 1.15)
were also manufactured with B4 C plates.
The success of this program was the
spark that led to over 20 years of armor
materials research and development activities.
Throughout this period, non-oxide ceramics
were studied extensively. Some of the earliest
work (Wilkins, Cline and Honodel, 1969;
Wilkins, 1979) showed that performance
against a 0.30 caliber armor piercing threat
(Figure 1.16) was largely determined by the
material's specific gravity. Based on the poor
performance of Si and Si02 , it appears that
Applications engineering 23
some minimal compressive strength or hard-
ness is required. Porosity and glassy phase
elimination also appear to be important. No
other properties could be correlated with the
observed performance. This result was con-
sistent with later studies as well (Viechnicki
et al., 1987; Rafaniello, Brubaker and Hoffman,
1989). As the threat level increased and the
ceramic was subjected to substantially higher
stresses, this simple relationship was no
longer valid. Figure 1.17 shows the relative
ballistic performance for several ceramics
against three threats (Hoffman and Epstein,
1988). While in all cases the non-oxides were
substantially better than Al2 0 3 , their relative
performance differed greatly. The anomalous
behavior of TiB2 (Vance, 1988) is particularly
fascinating. Attempts to rationalize these
results have been largely unsuccessful and
clearly reflect the complex mechanics of a
ballistic event, including the critical inter-
action between target and projectile materials.
Large market projections for ceramic armor
(Weatherall, 1990) were based on extending
armor technology to land-based vehicles. Alu-
minum nitride (AIN) showed considerable
promise as a high performance armor material
because of its potential for substantial cost
reductions (Young, Epstein and Hoffman,
1988; Rafaniello, 1992).
HIGH TEMPERATURE APPLICATIONS
Ceramic burners
The high thermal conductivity and high
emissivity in the infrared have made SiC the
material of choice as burner materials to
transfer heat efficiently to the surroundings
in furnaces. Gas-fired furnaces have long
used superalloys below ",,1223 K (950C) for
this purpose. These temperatures had been
limited by oxidation and creep of the superal-
loys. Silicon carbide (SiC), on the other hand,
has excellent creep resistance, oxidation resis-
tance and high temperature strength. In these
high temperature applications, SiC tubes are
24 Non-oxide materials: applications and engineering
AS TM 861 1
Wet Wheel Abrasion
2.0,--- - - - - - - - - - - - - - - - - - " " T ' " - - ----,1000
904

WC /Co-6 % 800 ..,

--
1.8
E
..,E '/ <D
Wear Limit o
o
~

..:: 1.6 600 ~

-
CI) CI
G; -I

e
to
CI)

E
:::I
CI 1.4 400 CI

...
CI)
>
...
CI CI)
c:ICI (I)

CI)

.:: 1.2 200 ~

wC/ Co
48
1 .00'-----~-~--..I...--~--.......
20 40 60
----...L..------I""""'..JO
80

Time, h
Figure 1.11 Field test results showing dramatic improvement in wear resistance for ROCTEC 100 mixing
tube.

100

~
Explosive
Compaction
10

.,
IV Hot
c.. Isostatic
c::J Rapid

-'"
Q.)
::::II
Omnidirectional
Compaction
Pressing

'"
Q.)
>-
c..
0.1

0.01
@
Hot Pressing

0.001
6 4 2 0 2 4
log (Duration), S

Figure 1.12 Comparison of time-pressure profile of ROC process with other pressure-assisted densifica-
tion methods.

Figure 1.13 Photomicrograph of binderless composite carbide, ROCTEC 100. (Photo courtesy of The Dow
Chemical Company, Midland, MI.)
internally heated by a combustion burner. The
heated SiC radiates heat to the surroundings.
Eclipse Inc. and Pyronics Inc. in the US pro-
duce these burners for commercial heat treat-
ment applications. The ceramic material used
for these burners is reaction-bonded silicon
carbide (RBSC).
Special crucibles
Titanium diboride (TiB 2 ) does not react
with molten copper, zinc or aluminum, and
therefore is used as a crucible material to
melt non-ferrous metals. Boron nitride (BN)
has been used for crucibles and boats for
molten metals as well as for break rings for
continuous casting of steel. Aluminum nitride
(AIN) is a useful ceramic for special applica-
tions since it is resistant to molten salts and
metals. Crucibles and containers made of
Applications engineering 25
AIN using aqueous-based processing are
shown in Figure 1.18.
Thermocouple protection tubes
Silicon carbide (SiC), B4 C and BN can be used
as thermocouple protection tubes and insu-
lating components.
ELECTRICALLY CONDUCTIVE CERAMICS
The electrically conductive or resistive
ceramics find use in a variety of electrical
and electronic applications. The high electrical
resistance of SiC, for example, has been capi-
talized in resistive heating applications. In
diesel-engine automobiles, a heater element
for glow plugs which can be heated rapidly
with concurrent high temperature durability
is highly desired. Alloying additions of TiB2'
26 Non-oxide materials: applications and engineering
Figure 1.14 One-piece boron carbide body armor developed in mid-1960s. (Photo courtesy of RA. Allie-
gro, Alltec Consulting, Inc., Northboro, MA.)
ZrB2' TiN and ZrN have been made to make
SiC-based ceramics with a range of electrical
resistivities. Additionally, a variety of sinter-
ing additives such as A120 3 , MoB 2 and B4 C
have been tried (Matsushita, Nakamura and
Harada, 1985). Igniters for natural gas fur-
naces and appliances, shown in Figure 1.19,
also exploit the benefits of these SiC-based
materials.
One of the earliest applications for ceramics
exhibiting controlled electrical resistance and
non-wettability to molten metals has been in
the area of metallization boats or evaporation
boats. Usually, these are intermetallic com-
pounds of TiB 2, containing BN and in some
cases AIN. The BN constitutes the resistant
part of the evaporation source (1.7 x
1013 ohm. cm) and enables the vaporization
operation to occur at relatively low currents
(Tonini, Grazzni and Merlini, 1980). Usually
the vacuum metallization is done with alu-
minum at temperatures between 1673 K
(1400C) and 1873 K (1600C). The type of
decay product during service is an important
consideration. Both TiB2 and BN decay to
solid amorphous boron and a gas (N2 and
Ti). The presence of boron is helpful to the
process because it retards the vaporization of
the subsurface material, thereby prolonging
its life (Wilder, 1981).
CORROSION RESISTANT APPLICATIONS
Silicon carbides (SiC) are very resistant to acids
and alkalis and therefore are used as mechan-
ical seal faces in demanding applications

Figure 1.15 Boron carbide armor development led to manufacture of crash-worthy helicopter seats. (Photo
courtesy of RA. Alliegro, Alltec Consulting, Inc., Northboro, MA.)
involving pumping chemicals. Additionally,
under oxidizing conditions, SiC forms a con-
tiguous surface layer of silica which prevents
further oxidation.
AUTOMOTIVE APPLICATIONS
The use of ceramics in automotive applica-
tions has received considerable attention.
The market potential has been estimated to
be enormous (Larsen et al., 1990). The initial
high cost due to low production volumes
and the economic and technological barriers
are being overcome but have severely ham-
pered the rate of progress that was antici-
pated. As techniques are refined, the relative
costs for component production are expected
to drop as shown in Figure 1.20. An exponen-
tial relationship is predicted with increased
Applications engineering 27
production volume or market penetration
during the commercialization of ceramic
turbocharger rotors.
The utility of Si3N4 has been demonstrated,
particularly in Japan, in a systematic manner
(Yoshida, Kokaji and Koga, 1989). Car makers
such as Isuzu, Mitsubishi, Mazda, Nissan and
Toyota introduced glow plugs, intake heaters,
hot plugs, rocker arm tips and turbocharger
rotors during the 1980s. Hamano and Yama-
moto (1984) and Kawamura and Yamamoto
(1983) have successfully used hot-pressed
Si3N 4 , because of its higher use temperature
(Hoffmann, 1995), to concurrently reduce
preheat time and idling noise. Kyocera
Corporation and NGK Spark Plug Co. Ltd.
have supplied such glow plugs to Japanese
automotive manufacturers. The ceramic glow
plug is capable of attaining an operating
28 Non-oxide materials: applications and engineering
1.4...---------------------.

1.2
Be2B.

~
c 1.0
CD
'u
:=w
u
~ 0.8
SiC.
ii
m
CD
>
;:; AD95
CIS A1203*
'i)
a: 0.6
Si

Si02

0.4

1000 2000 3000 4000 5000

Specific Gravity kg/m 3

Figure 1.16 Relative ballistic performance of hard-faced ceramic targets with 0.64 mm Al backing against
0.30 caliber AP rounds. (Adapted from Wilkins, Cline and Honodel, 1969.)

temperature of 1073 K (800C) within 2 s for
engine start and can attain temperatures as
high as 1323 K (1050C) in the initial start-up
period, exhibiting excellent high temperature
strength. Temperatures greater than 1173 K
(900 C) could be maintained for long times,
to aid combustion, without deteriorating the
glow plug (Figure 1.21) (Kawamura and
Yamamoto, 1983).
The glow plug experiences very high
temperatures for short durations. A similar
environment is experienced by the pre-com-
bustion cup. The rocker arm pad and the
valves experience severe impact stresses. The
turbocharger rotor is the most complex-
shaped ceramic to be manufactured reliably
to withstand centrifugal (rotational) stresses,
thermal stresses due to combustion, and
impact loading by combustion products. The
mechanical vibrational stresses, that are
common to any machinery, can, in addition,
introduce unexpected and random parasitic
stresses. It has become very common to con-
duct finite element stress analysis for any com-
ponent that will be used in the automotive
applications in order to help to design for
reliability, for ease of manufacture and for
ease of inspection.
 Applications engineering 29
2r---------------~----------------~----------------~
Threat 1 Threat 2 Threat 3

B4 C
~ SiC
AIN
r.d TiB2
r2l AI 2 0 3

o
Figure 1.17 Relative ballistic performance of several ceramic-faced targets against three threats.

Figure 1.18 Slip-cast parts formed from using aqueous-based aluminum nitride processing. (Photo cour-
tesy of Advanced Refractory Technologies, Inc., Buffalo, NY.)
30 Non-oxide materials: applications and engineering

Figure 1.19 Igniters made from sintered SiC are used in natural gas furnaces and appliances. (Photo cour-
tesy of Saint Gobain/Norton, Worcester, MA.)

During the 1970s and 1980s, many labora-
tories around the world took a systematic
approach to the development of ceramics for
various structural applications. Their efforts
were primarily evolutionary. The evolution
at ceramic vendors had occurred in terms of
development of high performance materials,
reliable and robust processes, and inspection
techniques. Implementation of revolutionary
concepts was largely lacking. However, a
primary user of ceramics, the automotive
industry, revolutionized their design through
the use of finite element stress analysis, the
application of probabilistic design method-
ology and novel joining methods. Implemen-
ted concepts which provided the needed
cushion for ceramics were successful mating
techniques of ceramics with metals and the
use of compliant layers. The technical per-
formance issues and the manufacturing for
reliability and performance were key issues
that were addressed during this period. A
 Applications engineering 31
120

100

~
80
E
:::I
E

-
...
CII
11.
80

II) 40
Figure 1.21 Silicon nitride ceramic glow plug.
0
0 (Photo courtesy of Nissan Motor Co., Ltd., Yoko-
20 suka, Japan.)

0 has been to enclose the ceramic in a metal ring

0 5 10
Market Share (%)
Figure 1.20 Ceramic turbocharger model for cost
reduction as a function of market share.
summary of the systematic introduction of
components by different automotive manu-
facturers is given in Table 1.3.
Pre-combustion cups (Kamiya et al., 1985)
(swirl chambers) and rocker arm tips
(Ogawa et al., 1986) made of Si3N4 were
successfully demonstrated during simulation
experiments as well as in real road conditions.
Toyota Motors started working on ceramic
swirl chambers since 1981. The material of
choice has been Si3N4 due to its high tempera-
ture stress and good fracture resistances. The
revolutionary change in design for the ceramic
15
so that the ceramic experiences compression.
The use of ceramic also allowed modification
of the operating parameters compared to the
metal chamber (Figure 1.22). The metal ring
helped distribute the temperature more uni-
formly around the ceramic surface, thereby
reducing the thermal stresses in the ceramic.
The adjustment of engine performance was
made in consideration of compression ratio,
boost pressure, injection timing and injection
quantity in order to utilize ceramic capabilities
at high temperatures. The power output could
be increased according to an increase in the
temperature of the combustion chamber.
Commercialization of Si3N4 and SiC
ceramic valves and guides progressed glob-
ally. Wills and Southam (1989) reported the
dynamometer as well as actual test results of

Table 1.3 Commercial introduction of ceramic automotive-related engine components

in Japan

Components Year of Engine Manufacturer

introduction

Glow plug 1981 Isuzu Kyocera

Swirl chamber 1983 Isuzu Kyocera
Intake heater 1983 Isuzu Kyocera
Rocker arm tip 1984 Mitsubishi NGK
Turbocharger rotor 1985 Nissan NTK
Link injector 1989 Cummins Toshiba
Cam roller follower 1993 Detroit Diesel Kyocera
Exhaust control valve 1993 Toyota Kyocera

Sources: 'Progress in structural applications of silicon nitride,' Hamano, Y., in Silicon-Based Struc-
tural Ceramics, Ceramic Transactions 42, ed. B. Sheldon and S. Danforth, 3-14, 1994. Reproduced by
permission of the American Ceramic Society, Westerville, OH. 'Design practices for structural
ceramics in gasoline engines,' Okajima, K. and Matsuda, R., in Engineered Materials Handbook,
Vol. 4, Ceramics and Glasses, 738, 1991. Reproduced by permission of ASM International.
32 Non-oxide materials: applications and engineering
Figure 1.22 Silicon nitride pre-cup with metal ring.
(Photo courtesy of Toyota Motor Corporation,
Sizuoka, Japan.)
Si3N4 valves installed in an Oldsmobile Cutlass
Ciera vehicle with accumulated miles in excess
of 20000. Simultaneously, Hori et al. (1989)
reported the advantages of using Si3N4 valves
in increasing the driving speed and reducing
the camshaft driving torque. Boecker et al.
(1992) developed hot isostatically pressed
reaction-bonded Si3N4 (HIPRBSN) for engine
valves. These were installed in a Mercedes
Benz 300 E and successfully road tested. This
unique material was reported to have an
average strength of 927MPa (135ksi) with a
Weibull modulus of 29. A joint demonstration
by NGK Spark Plug, Komaki, Japan, and GMC,
Warren, MI, was successful in using an Si3N4
valve component. The use of this ceramic
resulted in an approximate 20% increase in
maximum rotational speed. The ceramic-
modified engine provided a fuel efficiency
increase of about 3.5% in a 21 displacement
engine. The valve lifter showed very little
wear following more than 320000 km (200000
miles) in an automobile. Based on these results
and the properties of the ceramic, it was
concluded that such a ceramic would meet
the reliability requirement of large scale com-
mercialization (Tennery, 1989).
Silicon nitride (Si3N 4) ceramic cam fol-
lowers were successfully tested by Chrysler
Corporation, even though the valve lash was
deliberately increased to 0.76 mm to cause
severe shock to the ceramic rollers (Brooks,
1990). The ceramic part offers the ability to
withstand customer neglect of maintenance.
Additionally, it was demonstrated that plain
journal-bearing ceramic rollers can replace
the current needle-bearing metal rollers at
equivalent cost. Success has been demon-
strated by Detroit Diesel Corporation
(WARDS, 1992) in a new Series-50 bus
engine in which the fuel injectors are operated
through rocker arms with Si3N4 cam roller
followers. It was found that the hardness
and low coefficient of friction of Si3N4 reduces
wear in this highly stressed part. Based on this
success, efforts were extended to the next
generation version of the state-of-the-art
Series 60 engine. The objective was to obtain
cam roller followers with a usable life of 1.6
million km (1 million miles) at future load
levels. Operating under various conditions,
the laboratory tests were successful for over
3.2 million km (2 million equivalent miles).
The superior wear resistance also eliminated
the need for several expensive internally
machined oil passages. This longevity goal
was cost effectively achieved.
Ceramics have also been used as rocker arm
pads because of their superior resistance to
wear. As was mentioned previously, Si3N4
offers wear and impact loading resistances.
In a test conducted by NGK Technical
Ceramics, in 100 h of operation, a metal pad
had a tip wear of 50 J-Lm with a concomitant
100 J-Lm wear of the chilled iron cam nose.
However, under identical test conditions, the
wear on an Si3N4 pad was less than 5 J-Lm, with
the wear of the chilled iron cam nose less than
10 J-Lm. In other words, the ceramic was better
than the metal by an order of magnitude in the
performance of both wear pairs. An Si3N4
rocker arm pad is shown in Figure 1.23.
Perhaps the most demanding application in
the automotive segment is the ceramic turbo-
charger rotor. There are technical reasons for
the success in the market penetration for
ceramic rotors. They are 40% lighter in

Figure 1.23 A silicon nitride rocker arm pad.
(Photo courtesy of Nissan Motor Co., Ltd., Yoko-
suka, Japan.)
weight than the traditional metal rotor,
thereby reducing the moment of inertia by
35%. It contributes to reduced turbo lag,
improved acceleration response and increased
performance at all speeds. Higher tempera-
tures of up to 1273 K (1000C) help handle
CN-1
Figure 1.24 Silicon nitride rotor assemblies. The darker rotors on the left are made of silicon nitride
ceramic.
Applications engineering 33
increased exhaust temperatures with conco-
mitant improvement in fuel efficiency and
reduced emission even at high speeds. Silicon
nitride (Si3N 4 ) ceramic turbocharger rotors
were first commercialized in Japan. NKG
Spark Plug Co. Ltd. and Kyocera Corporation
led this development and supplied reliable
Si3N4 turbocharger rotors. Two rotor assem-
blies from Nissan Motors Corporation are
shown in Figure 1.24.
Since October 1989, Toyota Motors has been
very active in the Si3N4 turbocharger rotors.
Silicon nitride (Si3N 4) wheels - named CT26
- were used in 2.01 inline four-cylinder
engines, with a maximum power output of
165kW. In August 1990, another set of Si3N4
wheels - named CT12A - for 2.51 inline six-
cylinder engines were introduced, with a
maximum power output of 206 kW. In
October 1991, a CT20A rotor was introduced
34 Non-oxide materials: applications and engineering
for 3.0 1 inline six-cylinder engines. The CT26
type is the large wheel and CT12A is the small
wheel in the turbocharger series of Toyota.
The ceramic turbocharger efficiency was
almost the same as that of the metal wheel in
both the CT26 and CT12A types, while the
moment of inertia was reduced by about 60%
over that of the metal turbine wheel assembly
(Takama et al., 1992).
Improvements in injection molding and
closed-loop quality assurance procedures
were reported to have resulted in a three-fold
improvement in the reliability of Si3N4 rotors
when they were developed for Daimler-Benz
by the GTE Corporation (Bandyopadhyay
and Neil, 1990).
The development and application of
ceramics for the hot path components of gas
turbines, both automotive and stationary,
have been the field of active research starting
in the late 1970s. Significant advancement had
been made in demonstrating ceramic com-
ponent viability through thousands of hours
of both steady-state and transient testing,
Forming
Firing
Machining
Spin Testing
Overall
o 20
Figure 1.25 Data showing improvement in ceramic rotor yield over a decade for a gas turbine application.
(Adapted from Berenyl, Hilpisch and Groseclose, 1992.)
while operating up to full design speed, and
at turbine inlet temperatures up to 1644 K
(1371 DC). In a fourth generation design of a
ceramic gasifier rotor, Allison Gas Turbines
was successful testing a rotor made of Si3N 4.
The vanes and scroll assembly were made
from both SiC and Si3N 4, and the vane plat-
form was made from several Si3N4 variations
(Berenyl, Hilpisch and Groseclose, 1992).
Additionally, they also determined that the
overall processing yield of ceramic compo-
nents had increased steadily. This improve-
ment in manufacturing translates into lower
costs and faster product acceptance (Figures
1.25 and 1.26).
It is realized that automotive applications
require the delivery of reliable ceramic compo-
nents at competitive prices in comparison to
their metallic counterparts. Das and Curlee
(1992) examined two engine parts - roller
followers and turbocharger rotors - and per-
formed cost analysis. Their results indicated
that for Si3N4 components, the raw material
powder cost is the largest contributing factor
o 1980
I2l 1987
1992
40 60 80 100
Yield (%)
 Applications engineering 35

Forming

Firing
o 1980
~ 1987
1992

Machining

Overall

20 40 60 80 100
Yield (%)
Figure 1.26 Data showing improvement in ceramic scrolls yield over a decade for a gas turbine applica-
tion. (Adapted from Berenyl, Hilpisch and Groseclose, 1992.)

to the overall cost of the component, as shown lowering the powder cost, are essential to be
in Figure 1.27. Further analysis clearly showed competitive with metallic parts. However,
that technical improvements in processing other overall benefits offered by the use of
resulting in cost reduction, in addition to ceramics were not included in the model.

2.2% 1.6%

Labor
~ Materials
o Capital Charges
g Energy
D Other

Roller Follower Turbocharger Rotor

Figure 1.27 Ceramic component cost analysis. (Das, S. and Curlee, T.R., 'The cost of silicon nitride powder
and the economic viability of advanced ceramics,' Bull. Amer. Ceram. Soc., 71(7), 1103, 1992. Reprinted by
permission of the American Ceramic Society, Westerville, OH.)
36 Non-oxide materials: applications and engineering

Figure 1.28 CRYSTAR SiC diffusion components playa critical role in semiconductor processing. (Photo
courtesy of Saint Gobain/Norton, Worcester, MA.)

SEMICONDUCTOR PROCESSING resistance of SiCs (Waugh and Foster, 1985)

APPLICATIONS
In semiconductor wafer manufacturing, quartz
furniture is being used to place silicon wafers
in doping furnaces. However, the superior
mechanical strength, chemical and high
temperature inertness, and excellent creep
are attractive as alternate materials especially
since the doping is done nowadays at increas-
ingly higher temperatures. CRYSTAR SiC
diffusion components (Figure 1.28) are being
used in the most critical semiconductor appli-
cations (Norton Company, 1991). Another
product, called SUPERSiC, is being marketed

by SOUTHtech, Inc. (1991). There are electron-
ic grade a-SiC manufactured without the use
of binders, sintering aids or densifiers. The
processing has been specially designed to
allow the use of standard etching solutions
such as HF and nitric acid-HF without etching
the wafer carrier.
ELECTRONIC SUBSTRATES
As electronic devices become smaller and
more powerful, thermal management of
ceramic substrates and packages becomes
essential. Physical strength and low coefficient
of thermal expansion are also important in
these applications. When compared to the
typical substrate materials (Table 1.4), AlN's
comparatively high thermal conductivity and
coefficient of thermal expansion near that of
silicon make it ideally suited for the increas-
ingly important, high density, high power
components.
Some of the devices where AIN has been
effectively utilized by the world's leading
electronics companies include packaging for
a discrete RF device, automotive ignition
modules, ICBT modules, heatsinks for RF
transistors, multi-chip modules (MCMs),
substrates for laser diodes, quad packs, LSI
chip packages, and several PCA (pin grid
array) and BCA (ball grid array) compo-
nents (Carrou and Knudsen, 1994; Imura,
Ito and Terasawa, 1994; Iwase et al., 1994;
Matsuki et al., 1994; Palmer and Reed,
Applications engineering 37
1994). Aluminum nitride (AIN) substrate
packages from Carborundum Microelectron-
ics are shown in Figure 1.29.
SPECIAL APPLICATIONS
Laser mirror is an application that is ideally
suited for SiC because of its high section
stiffness, ultralow weight, and thermal stabi-
lity. It is also a more cost-effective alternative
to beryllium. United Technologies Optical Sys-
tems Division currently markets such mirrors
that can be polished to a surface roughness of
less than 1 nm (10 A). It is claimed (United
Technologies Optical Systems, 1991) that the
system integrity is maintained throughout
the high dynamic load operation by the
extreme stiffness of the mirror structure and
the absence of micro-yield in the SiC material.
The thermal properties of SiC resist deforma-
tion from varying temperatures six times more
effectively than the presently used mirror
materials - beryllium or aluminum.
Silicon carbide (SiC) is also well suited for
soft x-ray mirrors required for synchrotron
systems thanks to its high hardness, good
thermal properties and radiation resistance
(Mrowka and Rosser, 1982).
The conversion of thermal energy to electri-
cal energy is the well-known Seebeck effect. In
principle, it is possible to utilize this phenom-
enon for thermoelectric power generation. By
analyzing the results of electrical conductivity
as a function of temperature on porous a- and

Table 104 Properties of key ceramic materials for substrates and packages

Materials Density Strength Modulus RT thermal Thermal RT electrical RT dielectric

(kg/m 3 ) (MPa) (CPa) conductivity coefficient of resistivity constant at
(W/moK) expansion at (Docm) 1 MHz
25-400C

Alumina (92%) 3890 440 345 17 6.5 >1013 8.5

Beryllia (99.5%) 2850 220 260 260 7.5 > 1013 6.7
AIN 3260 320 320 160 4.1 >10 14 8.8
BN 1900 20 43 25 0 >10 14 4.1
SiC 3210 280 425 70 3.8 >10 12 40

RT: room temperature.

38 Non-oxide materials: applications and engineering
Figure 1.29 Aluminum nitride substrate packages. (Photo courtesy of Carborundum Microelectronics,
Phoenix, AZ.)
fJ-SiC, Koumoto et al. (1987) have concluded
that by appropriate microstructural design
and control, it would be possible to use SiC
materials in thermoelectric energy conversion.
The lOB isotope is a natural material for
nuclear shielding applications and B4 C pellets
have been historically used in this application.
A ceramic gun barrel is a goal by the makers
of gun systems. The design trade-off between
muzzle velocity and gun barrel bore tem-
peratures has resulted in gun systems which
operate at or near the melting point of steel -
which is the most commonly used gun barrel
material. A systematic design, fabrication and
testing approach has demonstrated that SiC
has the capacity to resist the erosive environ-
ment and the thermal shock associated with
high temperature propellant gases involved
in rapid fire (Durkee, 1992).
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CRITICAL POWDER CHARACTERISTICS 2
William Rafaniello

INTRODUCTION atomic transport mechanism (Kingery and

Berg, 1955; Coble, 1958; Johnson and Cutler,
The growth of advanced non-oxide ceramics
1963; Kuczynski, 1963; Johnson, 1970). These
can be directly traced to the availability of
pioneering studies consistently predicted the
high quality powders. Particle size reduction
substantial benefits of finer powders in
has been the primary powder feature that
densifying ceramics. This need is particularly
has allowed this technological development.
critical when working with covalent solids
Controlling phase and overall chemical
(Greskovich and Rosolowski, 1976). Theoretical
purity have also been important.
sintering rates were determined to be propor-
Non-oxide ceramics are generally employed
tional to 1lrn, where r is the average particle
where performance under extreme conditions
radius and the exponent, n, is either 3 or 4. A
is required. As described in Chapter 1, silicon
plot of the sintering rate constant for three
nitride (Si3 N 4 ) is the material of choice when
different-sized AlN powders (Figure 2.1)
high strength and toughness are required at
dramatically illustrates the benefits of fine cera-
high temperatures. When high thermal con-
mic powders (Komeya and Inoue, 1969).
ductivity and electrical insulation are needed,
While the availability of finer powders was
then aluminum nitride (AlN) would be the
necessary to achieve the desired sinterability,
non-oxide of choice. Tungsten carbide (WC)
it often was not sufficient (Brook, 1982). Co-
as part of a metal-ceramic composite or
incident with the development of improved
cermet with cobalt (Co) is used in many wear
powders were the important discoveries of
and cutting applications. The high tempera-
specific additives that enhanced the sinter-
ture creep resistance, oxidation resistance
ability of the non-oxide ceramics. Key
and corrosion resistance of silicon carbide
sintering developments for these advanced
(SiC) establish its application envelope.
non-oxide materials will be elucidated as well.
Prior to the introduction of this next genera-
tion of non-oxide powders, the commercial
opportunities were limited to relatively
TUNGSTEN CARBIDE (WC)
simple shapes that could be achieved by hot-
pressing. An increase in driving force was The first non-oxide material with significant
needed to overcome the slow densification market penetration was 'metal-cemented'
kinetics of the micron-sized powders. tungsten carbide (WC) (Spriggs, 1995). These
The sintering of ceramic powders has been ceramic-metal composites have been tradition-
studied extensively. Several sintering models ally considered as 'hard metals' rather than
were proposed depending on the prevalent advanced ceramics. However, particularly

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
44 Critical powder characteristics
(Temperature K)
2300 2200 2100 2000 1900
0.1 rl----t----t-----t---:-:-:-:-::-:-----L:---=-----,
AIN Sintering Rate
vs
Average Grain Size

~
;;
!!
'"
c:
0

...
(.)

iii 0.01
a::

...""
E
;;
0

i:i5

4.4 4.6 4.8 5.0 5.2 5.4

(1fT) x 104 (11K)

Figure 2.1 Sintering constant for three sizes of undoped AIN powders showing the dramatic benefits of
sintering with fine particles. (Komeya, K. and Inoue, H., 'Sintering of aluminum nitride: particle size
dependence of sintering kinetics,' J. Mat. Sci., 4, 1045-50, 1969. Reprinted by permission of Chapman
& Hall, London, UK.)

from a powder perspective, WC's commercial
importance justified its incorporation into this
text. The discovery by K. Schrater (1923, 1925)
that transition metal additions allowed WC to
be fully densified at low temperatures, '" 1773 K
(1500 0c), was critical to the growth of the hard
metal industry (Fischmeister, 1983). Schrater
(1923, 1925) also established a sintering proce-
dure for these materials that is still being uti-
lized (Schneider, 1989). Densification proceeds
by rapid diffusion of WC through the molten
metal binder phase (Kingery, Niki and Nara-
simhan, 1961; Warren and Walderon, 1972;
Meredith and Milner, 1976). This process is
considered to be the birth of modem liquid
phase sintering technology (German, 1985).
Because of the ease with which WC can be
densified, the development of sub micron WC
powders was not a necessary element of com-
mercialization. Powder grades commonly
used are fine, medium and coarse. These
have an average grain size of about 1 JLm,
1.5-2 JLm and 3-4 JLm, respectively. There are,
however, two submicron grades that are
employed in limited, specialized applications.
The ultrafine grade has an average grain size
of 0.25-0.4 JLm and micrograin powders are
about 0.8 JLm (Brookes, 1992). Instead of size,
the critical powder issue for WC involved COn-
trolling the tungsten-carbon (W-C) stoichio-
metry in order to optimize part performance.
EFFECT OF TUNGSTEN-CARBON
STOICHIOMETRY
From the W-C phase diagram shown in
Figure 2.2 (Rudy, 1969), there is a fairly
narrow stoichiometry range for We. When
the exact carbon content is not achieved,
either free carbon or di-tungsten carbide
 Tungsten carbide 45

4000
, '-3823
3800 2993:!:12
3020:!:12
3600

g 3400 l+C
...
.a 3200
W+l
~ 304910
: 3000 17;_ _2_98_3_:!:_12_ _::....::::;(":"-;:~~-====1".;.......;.-'--1
...
I-
2800 WC+C

2600

2400 WC

2200~ _ _~_ _~_ _~_ _~_ _~_ _~~

o 10 20 30 40 50 60
W Atomic % Carbon

Figure 2.2 Equilibrium diagram for W-C phase system. (Adapted from Rudy, 1969.)

(W 2C) is formed. In both cases, the properties HARD METAL COMPOSITIONS

of the densified hard metal products are less
than optimum. When W 2C is present, the
toughness of the sintered component is
reduced in two ways. Oi-tungsten carbide
(W 2C) is a more brittle phase than WC and it
often reacts with and partially depletes the
cobalt (Co) binder to form mixed (W, Co)
carbides (Exner, 1983). The presence of the
weaker eta phase (Co, W)6C, was shown to
have a dramatic impact on fracture toughness
for a WC-I0Co composition (Bolton and
Keeley, 1982; Cutler, 1984). The sensitivity of
this effect is diminished with increased Co
levels. The range of acceptable C content in
WC powders increases 70% by going from 6
to 10% Co (Guillermet, 1989). While fracture
toughness was not greatly affected by the
presence of free carbon, other properties,
such as strength and hardness, are negatively
impacted (Gurland, 1954). While not desir-
able, the presence of free carbon is preferred
over the tungsten-rich situation. This is parti-
cularly true when the desired minimization of
the WC powder oxygen content is considered.
There are numerous commercial hard metal
compositions (Brookes, 1992). Properties of
these materials can be tailored largely by con-
trolling grain size and the amount of binder
phase. The impact of grain size and Co content
on several mechanical properties is schemati-
cally represented in Figure 2.3. In general,
hardness and compressive strength increase
as the average grain size decreases and/ or
as the binder level decreases (Gurland and
Bardzil, 1955; Almond, 1983; Gomes, 1988).
These variables have the opposite effect of
the fracture toughness. The toughest hard
metals have high binder levels and larger
grains (Exner and Gurland, 1970; Chermant
and Osterstock, 1976). Transverse rupture
strength (TRS) tends to increase with binder
level, but is fairly insensitive to grain size in
the range typical for commercial hard metals
(Gurland, 1954; Gurland and Bardzil, 1955;
Gomes, 1988). The advantage that micro-
grained products offer is the ability to extend
the property envelope available for materials
46 Critical powder characteristics
en
en
...=
CI)
'C
~
:::c
Toughness
Figure 2.3 Schematic showing influence of binder content (Co) and average grain size on mechanical prop-
erties of WC-Co cermets.
engineers. With harder materials possible for
a given binder level, high abrasive wear resis-
tance at acceptable toughness levels can be
achieved with micrograined hard metals
(Pastor, 1987; Prakash, 1989).
Traditional WC-Co compositions can range
from 1.5 to 30wt% Co (Brookes, 1992) and
have microstructures with average grain
sizes of 1-5 p,m. Grain growth inhibitors are
used to prevent large flaw-limiting grains
from developing during the liquid phase sin-
tering process (Schubert, Bock and Lux, 1995).
The order of effectiveness for a given amount
of addition is from highest to lowest VC,
Cr3C2, NbC, TaC, Mo 2C, TiC and Zr-HfC
(Gomes, 1988). These carbide additions to the
WC-Co system usually result in harder and
stronger materials due to both changes in
microstructure and composition of the consti-
tuents (Prakash, 1989). These additions lead
to a finer, more uniform grain size and can
form ternary, mixed metal carbides and
Ultraline 0.5 #1m)
Micrograin (0.5-1 #1m)
solid solution phases, and/or modify the
binder phase. The tendency to form eta
phase is also substantially reduced because
an enhanced stoichiometry region for the
solid solution compositions can effectively
take up any excess tungsten.
The development of materials with micro-
grained structures has resulted in hard
metals with superior strength characteristics
and a multifold improvement in abrasive
wear life (Prakash, 1995). These improved
materials offer advantages in cutting iron
and steel under conditions where low speed
wear mechanisms are active (Pastor, 1987).
Microdrilling has been another application
that has benefited from this materials develop-
ment. As the opportunities for this type of
product expand, the availability of suitable
powders then becomes an issue. This develop-
ment would most likely lead to increased
demand for direct synthesis process alterna-
tives to the intensive powder milling required

for obtaining submicron, high quality
products.
While the WC-Co system dominates the
hard metals field, there are also some hard
metals based on TiC and other solid solution
compositions (Brookes, 1992). Synthesizing
titanium carbide (TixC) powders is more
straightforward because of the wide carbon
stoichiometry range that is available (Figure
2.4). In addition, Ni rather than Co, is used
as the primary metallic binder with (TixC).
Nickel does not form any reactive phases
with TiC. Titanium carbide can also form
extensive solid solutions with other cubic
carbides.
SILICON CARBIDE (SiC)
Silicon carbide (SiC) has a close-packed crystal
structure that, depending on the stacking
order, can exist in either cubic (ABCABC ... )
or hexagonal (ABAB ... ) orientations. Numer-
ous SiC polytypes have been identified
(Dobson, 1986); however, the lower order
1800 ~TI+ TIC
o 10 20 30 40
Ti Atomic % Carbon
Figure 2.4 Equilibrium diagram for Ti-C phase
system, showing wide stoichiometry region for
monocarbide TixC. (Adapted from Rudy, 1969.)
Silicon carbide 47
ones are the most significant. Using the
Ramsdell (1947) notation, the most common
SiC polytypes are 3C (cubic or (3 phase), 4H,
6H, 15R and 27R. The hexagonal (H) and
rhombohedral (R) forms constitute a-SiC and
vary by the stacking sequence in the [0001]
direction. Longer-period polytypes have
been observed during vapor or solvent pro-
cesses and typically involve the incorporation
of surface defects, leading to stacking faults.
The relative stability of these phases as a func-
tion of sintering temperature is shown in
Figure 2.5 (Williams et al., 1985). This figure
should be used as a guide only, since there
are numerous factors that can influence SiC
crystallography. In fact, isolated, phase pure
SiC is rare. Multiple combinations of' crystal
structures are much more common. X-ray
diffraction methods have been established to
monitor the relative concentrations of the
various polytypes (Bartram, 1975; Ruska et al.,
1979; Hubbard, 1982).
There are several SiC-based products with
significant commercial value. Many of these
products utilize metallic silicon as the binding
phase for SiC aggregates. While the amount of
residual silicon can vary from 1.5 to as much
as 30% depending on the fabrication process
(Knoch, Sigl and Long, 1990), even at the
lowest levels, mechanical strength diminishes
dramatically near the Si melting temperature
of 1683K (1410C) (Kennedy et al., 1973;
Schwetz, 1989). In order to obtain high tem-
perature creep resistance and excellent wear
characteristics in harsh environments, high
density, Si-free, SiC ceramics needed to be
developed. Silicon carbide (SiC), like many
of the other non-oxide ceramics, had been
extremely difficult to densify in its pure state
(Thuemmler, 1980).
50 60 EFFECT OF OXYGEN
Powder manufacturers must control oxygen
levels in order to meet their customers'
requirements for part fabrication. It is inevit-
able that high surface area SiC powders
48 Critical powder characteristics
SiC Ceramic Sintered with B,C, and AI
1.0
C-
o
:;::;
...ca
u
LL.
0.8
0
~
c 0.6
o
:;::;
::::I
.Q
'i:
U; 0.4
is
CI)
Q.
>-
>. 0.2
0
a...

0.0 SiC Polylypes

2000 2200 2400 o 4H
Sintering Temperature (K) ~ 6H
2200 2400 0 15R
2000 II ac
1.0

-...
disordered
C
.S!
u
ca 0.8
LL.

-
C;
>
c 0.6
0
:;::;
::::I

-
.Q
'i:
en 0.4
is
CI)
Q.
>-
>. 0.2
C;
a...
0.0
SiC Ceramic Sintered with Band C
Figure 2.5 Polytype development as a function of temperature for B4C and Al doped ,B-SiC. (Williams, R.,
Juterbock, B., Shinizaki, A., Peters, C. and Whalen, T., 'Effect of sintering temperature on the physical and
crystallographic properties of ,B-SiC,' Bull. Am. Ccram. Soc., 64(10), 1385-93, 1985. Reprinted by permis-
sion of the American Ceramic Society, Westerville, OH.)

contain significant levels of oxygen. Since the
oxygen is usually present as an oxide layer on
the surface of powder particles, values tend to
increase as the surface area of the powders
increases. Silicon carbide (SiC) powders have
a surface oxide layer of up to 10 nm thick.
Upon heating, the oxide layer can generate
silicon monoxide (SiO) vapors according to
the reaction (Danes, Saint-Aman and Cou-
durier, 1993):
SiC + 2Si02 ----> 3SiO + CO (2.1)
This can lead to particle coarsening due to
vapor transport of SiC (Jacobsen, Lee and
Fox, 1992) and effectively retard sintering.
While it is desirable for enhanced densifica-
tion kinetics for the powders to be as fine as
possible, excessive oxygen levels :::;2.0 wt%
effectively limit the average particle size to
~100nm (Hausner, 1980).
SINTERING DEVELOPMENTS
Sintering aid discoveries were critical to the
development of SiC ceramics. Aluminum
(AI) and Fe were shown to be effective aids
in hot-pressing SiC powders to high density
at a temperature of 2273 K (2000C) and a
pressure of 40 MPa (,,-,395 atm) (Alliegro,
Coffin and Tinklepaugh, 1956). While this
was an important first step, the key discovery
was by Prochazka (1974).
Prochazka (1975) established the benefits of
small additions of boron (0.4%) and carbon
(0.6%) to the sinterability of SiC compacts.
Carbon reduces the surface oxide layer on
SiC powders at temperatures low enough
such that particle coarsening is not a factor.
As part thicknesses increase, however,
carbon monoxide partial pressures are suffi-
ciently high locally to retard the oxide reduc-
tion. Coarsening again becomes a problem
and leads to severe density gradients in thick
parts. In order to compensate for this effect,
extraordinary heating schedules have been
shown to be necessary (Ness and Rafaniello,
1994). Boron (B) is believed to lower grain
Silicon carbide 49
boundary free energy, but it is unclear
whether a liquid is involved or not. Addition-
ally, B has limited solubility in SiC of about
0.2-0.4 wt% (Prochazka, Giddings and John-
son, 1975; Murata and Smoak, 1978), which
could enhance Si diffusion in SiC through
defect generation. With this recipe, pressure-
less sintered SiC ceramics could be prepared
with fine SiC powders (Figure 2.6), although
the role of these additives has been the subject
of much debate.
While other sintering aid formulations have
been developed for SiC ceramics (Negita,
1986), B and/or Al with C continue to be the
most significant combinations. Aluminum has
been shown to be as effective as B in produ-
cing SiC ceramics with the desired perfor-
mance characteristics (Boecker, Landfermann
and Hausner, 1979; Schwetz and Lipp, 1980;
Tanaka et al., 1985). The specific ratio required
will depend on powder characteristics and
processing conditions. Some of these develop-
ments utilized liquid phase sintering tech-
niques through oxide additions (Sasaki et al.,
1987; Cutler and Jackson, 1989; Hamminger,
Kruner and Boecker, 1992). Reactive sintering
involving aluminum oxycarbide was also
demonstrated (Jackson et al., 1989). However,
high temperature properties suffered because
of the presence of an oxide grain boundary
phase.
While these sintering aid formulations are
equally effective whether you start with pre-
dominantly a-SiC (Coppola and McMurtry,
1976) or ,B-SiC powders, microstructural
development is very different. Photomicro-
graphs of samples sintered with Band Care
presented in Figure 2.7. Since required sinter-
ing temperatures often overlap with the 3C to
4H crystallographic transformation tempera-
ture, large plate-like a-SiC grains grow
within the ,B-SiC grains. If allowed to grow
too rapidly, grain impingement can occur
trapping pores and limiting final density.
Starting with a-SiC powders tends to result
in a more equiaxed structure and final densi-
ties are often higher for powders with similar
50 Critical powder characteristics
3200

III

/:>lwL%C
3000
III

E-- 2800
Powder Properties
-
~
~
en
No Added C (WI %) Ill. a.-SiC +<>13-SiC
c Clotal 29.59 30.88
! 2600
C'ree 0.09 1.84
N 0.03 0.07
0 0.81 0.62
Si02 1.52 1.17
2400 SA(m2/g 11.7 12.4

2200
Sintered at 2423K (2150"C) for 1hr
All samples contained 3 wt % C, except where noted

2000 0 II --'----'
1 2 5
Boron Carbide Addition (wt %)
Figure 2.6 Sintered densities at 2423 K (2150 DC) for 1 h, for a- and ,6-SiC powders as a function of B4 C and
C additions.

surface areas. Densification results showing
this effect are given in Figure 2.8.
EFFECT OF IMPURITIES
The influence of impurities on the elevated
temperature phase transformations and the
dynamics of microstructural development
are issues that must be understood and con-
trolled to ensure the preparation of high
quality ceramics. Particularly since, coincident
with these phase changes, exaggerated grain
growth is often observed. These large plate-
like grains that form ultimately lead to
strength limiting flaws. Transition metals, Al
and N would be the most common impurities
found in SiC powders. Aluminum tends to
stabilize the hexagonal modifications, particu-
larly the 4H structure (Shinozaki et al., 1988),
while boron stabilizes the 6H form (Kistler-De
Coppi and Richarz, 1986). Nitrogen (Jepps
and Page, 1983) and the transition metals pro-
mote the formation and the stability of the
cubic structure. This influence can be both
kinetic as well as chemical in nature. Alumi-
num and, to a lesser degree, boron can be
Figure 2.7 Photomicrographs of sintered SiC, showing effect of powder type and sintering additives on grain morphology. Samples prepared
with {3-SiC (A, C) powder resulted in elongated grains, whereas samples with a-SiC powder resulted in a more equiaxed microstructure (B,
0). For both powders, the addition of 1 wt% Al (C, 0) resulted in substantial overall grain growth and enhanced the formation of large
elongated grains. All samples contained 1 wt% B4 C and 3wt% C and were sintered at 2423K (2150C) for 1 h.
52 Critical powder characteristics
3200

3000

'1; 2800 Powder Properties

~ (wt %) a-SiC ~ 13-SiC
~
en
Ctotal 29.59 30.88
~ 2600
Clree 0.09 1.84
N 0.03 0.07
0 0.81 0.62
Si0 2 1.52 1.17
2400 SA(m2/0) 11.7 12.4

2200
All samples conlained 3 wi % C and 1 wt % B4C
Sinlered in Ar aim for 1hr

2000L--2~20-0---------2~30-0---------2~40-0---------25~0-0------

Temperature (K)
Figure 2.8 Sintered density as a function of temperature for a- and ,a-SiC powders containing 1 wt% B4 C
and 3wt% C.

accommodated into the SiC lattice. The solu-
bility limit of Al in SiC has been reported to
be about 1.0 wt% (Mitomo, Inomata and
Kumanomido, 1970; Tajima and Kingery,
1982). A detailed description of the micro-
structural changes that traditionally coincide
with the solid state sintering of SiC ceramics
is given by Shin ozaki and Kinsman (1978).
EFFECT OF PARTICLE SIZE AND METHOD
OF SYNTHESIS
There are powder specifications which must
be met in order to achieve the product quality
needed for the demanding applications in
which SiC is used. Powders with a surface
area 5-15 m 2 / g are needed to obtain high
density sintered parts (Prochazka, 1974). This
value can be achieved through milling or by
direct synthesis. While powders with a-
(hexagonal or rhombohedral unit cells) and
13- (cubic) SiC forms are available with this
minimum surface area, the a-type powders
are exclusively milled (Schwetz, 1989). Suit-
able j3-type powders can be prepared using
either approach, but as synthesized products
are more typical. An additional advantage
that powders synthesized directly have is
that in some cases the chemistry can be
modified to incorporate the appropriate
levels of free carbon and boron needed for
sintering.

While there appears to be little performance
distinction between ceramics prepared from
a- or ,a-SiC powders, differences in micro-
structural development can be dramatic and
a-SiC powders may allow for a broader pro-
cessing window. A reflection of the advanced
state of powder technology is that SiC can be
sintered to near theoretical density without
additives, but with pressure assistance. If the
average grain size was less than 0.6 /-tm, glass-
encapsulated a- or ,a-SiC powders could be
hot isostatically pressed (heated at ~2273 K
(1950C) in 150MPa (rv 1480atm) argon pres-
sure) to near theoretical density (Homma,
Yamamoto and Okada, 1987).
Even with fine SiC particles and the appro-
priate additives, sintering temperatures near
2273 K (2000 C) are needed to achieve full
densification. This fact also suggests that the
particle size distribution must be narrow and
that particles substantially greater than 1 /-tm
cannot be tolerated (Carlstrom et ai., 1983).
Additional considerations for achieving high
sintered densities with SiC powders include
the temperature profile and sintering atmo-
sphere (Greskovich and Prochazka, 1987).
SILICON NITRIDE (Si3 N 4 )
The unique combination of high fracture
toughness, lightweight, good high tempera-
ture properties (Hoffmann, 1995), excellent
thermal shock resistance and good tribological
characteristics make silicon nitride (Si3N 4) the
primary candidate for high performance
structural applications. Interest in Si3N4 as a
high temperature material started in the late
1960s to early 1970s. During this period,
even with extreme pressures and tempera-
tures, densification of Si3N4 particles was
difficult (Prochazka and Rocco, 1978). Since
Si3N4 dissociates at about 1773 K (1500C), a
temperature below which sintering would
not be expected to occur, significant technical
achievements were required to reach its status
as a reliable, high performance material.
Highly sinterable powder is important
Silicon nitride 53
because of the limit imposed by the Si3N4
dissociation temperature.
Silicon nitride (Si3N 4) has primarily two
crystallographic modifications (Jack, 1973).
Both forms consist of silicon surrounded by
four tetrahedrally oriented nitrogen atoms
and each nitrogen is part of three tetrahedra.
Beta (,8) Si3N4 is the high temperature phase
and has a hexagonal unit cell with an
ABAB . .. stacking sequence of Si-N layers.
This packing results in long continuous chan-
nels that run parallel with the c-direction.
Alpha (a) Si3N4 is also hexagonal, but the
Si-N layers have a stacking sequence of
ABCD . .. where the CD layers are shifted rela-
tive to layers AB in the c-plane. This shift
creates closed interstitial holes that can accom-
modate large cations.
Jack (1973) and Oyama (1972) indepen-
dently identified an important new class of
materials based on solid solutions of Si3N 4,
referred to as 'SiAlONs'. SiAlON is an
acronym for the prevalent solid solution
components, silicon, aluminum, oxygen and
nitrogen. While both species can readily
accept oxygen and aluminum substitutions,
it is only the a form that contains other
metals incorpQrated into the structure. Com-
positions with the a' -SiAlON crystal structure
have been prepared with most of the rare and
alkaline earth elements (O'Reilly et ai., 1993).
Since the sintering aids can be incorporated
into the SiAlON grains, the absence of a
grain boundary phase leads to better creep
and corrosion resistance. Because of their
similar chemistries, the SiAlONs are often
included in analyses of Si3N4 ceramics. How-
ever, in this work, these materials will be
discussed only superficially. A retrospective
and prospective on this subject is given by
Jack (1993).
SINTERING DEVELOPMENTS
Discoveries of sintering additives that enabled
dense Si3N4 ceramics to be manufactured
were key and enabling accomplishments. In
54 Critical powder characteristics
addition, the use of several pressure-assisted
densification techniques was developed to
facilitate densification and improve Si3N4
properties. Hot pressing (HP) (Deely, Herbert
and Moore, 1961; Lumby and Coe, 1970;
Lange, 1973; Komeya and Noda, 1974), gas-
pressure sintering (GPS) (Mitomo, 1976;
Greskovich, 1981) and hot isostatic pressing
(HIP) (Larker, Adlerborn and Boham, 1977;
Wills and Brockway, 1981) are all successfully
employed to produce high strength Si3N 4-
based ceramics. Once it was established that
these materials could be densified, an under-
standing of the dominant sintering processes
and mechanisms for microstructural develop-
ment became the focus of much research activ-
ity. The flow of information from the ceramic
research community led to significant
advances in powder quality as the critical
characteristics were identified. This interrela-
tionship between powder properties, ceramic
morphology and mechanical performance will
be further elucidated.
While solid state sintering of Si3N4 has been
demonstrated (Greskovich, 1979; Kanzaki,
1986; Ge, Xia and Chen, 1993), the discovery
of liquid phase sintering formulations was the
enabling technological achievement needed
for preparing high performance Si3N4 cera-
mics. Liquid phase sintering is the common
option employed for densifying Si3N4 cera-
mics because of its unlikely combination of
low solid state diffusion from strong covalent
bonds with a relatively low dissociation tem-
perature. Liquid phase sintering consists of
three phases (Kingery, 1959). Rearrangement
occurs early in the sintering cycle and is con-
trolled by capillary forces generated by the
formed liquid. The dissolution-precipitation
phase is next and the point in which the
unique microstructures that have been engi-
neered begin to evolve. The final step in the
process is coalescence of the grains and pore
removal. For liquid phase sintering to occur,
the following three conditions must be met:
(1) a liquid phase must be present at the sinter-
ing temperature; (2) there should be some
solubility of the solid in the liquid; and (3)
the liquid phase should wet the solid
(Mitomo, 1986). Silicon nitride (Si3N 4) formu-
lations that have evolved exemplify these char-
acteristics.
The first successful sintering formulation
for Si3N4 contained magnesium oxide (MgO)
(Deeley, Herbert and Moore, 1961). However,
MgO is an extremely refractory oxide that has
a melting point (rv 3100K; 2827C) above the
Si3N4 dissociation temperature at ambient
nitrogen pressures. Therefore, a second com-
ponent must be present with MgO to generate
the prerequisite liquid phase at the sintering
temperature. Silicon oxide present on the sur-
face of Si3N4 reacts with the sintering addi-
tives to form the essential liquid phase.
Liquid formation temperatures for several
reactive oxides with silica and Si3N4 are
shown in Table 2.1 (Riley, 1985). Nitrogen
solubility into the formed glass is also indi-
cated, since the presence of Si3N4 enhances
liquid formation. The amount of surface
oxide present will clearly affect the grain
boundary chemistry. The interaction of the
sintering aids with the surface oxide on the
Si3N4 powder generates the interfacial
chemistry that then helps dictate the ceramic
morphology and part performance. The
criticality of the surface oxide then establishes
one of the key powder traits that must be
controlled within a consistent and narrow
range. Oxygen contents of 1-2 wt% have
been reported to be preferred in order to
enhance densification and optimize mechani-
cal properties (Franz et al., 1989).
While numerous sintering formulations
have been developed for Si3N4 ceramics
(Anderson and Bratton, 1977; Lorenz, Weiss
and Petzow, 1982; Negita, 1985; Sanders and
Mieskowski, 1985; Komeya, 1993), the most
studied and utilized formulations include
some combination of yttria (Y203) and alu-
mina (AI20 3) (Komeya and Noda, 1974;
Mitomo and Mizuno, 1986; Woetting and
Ziegler, 1986; Kawashima et al., 1991). This
system appears to offer the ceramic manufac-
 Silicon nitride 55
turer the greatest latitude in terms of powder system is closed (silicon vapors cannot
characteristics and processing parameters in escape). The thermodynamic stability of
preparing Si3N4 ceramics for room and mod- Si3N4 as a function of temperature and pres-
erate temperature applications. The relative sure is represented schematically in Figure
ratio of these compounds has been varied 2.10. Pressure-assisted densification, either
depending on powder characteristics, process- GPS or HIP, also typically lead to either
ing conditions and desired properties. higher toughness or strength materials,
The nature of the sintering additives and respectively. The improvements in mechani-
resulting grain boundary phase have a pro- cal properties can also be maintained up to
found influence on the density, microstruc- higher temperatures because the amount of
tural development and properties of the sintering additives (liquid phase) required
sintered parts. Although not as well defined, for densification is less (Tajima, 1993).
the grain boundary phase composition can
have as much influence on its mechanical
EFFECT OF PARTICLE SIZE
performance as the grain morphology. This
effect has been particularly well documented High surface area powders are necessary to
for high temperature property measurements achieve acceptable sintered densities for the
(Tsuge, Nishida and Komatsu, 1975; Ander- desired level of performance (Woetting and
son and Bratton, 1977; Lange, 1983; Komeya, Ziegler, 1983). For advanced engineering
1993). In Figure 2.9, high temperature applications, the average particle size and
(1673 K, 1400C) flexure strength for Si3N4 surface area should be substantially less than
ceramics prepared with rare earth oxide addi- 0.5 pm and above about 10 m 2/ g, respectively.
tions are shown as a function of the metal ionic The particle size distribution (PSD) should be
radius. The eutectic melting temperatures for well characterized since it is one of the impor-
these oxides are also given. tant parameters that controls microstructural
Multiple component systems have been development in Si3N4 ceramics (Hirotsuru,
developed to achieve an optimum combina- Isozaki and Yoshida, 1994). Large ceramic
tion of processibility and performance grains have been shown to be strength limit-
(Pyzik, Carroll and Hwang, 1993). The ing flaws in Si3N 4. Limiting the size of the
additives consist of glass formers, viscosity starting powder to submicron particles helps
modifiers and nucleation catalysts. Formu- limit the size of the resulting strength limiting
lations containing A120 3 yield products that flaws. While it has been recognized that the
contain (3'-Si3N 4 or SiAlON depending on fracture toughness of Si3N4 increases with
the level of aluminum in solid solution. grain diameter, there is a practical limit near
When the alternate MgO is used instead of
A1 20 3, the solid solution phases are not
formed due to its limited solubility into (3- Table 2.1 Liquid formation temperatures for sev-
eral reactive oxides with Si02 and Si3N4 (adapted
Si3N4 (Jack, 1976; Lange, 1978).
from Riley, 1985)
Traditionally, powder beds have been
employed to surround the part in a 'protective Oxide M xOy-Si02 MxOy-SiOrSi3N4
envelope' that acts to suppress decomposition (K (OC)) (K (OC))
and weight loss. This is also the goal of gas
pressure sintering (GPS). By increasing the MgO 1816 (1543) 1663 (1390)
Y203 1923 (1650) 1753 (1480)
N2 pressure to 1 MPa (rv l0atm), Si3N4 is
CaO 1708 (1435) 1708 (1435)
stable up to about 2100 K (1823C). Even Al20 3 1868 (1595) 1743 (1470)
higher temperatures can be used if higher Ce02 1833 (1560) 1733 (1460)
nitrogen pressures are maintained and the
56 Critical powder characteristics
10/-tm because of the strength limiting effect
(Kawashima et al., 1991).
EFFECT OF a/f3 PHASE RATIO
The relative Si3N4 a/ (3 phase ratio is another
important powder property that must be
controlled. Lange (1979) first recognized the
importance of this ratio in engineering micro-
structures with long, acicular grains. It was
reported that the use of primarily (3-Si3N4
powder resulted in a more equiaxed micro-
structure, since normal grain growth is
involved (Mitomo et al., 1990). Powders with
high levels of alpha phase lead to a bimodal
grain structure, consisting of several long
whisker-like grains in a relatively fine-grained
matrix. This type of self-reinforced structure
(SRS) contributes significantly to the relatively
high, from a ceramic perspective, fracture
toughness (Hirotsuru, Isozaki and Yoshida,
1994) measured for Si3N 4. Reported fracture
toughness values have ranged between 4 and
12 MPa . m 1/2. The lower toughness Si3N4
materials have relatively equiaxed grains
(Wills and Brockway, 1981), while the tougher
materials have a more composite-like appear-
ance. This distinction can be seen in Figure
2.11 where photomicrographs of fracture
surfaces for two Si3N4 ceramics are shown.
The fine-grained material has a toughness
value of about 6 MPa . m 1/2, while the material
with the duplex structure has a fracture tough-
ness of about 9.5 MPa . m 1/2. These needle-like
grains grow out of the formed liquid-grain
boundary phase that also contained dissolved
a-Si3N4 grains. Grains with the proper orien-
tation to promote the columnar growth then
form from (3-Si3N4 nuclei. A schematic of
this process is shown in Figure 2.12. While
several energy models have been proposed
to explain this growth phenomenon, the
improved resistance to crack propagation of
the resulting microstructures has been attribu-
ted to crack bridging, crack deflection and/ or
grain pull-out (Becher et al., 1993). Some of
these mechanisms can be seen in Figure 2.13,
where a crack path through an SRS Si3N4
ceramic is shown.
The size and distribution of (3-Si3N4 particles
also greatly influences the final microstructure
(Mitomo et al., 1990; Mitomo and Uenosono,
1992; Hoffman and Petzow, 1993). There
appears to be an optimum level of (3-Si3N4
that creates a microstructure with the highest
fracture toughness. Too little (3-Si3N4 leads to
coarse equiaxed grains, while too much results
in a finer microstructure due to impingement
of growing grains. Duplex microstructural
development for Si3N4 ceramics was thought
to be fundamentally linked with the alpha to
beta transformation. However, ceramics of
high toughness have been prepared from
100% (3-Si3N4 powders (Hirosaki, Akimune
and Mitomo, 1993). This was accomplished
by adding controlled levels of large (3-Si3N4
particles to fine powders that allowed the com-
posite-like, duplex microstructure to develop
through a normal grain growth phenomenon.
EFFECT OF IMPURITIES
As in other advanced non-oxide ceramics,
there are some specific powder issues that
are directly related to the method used to
produce those powders. Metallic inclusions
and hard agglomerates have been identified
as primary sources for the strength-limiting
flaws in Si3N4 ceramics (Pasto, 1984). The
prevalence of iron inclusions or formed iron
silicides in direct metal-nitrided powders
greatly limited their acceptance for high per-
formance applications. Free or residual silicon
has been a concern for these powders as well.
However, these problems also provided clear
guidelines for powder quality improvements.
There has been a significant effort to mini-
mize the carbon content of Si3N4 powders.
The carbon levels have been typically near
0.1 wt%. However, the form of carbon that is
present is unclear. It could be free graphite
or bound as part of a carbide. In any case,
carbon has been shown to impede the
sinterability of Si3N4 ceramics (Franz et al.,
 Silicon nitride 57

--
2000,----------------------------------,
::.c::
'"
'E
....
s .
+.

.....

.
.. ".
.......................
CI.. 1900 '
en

==
a:; '"
~ ................. .
::E .. .....
~
c.:I
1800 ". ."
...... .. ...... ~ ..
oS
::::II
.- .-
...... . . , , - ' - ........ - 1

LLI

8c Yb Er Dy 8m Pr e
1700
Y Gd Nd La
600

-ca
CI..
t:.

~
::.c:: 500
.....
C":I

--
,....
CD

ca
.c
400
...=
en

-...
CI)

C I)

C;
t:.

::::II
>< 300
CI)
t:.
u::::
~

200
0.08 0.09 0.10 0.11
Ionic Radius (nm)
Figure 2.9 Study of rare earth sintering additives for silicon nitride. High temperature strength correlated
to eutectic melting point in Si3N4-MxOy-Si02 system and ionic radius of metals.

1989). Carbon can change the localized glass many of these will be addressed in later
chemistry by reducing the surface oxide or chapters, three approaches have been shown
added materials. The sintering behavior to be commercially viable. The basic chemis-
could also be hindered by coarsening of the tries involved for these three processes are
Si3N4 particles by SiO vapor transport. summarized in Table 2.2. Typical powder
characteristics and the effect on sinterability
and performance have been summarized
EFFECT OF SYNTHESIS METHOD
previously (Woetting and Hausner, 1983; Hof-
While there have been numerous methods for mann et al., 1993; Woetting, Feuer and Gugel,
synthesizing Si3N4 powders attempted, and 1993).
58 Critical powder characteristics
Pressure PN2 (Atmospheres)
10-3 10.2 10.1 10 101 102 103
10.2 3

10-3 2

-..'" SI(I) +SI(V) +N2(g)

-
QJ
as
-=CI.
-
--
'"0
. SbN4(S) + SI(S)
Ie
0 a..
~ +SI(I) +SI(V) Ci.i
Ci.i +N2(g) 1 a..
Q.
~
as
; .....
Q

..
'"""as
2

/;
Q.

3
SI(S) +SI(V)
+N2(g) 4

5
2 3 4 5 6 7 8
LOG p~ (Pa)
Figure 2.10 Thermodynamic stability diagram for Si3N4 as a function of N2 pressure, Si(v) pressure and
temperature.

Powder specifications (targets) that have
evolved are summarized in Table 2.3 (Hof-
mann et al., 1993). However, these require-
ments will continue to change until the
interrelation between powder properties,
processing, microstructure and performance
are explicitly determined. The complexity
of the situation is illustrated in Figure 2.14
(Kanzaki, 1986).
ALUMINUM NITRIDE (AIN)
While aluminum nitride (AlN) had been eval-
uated in a number of applications since it
was first synthesized in the 19th century
(Briegleb and Geuther, 1862), it was the recog-
nition of its potential as a highly thermally
conductive dielectric material that established
it as an important advanced ceramic (Slack,
1973). The theoretical thermal conductivity
value for single crystal AIN was estimated
to be k=319W/mK (Slack et al., 1987).
While thermal conductivities up to about
k = 285 W 1m K (Guiton, Volmering and Kil-
linger, 1992) have been reported for polycrys-
talline AlN, nearly 20 years of technological
advances were necessary to reach this point.
Many of these steps involved improvements
in powder quality and the establishment of a
thorough understanding of the interrelation-
ship between powder qualities, processing
conditions, microstructural characteristics
and performance. This compilation of knowl-
edge was obtained in a relatively modest time

Figure 2.11 (Opposite) Fracture surfaces of silicon nitride ceramics showing range of microstructures
possible. Material (L), with large elongated grains has a measured fracture toughness of ~9 MPa. m 1/2
While material (F), with a fine, more equiaxed microstructure had a fracture toughness of ~6 MPa . m 1/2.
Aluminum nitride 59
60 Critical powder characteristics

-.
Sintering
a-Si3 N4 Additives
Si0 2- _ g eGO Heat
...
+ 0:(8

sur'ac;s--,...

containing consisting 01 Oxynitride Glass

-5% p-Si3N4 nuclei glass formers, viscosity Dissolves fine a-Si 3N4
Q modifiers and
nucleation catalysts Reprecipitates as columnar
P-Si 3N4Grains

Figure 2.12 Schematic showing microstructural development for self-reinforced silicon nitride (SRS) cera-
mics. Fine o:-Si3N4 particles are dissolved in molten glass, from which columnar ,B-Si3N4 grains grow.
Chemistry of glass directly impacts sintered density, microstructure and ceramic properties. The grain
boundary composition is controlled by surface oxide of Si3N4 powder and oxide additions. (Pyzik, A.J.,
Carroll, D.F. and Hwang, c.J., 'The effect of glass chemistry on the microstructure and properties of self-
reinforced silicon nitride,' in Silicon Nitride Ceramics - Scientific and Technological Advances, MRS Symp. Froc.,
Vol. 287 (eds I.-W. Chen, P.F. Becher, M. Mitomo, G. Petzow and T.-S. Yen), pp. 411-16, 1993. Reprinted
by permission of the Materials Research Society, Pittsburgh, PA.)

period and was led by pioneering efforts at
Toshiba, Tokuyama Soda, General Electric
and NEC. Later, Carborundum, Sumitomo
Electric and The Dow Chemical Company
also made significant contributions.
SINTERING DEVELOPMENTS
As with other advanced non-oxide ceramics,
the availability of high quality powders was
crucial to the development of AIN ceramics.
The initial hurdle to overcome was the fabrica-
tion of high density AlN parts. Hot pressing
was successfully used to prepare dense AlN
(Taylor and Lenie, 1960); however, these
results could not be consistently duplicated
by others. Conflicting sintering observations
were attributed to differences in powder char-
acteristics. It was thought that at least 2 wt%
oxygen was needed to densify AIN without
any sintering additives (Sakai and Iwata,
1977; Prochazka and Bobik, 1980). Other fac-
tors, such as a broad particle size distribution
and the presence of large aggregates, were
also reported to be particularly detrimental
(Culbertson and Mathers, 1982). Since the
thermal driving force available for AlN densi-
fication is limited to about 2273 K (2000 C), it
was felt that high surface area powders were
also needed. However, as higher quality pow-
ders became more readily available, conclu-
sions regarding the inherent sinterability of
AlN had to be modified. High density parts
were prepared by pressureless sintering with-
out additives using an AIN powder that had a
surface area of about 3 m 2 / g with a narrow
particle size (O.2-1.0/Lm) distribution (Kura-
moto, Taniguchi and Aso, 1989).
These observations would suggest that AIN
self-diffusion is relatively fast and is some-
what unique among the more traditional
non-oxide ceramics discussed previously.
For submicron powders, atomic diffusion
appears to be sufficiently rapid to enable
densification. Under these conditions, grain
boundary diffusion dominates and sintering
 Aluminum nitride 61

Figure 2.13 Photomicrograph showing crack path in silicon nitride: many of the possible mechanisms for
fracture toughness enhancement in silicon nitride are evident. (,Technology of self-reinforced silicon
nitride,' Pyzik, A.J. and Carroll, D.F. Reproduced, with permission, from the Annual Review of Materials
Science, Vol. 24, pp. 189-214, 1994, by Annual Reviews, Inc., Palo Alto, CA)

with densification occurs (Komeya and Inoue,
1969). However, this could be misleading
based on the prevalent oxide character of
AlN powder surfaces (Slack and McNelly,
1976; Paquette et al., 1990; Seitz et al., 1991).
While the impact of the oxide surface on
densification and thermal conductivity will
be addressed later, the absence of sintering
additives does not preclude the presence of a
liquid phase. The sinterability implies that
AIN has a relatively high atomic diffusion
rate. This result could have been anticipated
since the large electro negativity difference
between the elemental constituents, alumi-
num and nitride, suggests that the bond
strength is less covalent in nature than other

Table 2.2 Commercial synthesis routes for Si3N4 powders

Synthesis method Chemistry

Nitridation of silicon 3Si(s) + 2N2(g) -> Si3N4(s)

Carbothermal reduction and nitridation
Imide decomposition
flH = -732 kJ / mol (1600 K; 1323 0c)
3Si02 (s) + 6C(s) + 2N2(g) -> Si3N4(s) + 6CO(g)
flH = 1268kJ/mol (1700K; 1423C)
SiCl4(g) + 6NH3(g) -> Si(NH)z(s) + 4NH4Cl(S)
3Si(NH)2(s) -> Si3N4(s) +2NH3(g)
(1473-1773K; 1200-1500C)
62 Critical powder characteristics
Table 2.3 Targeted Si3N4 powder specifications
Property Requirement
Particle size 0.S-O.8p,m
mean grain diameter
Distribution Narrow
Maximum ::;2p,m
Chemistry
Metals ::;0.01 wt% total metals
(Fe, Ti etc.)
Oxygen ::;2.0wt%
Carbon <0.02 wt%
Phase composition High O! content
(>90% but ::;98%)
Source: Hoffman, M.J. and Petzow, G., 'Microstructural
design of Si3N4 based ceramics,' in Silicon Nitride Ceramics
- Scientific and Technological Advances, MRS Symp. Proc., Vol.
287 (eds I.-W. Chen, P.F. Becher, M. Mitomo, G. Petzow
and T.-S. Yen), pp. 3-14, 1993. Reprinted by permission
of the Materials Research Society, Pittsburgh, PA.
advanced non-oxide materials. Its ionicity is
also reflected by a larger band gap and higher
dielectric constant (Cormack, 1989). Weaker
atomic bonding would also help rationalize
substantially lower hardness values measured
for AlN compared to these other ceramics.
It has been shown that given the appropri-
ate powder characteristics and processing
conditions, AlN can be sintered without
additives to high density. However, the
effect of additives on the pressureless sinter-
ing of AlN has been studied extensively (Pro-
chazka and Bobik, 1980; Komeya, Inoue and
Tsuge, 1981; Schwetz, Knoch and Lipp,
1983). Alkaline earth and rare earth com-
pounds were consistently found to be the
most effective sintering additives. The exten-
sive work by Komeya and co-workers at
Toshiba is summarized in Table 2.4.
One obvious commonality of the rare and
alkaline earth additives is that a mixed metal
aluminate is formed during the sintering pro-
cess. The aluminates form through a reactive
process between the sintering additive and the
oxygen containing surface layer of the AlN
particles. Some systems, such as CaO-Alz03
and Yz0 3-Alz0 3 have several stable mixed
metal oxide compounds. The aluminate
species that form will depend on the oxygen
content of the AlN powder, the amount of
sintering aid added and the processing condi-
tions (Guiton, Volmering and Killinger, 1992).
It has been recognized that the maximum
sintering rate often coincides with the onset
of melting for the specific aluminate(s).
It has been shown by high temperature x-
ray diffraction studies that in the YZ0 3-
Alz0 3 system, the reactive aluminates form
prior to the onset of melting (Hubbard et al.,
1992). While not considered a model example
for liquid phase sintering (Komeya, 1985),
AlN densification with these additives clearly
proceeds through a traditional sequence of
first particle rearrangement, then solution-
reprecipitation and finally grain growth
(Kuramoto, Taniguchi and Aso, 1989). Recent
work (Kim, Kim and Kim, 1995) has also
shown that improvements in distribution of
the sintering additives allows for higher den-
sification rates.
Criteria established for identifying suitable
AlN additives using thermodynamic consid-
erations included: (1) chemical compatibility
at the sintering conditions; and (2) the forma-
tion of a liquid phase below about 2000 K
(1727C) to enhance densification (Schuster,
1987). The findings of this theoretical analysis
were consistent with previous experimental
observations.
EFFECT OF OXYGEN
In electronics, the utilization of AlN was criti-
cally dependent upon achieving a minimum
thermal conductivity of k = 150 W / m . K.
There are numerous paths that one can take
to achieve this performance target, but the
suitability of these options is greatly influ-
enced by the characteristics of the AlN
powder. Specifically, the oxygen content of
the starting AlN powder plays a very signifi-
cant, if not enabling, role (Guiton, Volmering
and Killinger, 1992). The importance of
oxygen impurities on lowering the thermal
 Aluminum nitride 63

Starting Powder Ic::-------- Powder characteristics: particle size,

distribution, shape, specific surface area,
aggregation
Chemical composition: stoichiometry,
impurity types, quantity, distribution

Crystallinity: a-phase,
~-phase, amorphous

Mixing . . . . . . , , - - - - - - - Sintering aid: types, quantity,

particle size, purity

Mixing method: homogeneity,

contaminants (type and quantity)

Molding 1-_ _ _ _ _ _ _ Molding method: additives,

homogeneity, density of green body

Solid state}
Sintering .. { Sintering ~ethod: furnacing, temperature,
Liquid phase pressure, time, atmosphere, cycle

~
.
Grain boundary phase:
amorphous, crystalline

Chemical composition, quantity, melting point

(eutectic point, softening point), viscosity,
wettability, reactivity (solubility)

Figure 2.14 Schematic of numerous parameters involved in the fabrication of reliable, high performance
Si3N4 ceramics.

conductivity of AlN was recognized early
(Borom, Slack and Szymaszik, 1972) and con-
tinues to be of critical importance, particularly
for fine submicron powders (Watari et al.,
1995).
There are effectively three forms of oxygen
present in AIN powders. Adsorbed water
would be one source. However, under typical
processing conditions, this oxygen source
rarely influences product quality since it is
easily removed by heating at modest tempera-
tures, ",373 K (100 e). Oxygen can also be
present on the powder surface. The nature of
this oxide coating has profound effects on
powder handling, processing and overall
ceramic quality. Details of these interactions
will be discussed below. The third oxygen
form present in AIN is dissolved in the
matrix. Oxygen substitution for nitrogen in
the wurtzite structure leads to Al vacancies.
Equation 2.2 demonstrates this effect using
the Kroger-Vink notation:
64 Critical powder characteristics
Table 2.4 Results of AlN sinteringa with various Above a few percent oxygen, lattice strains
additives become sufficient to disrupt the wurtzite crys-
tal structure. First a distorted wurtzite struc-
Aid Density X-ray phases b
(5wt%) (%TD)
ture is formed. Then higher order hexagonal
polytypes develop. At still higher oxygen
Category I levels, the aluminum oxynitride spinel,
BN 76 AlN, X, BN AION, becomes stable (McCauley and
SI3N4 70 AlN, X, Si3N4 Corbin, 1983).
MgO 65 AIN, X,? The theoretical thermal conductivity value
Si02 65 AIN, X,?
was estimated to be k = 319W1m K for
Mn02 72 AIN, spinel
SiC 65 AIN, ? single crystal AlN at room temperature
AI-silicate 77 AIN, X,? (Slack et al., 1987). Phonon conduction, being
Mg-silicate 73 AlN, X,? the primary heat transfer mechanism in AlN,
is easily disrupted by microstructural anoma-
Category II lies like grain boundaries and lattice defects.
TiN 81 AIN, X, TiN The aluminum vacancies generated by the
ZrN 81 AIN,X, ZrN presence of oxygen contamination act as
HfN 79 AIN, X, HfN, spinel
defect sites which severely limit phonon con-
Ti02 78 AIN, X, TiN, spinel
zr02 81 AIN, X, ZrN, spinel duction (Slack, 1973). This is one of the
Al20 3 81 AlN, X, spinel primary reasons why oxygen control is critical
Cr203 80 AIN, spinel for achieving high performance AlN ceramics.
NiC03 86 AIN, Ni3N, spinel Advanced analytical methods allowed the
zrC 79 AIN,X, ZrN oxygen dissolved in the AlN lattice to be
TiC 80 AIN, X, TiN determined for samples in which the bulk
Ni 78 AIN, X, Ni3N
thermal conductivity was also measured
(Potter, Knudsen, Tou and Choudhury, 1992).
Category III
CaC03 98 AIN, CaAI40 7 , The experimental results are compared to the
CaAl20 4 predicted relationship in Figure 2.15.
SrC03 95 AIN, ? Understanding the role of oxygen contami-
BaC03 96 AIN, BaAI120 19 , nation in determining thermal conductivity
BaAl20 4 was a pivotal contribution, since it helped
Y203 97 AlN, Y3AIs0 12 , lead to the discovery of appropriate sintering
spinel
additives that allowed AlN to achieve high
La203 98 AlN, LaAI03, ?
Ce02 96 AlN, CeAI03, ? thermal conductivity. Rare and alkaline earth
Pr0 2 97 AlN, PrAI03, ? elements, particularly yttrium (Y) and calcium
Nd 20 3 98 AlN, NdAI03, ? (Ca) containing compounds, were shown to be
Sm203 97 AIN, SmAI03, ? highly effective in densifying AlN ceramics.
Gd20 3 96 AIN, GdAI03, ? These compounds provide the needed fast
DY2 0 3 95 AIN, Dy3AIs012 diffusion route for liquid phase sintering and
aSintering conditions: 1800C, 30min, I atmN2 also acted as an oxygen sink. The effectiveness
bX = AlN polytype; ? = unknown phase. of these compounds in capturing oxygen from
Source: Komeya, K., 'Development of aluminum nitride the AlN matrix was theoretically verified
ceramics,' Ceramics (Japan) Seramikkusu, 20(6), 506-12,
1985. Reprinted by permission of The Ceramic Society usin'g' thermodynamic principles (Virkar,
of Japan, Tokyo, Japan. Jackson and Cutler, 1989). It was predicted
and experimentally verified (Figure 2.16) that
thermal conductivity should increase when
the Y-rich aluminates are present.
 0.0 0.2 0.4 0.6 0.8 1.0
Lattice Oxygen (wt %)
Figure 2.15 Results of two advanced analytical methods, electron microprobe and secondary ion mass
spectroscopy (SIMS) verify the critical role oxygen contamination in the AIN lattice has on bulk thermal
conductivity. (Potter, G.E., Knudsen, A.K., Tou, J.e. and Choudhury, A., 'Measurement of the oxygen and
impurity distribution in polycrystalline aluminum nitride with secondary ion mass spectrometry,' J. Am.
Ceram. Soc., 75(12), 3215-24, 1992. Reprinted by permission of the American Ceramic Society, Wester-
ville,OH.)

EFFECT OF IMPURITIES has a negative influence on sinterability (Hor-

Other chemical factors that affect AlN powder
quality include the carbon level and trace
levels of impurities, primarily Ca, Si and Fe.
Like oxygen, carbon may be present in several
forms. There can be free carbon as a result of
incomplete reaction or contamination from
furnace hardware. Since AI2(OC) is isostruc-
tural with AlN and completely miscible, there
is potential for carbon to substitute for N in the
wurtzite lattice (Kuo and Virkar, 1989). There
may also be some amorphous carbon as a by-
product of an organic residue. While carbon
can disrupt the color of AlN parts, its primary
impact occurs during sintering. Through the
reduction of the oxide phases and generation
of CO, carbon promotes coarsening and hence
vath, Witeck and Harmer, 1989). However,
since carbon can facilitate oxygen removal,
thermal conductivity can be enhanced.
Silicon can substitute at Al sites in the AIN
lattice and disrupt thermal conductivity. As
shown in equation 2.3, Al vacancies are gener-
ated when silicon enters the lattice. This effect
was most significant when Y203 was used as
the primary sintering aid (Baranda, Knudsen
and Ruh, 1993). In earlier work, it was shown
that high strength ceramics could be produced
from silica containing Y20rdoped AlN
(Komeya and Inoue, 1971; Komeya and
Noda, 1974). This improvement was attributed
to the formation of needle-like grains that were
identified as higher order SiAION polytypes as
well as a distorted wurzite structure (Komeya,
66 Critical powder characteristics
en Content - AIN Powder
Powder Surface Lattice Total Relative Grain Boundary Amounts Estimated
A 0.63 0.45 1.08 From X-ray Diffraction Peak Intensities
B 0.58 0.37 0.95
200 C 0.40 0.36 0.76 Powdar

0
--
i2' A

-
E B
~ 180
~
-0 C

>
~ 160
-0 0.\1
=
"1:lI
I: o tJ.
CI

..
c.:I
ii 140
E
CD
.c
I- 120

100~L-~----~---.----'----''-+---.----r---.---.---''---~
o 1 234 2Y203 0 AI203 Y203oAI203 3Y2030 5AI203
Y203 Addition (wt%) Phase Chemistry
Figure 2.16 The thermal conductivity (TC) of three AlN powders having different oxygen characteristics
are studied as a function of added Y2 0 3 . TC increases with Yenrichment of grain boundary phase. (Guiton,
T.A., Volmering, J.E. and Killinger, K.K., 'Optimization of aluminum nitride thermal conductivity via
controlled powder processing,' in Better Ceramics through Chemistry, MRS Symp. Froc., Vol. 271 (eds M.J.
Hampden-Smith, W.G. Klemperer and c.J. Brinker), pp. 851-56, 1992. Reprinted by permission of the
Materials Research Society, Pittsburgh, P A.)

Inoue and Tsuge, 1974):
Si02 ~ SiAl + 20N + V AI
In addition to Si, Fe was also shown to
decrease thermal conductivity in AIN (Kura-
moto et al., 1985). Therefore, there was signifi-
cant emphasis on maintaining powder purity
to maximize thermal conductivity. However,
later experiments that extensively studied
the effect of transition metal additions
seriously questioned the necessity of high
purity powders. It was shown that AIN cera-
mics with thermal conductivities between
k = 150 and 250 W / m . K could be prepared
with 3.0 wt% Y203 and 0.3 wt% of the metal
impurities (Kasori, Veno and Tsuge, 1994).
There is also some concern for the concentra-
tion of trace radioactive elements in AIN. In
sensitive electronic devices, stray o:-particle
emIssIons from V and Th may cause soft
errors (May, 1979).
(2.3)
EFFECT OF SYNTHESIS METHOD
During the emergence of AIN technology,
several powder-specific biases developed
that were attributed to the synthesis method
employed. Carbothermal reduction and
metal nitridation were the two manufacturing
methods that received the most attention. The
AlN powders that were produced in this time
period were fundamentally different in
several critical categories and these distinc-
tions seemed to be more dependent on the
manufacturing method rather than the manu-
facturer (Rafaniello, Paquette and Rey, 1990).
Common observations of carbothermally pro-
duced powders were fine, uniform equiaxed
particles, low metallic impurities and higher

carbon and oxygen levels. The parts produced
from these powders were more easily sin-
tered, had better color uniformity, but started
with a lower green density. Ceramics made
with nitrided aluminum powders were at the
opposite end of the spectrum for these areas
(Skeele and Rafaniello, 1990). In addition, the
hydrolytic stability was lower for the nitrided
powders (Kuramoto, Taniguchi and Aso,
1989) but high thermally conductive compo-
nents could be prepared using either type of
powder (Weimer et al., 1994).
Since these distinctions were significant,
there was a concern that the AlN materials
were in fact fundamentally different. Efforts
to refute this premise were largely successful
(Ponthieu et al., 1991). Specific unit operations
in the respective manufacturing processes
were primarily responsible for the unique
character of the AlN powders. Excess carbon
is often used during the carbothermic reduc-
tion operation. Removal of this undesirable
by-product consisted of an oxidation step
at modest temperatures, <1273 K (1000C).
While this step effectively removed the
carbon, it also oxidized the surface of AlN
particles sufficiently to form a contiguous
AION layer that was highly resistant to hydro-
lytic attack (Paquette et al., 1990). This step is
unique to carbothermally prepared powders.
It would not be typically used for AIN pre-
pared by direct nitridation. Hence, reactivity
with moisture is greatly reduced for carbo-
thermally synthesized powders. The chemis-
try of this reaction, shown in equation 2.4,
while undesirable in high-tech ceramics, was
responsible for the first commercial use of AIN
as a fertilizer (replenishing nitrogen in the
soil) (Hershman, 1916):
AIN + 3H2 0 ----> AI(OHh + NH3 (2.4)
Reactivity of nitrided powders is usually
intensified by the milling or finishing opera-
tion that has been traditionally used. These
processes generate fresh surfaces which are
significantly more sensitive to moisture attack
and the release of ammonia. The milling
Summary 67
procedure is effective in reducing the average
particle size of the powder. The broad particle
size distribution leads to higher density green-
ware, but the sinterability of these powders, as
discussed earlier, is adversely affected by the
presence of even small amounts of large AIN
particles, about 5-10 /-tm (Skeele and Rafa-
niello, 1990). If the surface oxide could be
stabilized and made contiguous, and the
particle size distribution narrowed (eliminat-
ing large particles), then the quality of AIN
powders prepared by direct metal nitridation
could be substantially enhanced.
SUMMARY
The use of ceramics has been and will con-
tinue to be limited to applications in severe
environments that require wear resistance,
chemical resistance or thermal refractoriness.
Finding the appropriate ceramic solution
necessitates a thorough understanding of the
critical powder issues for that material and
application. Through this knowledge base,
the engineer can make effective and efficient
choices for selecting raw materials and unit
operations.
Each non-oxide ceramic has a unique criteria
set that must be met to obtain the targeted
property value. Controlled chemistry and
fine-grained powders are essential elements
for all advanced ceramics. For engineered
non-oxide ceramics, regulating carbon content
and surface and bulk oxygen are specifically
important. Overall powder purity, primarily
assessed by the amount of transition metals
present, can be critical for some applications.
However, in order to achieve the acceptable
cost-performance thresholds that will allow
the continued growth of non-oxide ceramics,
impurities need to be managed appropriately,
but not excessively.
Process innovation must continue to bring
total ceramic manufacturing costs down and
increase product volumes. Finally, new
design approaches must be implemented
that extract more value from these advanced
68 Critical powder characteristics
non-oxide ceramics and go beyond simple
material substitution.
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PART TWO
CARBOTHERMAL REDUCTION
SYNTHESIS PROCESSES
Carbothermal reduction is the primary chem-
istry practiced commercially for the synthesis
of many non-oxide ceramic powders, particu-
larly carbides such as silicon carbide (SiC) and
boron carbide (B4 C). Part Two begins with a
review of the thermochemistry and kinetics
(Chapter 3) of the carbothermal reduction
synthesis of carbides, nitrides and borides.
This is followed by an in-depth review of
SiC powder synthesis as practiced by the
Acheson process (Chapter 4) at the turn of
the century and as currently operated in
today's improved commercial plants. In
Chapter 5, the electric arc furnace process is
reviewed with particular attention given to
the commercial manufacture of B4 C powder.
The development of advanced continuous
carbothermal reduction reactors is then pre-
sented in Chapters 6 (pusher and moving
bed reactors), 7 (rotary tube reactors) and 8
(fluidized bed reactors).
OVERALL PROCESS
In general, the carbothermal reduction reac-
tion occurs between a carbon source and at
least one metal oxide. The carbon source can
include petroleum coke, purified graphite,
carbon black, or the residue from a pyrolyzed
organic material such as a polymer, cellulose,
or a carbohydrate, among others. The reactions
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
are typically carried out at atmospheric pres-
sure, but very high temperatures which are
close to if not above the melting temperature
of common steel. A crude reaction product
powder from the reactor typically comprises
the desired non-oxide powder, unreacted resi-
dual excess reactant, trace quantities of the
limiting reactant, and chemical impurities
which were present in the starting raw
materials. By-product carbon monoxide gas
is also generated by the reaction. In some pro-
cesses operation is carried out in vacuum,
whereby carbon monoxide (CO) and certain
impurities are removed during the reaction
step. Either the carbon or metal oxide reactant
component can be used in excess. The excess
component is typically selected on the basis
of how easily it can be removed from the
desired product powder in post processing
purification steps.
High reaction temperatures for these reac-
tions provide engineering challenges with
regard to processing, particularly reactor
design. In addition to the reactor, process con-
siderations include the steps of preparing
reactant precursors for reaction and the finish-
ing of crude reacted powder to a final product.
The preparation of precursors is not included
in this text, but obviously depends upon the
type of reactor being used. Precursor prepara-
tion can be simply the mixing of the carbon
76 Carbothermal reduction synthesis processes
and metal oxide in blenders to provide an
intimately mixed powder. This simple
method is quite suitable for processes such
as the Acheson process or the arc furnace
process. Other processes, such as rotary tube,
moving bed, or fluidized bed reactor pro-
cesses, require a more aggregated precursor
which can be prepared by pelletizing or
spray drying. Finishing steps typically
depend on a number of issues including the
best methods to remove the excess reactant
and the desired purity and particle size of
the final product. Typical post processing
finishing steps may include grinding, leach-
ing, calcination, filtering, decanting, drying,
de-agglomeration and lot blending to attain
final product specification. Some of these are
reviewed in Part Seven.
SAFETY ISSUES
Specific safety concerns for carbothermal
reduction synthesis include, but are not
limited to, the handling of fine dusts (indus-
trial hygiene as well as dust explosion consid-
erations), by-product CO and other toxic
gases, asphyxiating inert gases and the opera-
tion of high temperature graphite reactors.
Proper dust collection equipment (bag fil-
ters, scrubbers etc.) and personal protection
equipment (respirators) are a must around
powder blending, collection, milling and
packaging operations. Submicron-sized pow-
ders which are handled in various unit opera-
tions have the potential of being respirable.
The Material Safety Data Sheets (MSDS) for
the specific compounds being handled need
to be reviewed and the appropriate guidelines
followed. Some powders have lower allow-
able concentration levels in the air than
others and need to be handled more strin-
gently. Clean-up of certain powders may be
better suited by wet methods than by sweep-
ing. Also, the use of more expensive high
efficiency particulate air (HEP A) vacuum
filtering equipment needs to be considered
for such powders as crystalline quartz. In
general, proper exhaust system design and
personal protective equipment should be
used to reduce dust hazards.
Carbon monoxide (CO), the by-product of
all carbothermal reduction reactions, is a
colorless, odorless, toxic, flammable gas and
needs to be properly monitored and disposed
of. Area CO monitors need to be installed
around reactors and other equipment contain-
ing CO so as to warn operating personnel of
gas leaks in process areas. Carbon monoxide
(CO) should be burned to carbon dioxide
(C0 2) using the appropriate oxidation equip-
ment, such as low temperature flares. Cyano-
gen (C 2N 2) and hydrogen cyanide (HCN) are
other toxic gases which can form as by-
products. The C2N 2 can form in the furnace
interior where N2 can react with carbon-
based insulating materials or structural com-
ponents at high temperatures. The formation
of HCN can result from the reaction of any
residual moisture (H 20) in the feed solids or
inlet inert gases with carbon and N 2. Portable
CO and HCN detectors need to be used prior
to maintenance work on and around furnaces
in order to insure that working areas are free
of these toxic gases.
Large quantities of inert gases such as nitro-
gen (N 2) or argon (Ar) are often flowed
through the insulation and processing areas
of non-oxide ceramics synthesis reactors to
protect them from oxidation. These gases are
meant to displace oxygen inside of pieces
of processing equipment. They can cause
asphyxiation in stagnant areas if they are
allowed to build up outside of the equipment.
Area oxygen monitors should be used to
protect operating personnel from inert gas
asphyxiation. Proper ventilation needs to be
available so that CO gas from any leaks and
inert purge gases do not waft and build up
in the process areas.
High temperature graphite reactors are
commonly used for the carbothermal reduc-
tion synthesis of non-oxide ceramic powders.
They are usually operated at temperatures up
to and above 2273 K (2000C). Proper water

cooling, including appropriate back-up sys-
tems to insure continuous flow, are essential
for properly cooling the furnace structure
and maintaining mechanical integrity. In
addition to the potential for thermal burns,
other hazards include the leakage of air or
cooling water into these units. Air leakage
into a hot reaction vessel will not only result
in oxidation of the reactor internals and insu-
lation, but also presents hazards associated
with the generation of CO, including cata-
strophic combustion. Similar concerns exist
Safety issues 77
for cooling water leakage, which may,
depending upon the operating temperature,
produce large quantities of gaseous steam or
CO and H2 directly. Furnace design should
be such that water leakage, such as from
weld failures, will be outside the shell, away
from reactant materials. Any immediate
generation of steam or CO and H2 by such
reaction will need to be vented using properly
designed pressure relief devices. Dew point
and oxygen analyzers should be used to moni-
tor for air or water leaks within the process.
THERMOCHEMISTRY AND KINETICS 3
Alan W. Weimer

INTRODUCTION shown schematically in Figure 3.1. The

enthalpy change (tJI) of each overall reaction,
The manufacture of non-oxides by carbo-
for ~G=O (at P=O.lMPa (1atm, is also
thermal reduction can be carried out in a
included in the table. Thermodynamically,
variety of ways to synthesize carbides, borides
the overall reactions are not favorable unless
and ni~ides. Carbides are manufactured by
t~e standard free energy change is negative
the hIgh temperature reaction between
(1.e. ~G < ~) .. Therefore, at atmospheric pres-
carbon and metal oxides alone. The synthesis
sure, the mimmum temperatures required for
of borides requires either that elemental boron
t~e .various overall reactions to occur at equi-
is present or that the metal oxide or carbon
libnum are those shown in Table 3.1. In
source contains boron, while reaction includ-
practice, temperatures above the minimum
ing nitrogen or a nitrogen containing species is
are required to promote reaction at a reason-
necessary to produce the nitride materials. In
able rate. Since these reactions are reversible
all cases, the reactions are highly endothermic,
it is desirable to remove the by-product CO
have carbon monoxide (CO) as a reaction by-
produced in the process.
product and are thermodynamically favorable
The range of (1) enthalpy changes for the
at only very high temperatures.
overall reactions, (2) molar ratios of by-
This chapter presents an overview of the
product CO produced to the non-oxides and
thermochemistry and kinetics of carbothermal
(3) temperatures required to carry out the
reduction reactions to produce carbides, bor-
reactions is broad for the carbides, borides
ides and nitrides. Free energy and enthalpy
and nitrides alike.
change considerations are reviewed as well
For the carbides, Mo2C can be manufac-
as reaction rate expressions which have been
tured at temperatures above approximately
a.rplied to carbothermal reduction systems.
T. = 742 K (469C) (at atmospheric pressure)
Fmally, the synthesis of B4C, SiC, AlN and
VIa
Si3N4 is reviewed in detail.
2Mo03 + 7C ---+ Mo2C + 6CO (3.1)
THERMOCHEMISTRY while temperatures above T = 2239 K (1966 C)
are required for the manufacture of A4C3:
The overall carbothermal reduction reactions
2Al20 3 + 9C ---+ Al4C3 + 6CO (3.2)
to produce some carbides, borides and
nitrides are summarized in Table 3.1. The In addition, the synthesis of B4C (~H =
free energy change (~G) associated with ~29901 kJ/kg) requires approximately 13
each reaction at atmospheric pressure is times the energy required to produce WC

Carb~de, Ni~ride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published m 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
80 Thermochemistry and kinetics
Table 3.1 Carbothermal reduction reactions to produce carbides, borides and
nitrides

Reaction Tat ~G = 0 Mf at ~G =0
(K(OC)) (kJ/kg)

(a) Carbides
2A120 3 + 9C -> A14C3 + 6CO 2239(1966) +16478 (A4C3)
2B 20 3 + 7C -> B4C + 6CO 1834(1561) +29901 (B4C)
3Cr203 + 13C -> 2Cr3C2 + 9CO 1383 (1110) + 5966(Cr3C2)
Hf02 + 3C -> HfC + 2CO 1934(1661) + 3265(HfC)
2Mo03 + 7C -> Mo2C + 6CO 742(469) + 7114(Mo2C)
Nb20 S + 7C -> 2NbC + 5CO 1228(955) + 4928(NbC)
Si02 + 3C -> SiC + 2CO 1788 (1515) + 14 688 (SiC)
Ta20s + 7C -> 2TaC + 5CO 1381 (1108) + 3006(TaC)
Ti02 + 3C -> TiC + 2CO 1555(1282) + 8663(TiC)
V20 S + 7C -> 2VC + 5CO 932(659) + 6180(VC)
W03 + 4C -> WC + 3CO 950(677) + 2338(WC)
zr02 + 3C -> zrC + 2CO 1930(1657) + 6258(ZrC)
(b) Borides
Alz0 3 + 12Bz0 3 + 39C -> 2AIB12 + 39CO 1852(1579) +36012 (AIB12 )
CrZ03 + BZ0 3 + 6C -> 2CrB + 6CO 1550(1277) + 11 909 (CrB)
Cr203 + 2B20 3 + 9C -> 2CrB 2 + 9CO 1639(1366) + 15879 (CrB2)
Hf02 + BZ0 3 + 5C -> HfB2 + 5CO 1772(1499) + 6961 (HfB 2)
Nb20 S + 2B20 3 + 11 C -> 2NbB2 + 11 CO 1456(1183) +11194(NbB 2)
Ta20S + 2B20 3 + 11 C -> 2TaB2 + 11 CO 1585(1312) + 6793 (TaB 2)
Ti0 2 + B20 3 + 5C -> TiB2 + 5CO 1582(1309) +17980 (TiB2)
2Ti02 + B4C + 3C -> 2TiB2 + 4CO 1260(987) + 6056(TiB 2)
V20 S + B20 3 + 8C -> 2VB + 8CO 1229(956) +12211 (VB)
V203 + 2B20 3 + 9C -> 2VB2 + 9CO 1573(1300) + 15091 (VB2)
zr02 + B20 3 + 5C -> ZrB2 + 5CO 1770(1497) + 12212 (ZrB2)
(c) Nitrides
Al20 3 + 3C + N2 -> 2AlN + 3CO 1960(1687) +8150 (AIN)
B20 3 + 3C + N2 -> 2BN + 3CO 1292(1019) +7779 (BN)
Cr203 + 3C + N2 -> 2CrN + 3CO 1501 (1228) +4121 (CrN)
2Hf02 + 4C + N2 -> 2HfN + 4CO 1955(1682) +2556 (HfN)
4Mo03 + 12C + N2 -> 2Mo2N + 12CO 769(496) +3628 (Mo2N)
Nb20 S + 5C + N2 -> 2NbN + 5CO 1231 (958) +3976 (NbN)
3Si02 + 6C + 2N2 -> Si3N4 + 6CO 1820(1547) +8954 (Si3N 4)
Ta20S + 5C + N2 -> 2TaN + 5CO 1408 (1135) +2447 (TaN)
2Ti02 + 4C + N2 -> 2TiN + 4CO 1453 (1180) +6058 (TiN)
V20 S + 5C + N2 -> 2VN + 5CO 806(533) +4304 (VN)
2Zr02 + 4C + N2 -> 2ZrN + 4CO 1901 (1628) +4619 (ZrN)

(fiR = +2338 kJ /kg) per mass of non-oxide Likewise, the amount of by-product CO
produced according to produced on a molar basis for manufacturing
Al4 C3 , B4 C and Mo2 C is three times the
2B2 0 3 + 7C ---+ B4 C + 6CO (3.3) amount produced for the manufacture of
W03 + 4C ---+ WC + 3CO (3.4) HfC, SiC, TiC and ZrC (Table 3.1(a.

In general, the energy required to manufac-
ture the borides (from B20 3 ), relative to the
corresponding carbides, is greater per mass
of boride product because of the requirement
that carbon reduces the corresponding metal
oxide in addition to reducing the required
amount of B20 3 . For example, the manufac-
ture of ZrB2 requires 12212 kJ /kg ZrB2 (equa-
tion 3.5) while the manufacture of ZrC
requires only 6258 kJ /kg ZrC (equation 3.6):
Zr02 + B20 3 + 5C ----> ZrB2 + 5CO
Zr02 + 3C ----> ZrC + 2CO
Titanium diboride (TiB z) can be manufac-
tured according to either reaction 3.7 (using
B20 3 ) or reaction 3.8 (using B4C):
Ti0 2 + B20 3 + 5C ----> + 5CO
TiB2
2Ti02 + B4C + 3C ----> 2TiB2 + 4CO
The two methods are very similar; however,
reaction of B4C generates less by-product CO
and requires lower temperatures and less
energy relative to reaction of B20 3 . Reaction
through B4 C is the preferred method of man-
ufacture because of the processing difficulties
generally encountered with the presence of
low melting B20 3 (Kim and McMurtry,
1985). Since reaction 3.7 is one-half of the
sum of reactions 3.3 and 3.8, the total energy
requirement and CO generation for the two
routes are identical.
The synthesis of nitrides by carbothermal
reduction and nitridation (i.e. carbothermal
nitridation) generally requires less energy
and less carbon relative to synthesis of the
corresponding carbides. For example, the
manufacture of TiN according to
2Ti02 + 4C + N2 ----> 2TiN + 4CO
requires 6058 kJ /kg compared to 8663 kJ /kg
which is required for the manufacture of TiC
according to
Ti02 + 3C ----> TiC + 2CO (3.10)
In addition, only two-thirds of the carbon is
required for equal molar amounts of product.
Kinetics 81
Some relative cost differences for the manu-
facture of competing ceramics can be seen on
the basis of thermochemical considerations.
For example, SiC via
Si02 + 3C ----> SiC + 2CO (3.11 )
and B4C according to equation 3.3 both
require similar high temperatures for syn-
thesis (T > 1788 K (1515C) and T > 1834 K
(1561C), respectively). However, SiC
requires less than half the energy for manu-
(3.5)
facture (.()'H = 14688 kJ /kg SiC vs tl.H =
(3.6) 29901 kJ /kg B4C) and, on a molar basis,
generates only about one-third the amount of
by-product CO (2 moles CO/mole SiC vs 6
moles CO/mole B4C). The lower energy and
carbon usages contribute to SiC being of
(3.7) lower cost than B4C.
Although thermodynamics can predict
(3.8) when a reaction will not occur, it cannot
predict whether a reaction will indeed occur
in practice. Activation energies, diffusional
resistances, and other reaction kinetic con-
siderations may prevent a reaction which
otherwise should occur.
KINETICS
Although final reaction equilibrium products
are determined solely from the temperature,
pressure and chemical species present, the
mechanism and rate depend on a number of
additional variables. These variables include
particle size, the degree of mixing of reactants,
diffusion rates, gas concentration, porosity,
and the presence and level of impurities or
catalysts.
Contrary to the solid-solid reaction mecha-
nism one would first envision for the overall
(3.9)
carbothermal reduction reactions shown in
Table 3.1, the reaction mechanism generally
includes fluid-solid and fluid-fluid inter-
mediate reactions. In general, fluid-solid
reactions are believed to be of primary impor-
tance in the synthesis of many carbides (i.e.
SiC, B4C) while fluid-fluid reactions are
extremely important in the synthesis of
82 Thermochemistry and kinetics
600

400 - AI4C3
...., -+ B4C
.::t:-
-0- Cr3C2
Q)
200
0>
C
-- HfC
ro ---- M02C
.c
U -+- NbC
>-
0> 0
..... -0- SiC
Q)
c
W -*- TaC
Q)
..... TiC
..... -200
Q)
LL
.+ VC
'0 WC
-400
..x.. zrC

1200 1400 1600 1800 2000 2200

(a) Temperature, T(K)

600
500
...... --0....
400 '''0. - AIB12
...... '0......
........ ...0......
-+ CrB
300
~ .... -0- CrB2
Q)
200
ro
0>
C ..............
".
-- HfB2
.s::. 100 M. '. ---- NbB2
."9(;.......
U ....... -+- TaB2
>-
0> 0
..... -0- TiB2 (1)
Q)
c -100
w -*- TiB2 (2)
Q)
Q) -200 ..... VB
.....
LL
-300 0 VB2
x ZrB2
-400

-500
-600 '.
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
(b) Temperature, T(K)
Figure 3.1 Free energy change vs temperature for carbothermal reduction reactions to produce (a) carbides
(Table 3.1(a; (b) borides (Table 3.1(b; (c) nitrides (Table 3.1(c.
 Kinetics 83
600

400 -AIN
-+- BN
~ -0- erN
Q)
0') 200
c: HfN
as
..c:
""*""
0 M02N
>- 0
e>
Q)
-+- NbN
c:
W -0- Si3N4
Q)
~
-200 -*- TaN
LL.
.+. TiN
-400 '0' VN
X ZrN

1200 1400 1600 1800 2000 2200

Temperature, T(K)
Figure 3.1(c)

certain nitrides (i.e. Si3 N 4 ). Direct solid-solid
reactions occur, but are limited to sites where
carbon and the metal oxide are in direct con-
tact. The fact that many of these reactions are
intrinsically fast and that complete conversion
of either the metal oxide or carbon occurs with-
out substantial excess of the other component
available is evidence that solid-solid reactions
do not dominate the process.
This section contains a simplified overview
of the types of reaction rate expressions
reported by various investigators for carbo-
thermal reduction reactions. These rate expres-
sions are generally based upon the findings
that either internal or external diffusion of reac-
tants, nuclei growth or chemical reaction con-
trols the overall process. A more thorough
treatment of this complex subject is contained
in several excellent texts (Doraiswamy and
Sharma, 1984; Harrison, 1969; Levenspiel,
1972; Szekely, Evans and Sohn, 1976).
The reaction rate equations to be discussed
below are grouped under different controlling
mechanisms, but can all be represented by the
expression
F(X) = kt (3.12)
where
(3.13)
The reaction rate constant, k, accounts for
the effect of temperature on the reaction,
while the form of the expression, F(X),
accounts for virtually all other effects
including composition, diffusion and particle
size. Values of the activation energy, EaJ
reported for carbothermal reduction reactions,
are generally high (200 to 800 kJ / mol), indi-
cating a high degree of temperature sensi-
tivity. ko is the Arrhenius pre-exponential
factor.
PRODUCT LAYER DIFFUSION CONTROL
Jander (1927), Ginstling and Brounshtein (1950)
and Carter (1961) have developed reaction
84 Thermochemistry and kinetics
Table 3.2 Reported models for carbothermal reduction reactions

Reaction model Expression Application

Product layer diffusion control

Jander (1927) kt = [1 - (1 - X)1/3f SiC: van Dijen and
Metselaar (1991)
Si3 N 4 : Mori, Inoue and Ochiai
(1983)
CaC 2 : Tagawa and Sugawara
(1962)
Ginstling and AIN: Hirai et al. (1989)
Brounshtein (1950) UC 2 : Lindemer, Allen and
Leitnaker (1969)
Carter (1961) 2 - [1 + (2 - 1)Xf/3 - (2 - 1)(1 - X)2/3 SiC: van Dijen and
kt= 2-1 Metselaar (1991)
TiN: Li and Riley (1991)

Nuclei-growth control
Avrami _(kt)m = In(1 - X) B4 C: Weimer et al. (1992)
(1939, 1940, 1941) SiC: Ono and Kurachi
(1991)
Si3 N 4 : Weimer et al. (1996)

Si3 N 4 : Zhang and Cannon

kt3 =_X_ (1984)
~X+1

Phase boundary reaction control, spherical symmetry

Jach (1963) kt = 1 - (1 - X)1/3 AIN: Lefort et al. (1985)
Lefort and Billy (1993)
Sepulveda, Folkerts
and Kelley (1989)
Si3N 4 : Liou and Chang (1995)
SiC: Shimoo, Sugimoto and
Okamura (1990)
Weimer et al. (1993)
WC: Alonso et al. (1987)
Fe: Rao (1971)

Order of reaction

kt = _1_ ( 1 -1)
n-1 (l_X)n-l
B4 C: Pikalov (1988)

Zero order
dX=k SiC: Klinger, Strauss and
dt Komarek (1966)
Viscomi and Himmel
(1978)
First order
kt = In(l - X) TiN: White et al. (1992)

Table 3.2 Continued
Reaction model
Decomposition dX = k(1 _ X)a
dt
dX =kXb
dt
Austin and Rickett (kt)" = 1 ~X
(1939)
ktd =X
models for product layer diffusion controlled
solid-solid and solid-fluid reactions:
kt = [1 - (1 - X)1/3f
kt = 1 - ~X - (1 - X)2/3
Z - [1 + (Z -1)X]2/3 - (Z - 1)(1 _ X)2/3
kt= Z-1
These models were derived on the assump-
tion that (1) the reactant particles are spherical,
(2) the spherical particles are immediately
covered with a continuous product layer and
(3) the reaction rate is controlled by bulk
diffusion of the mobile reactant through the
product layer. The derivation of equations
3.14 and 3.15 also assumes that the size of
the particles remains unchanged during
the course of the reaction. On the other
hand, equation 3.16 accounts for the change
in volume due to reaction through intro-
duction of the volume change parameter, Z.
Equation 3.16 is preferred when product
layer swelling significantly increases the
diffusional resistance of the mobile reactant.
These models have been found to be very
applicable in correlating experimental data
for various carbothermal reduction reactions
(Table 3.2).
Kinetics 85
Expression Application
SiC: Klinger, Strauss and
Komarek (1966)
SiC: Khalafalla and Haas
(1972)
SiC: Kuznetsova,
Dmitrenko and
Kokurin (1980)
NUCLEI-GROWTH CONTROL
The nucleation and growth effects are com-
monly combined into a single mechanism
(3.14)
called nucleation kinetics. This mechanism
has been used quite successfully in the study
(3.15)
of phase changes (i.e. crystallization) or the
decomposition of solid materials. An exten-
sive explanation of this mechanism is given
by Avrami (1939, 1940, 1941). Tompkins
(3.16)
(1976) indicates that the Erofeyev (1946)
approximation of Avrami's expression is
adequate for describing most kinetic data of
the nucleation type.
The form of the Erofeyev (1946) equation is
-(kt)m = In(1 - X) (3.17)
The nucleation kinetic mechanism is based
on the activation of reaction sites, followed by
growth of the 'product' nuclei through
chemical reaction. The parameter m accounts
for the reaction mechanism, number of nuclei
present, composition of parent and product
phases, and geometry of the nuclei. It
indicates the order of the time dependence of
the nucleation and the number of growth
directions (Strnad, 1986). When nucleus
activation is the rate limiting step, m ---+ 4.
When isotropic three-dimensional nucleus
growth is the rate limiting step, then m ---+ 3.
For one-dimensional rod-like growth, m ---+ I,
86 Thermochemistry and kinetics

-1 -2

-3 -4

-5 -6
C?
"C'
ca c..
:3-
c.. -7 -8 ---
:2:
c..
0 0,....
,....
Ol Ol
0 0
...J -9 -10 ...J

-11 -12

.
. ~t
-13 -14
... 2
I.'

800 1200 1600 2000

(al Temperature, T(K)
Figure 3.2 (a) Bz0 3 vaporization in 10- 10 Pa (10- 15 bar) Oz below 1923 K (1650 C) and vaporization of B-
Bz0 3 mixture above T = 1923 K (1650 C); (b) SiOz vaporization in 10-10 Pa (10- 15 bar) Oz; (c) Al z0 3 vapor-
ization in lO- lO Pa (10- 15 bar) Oz below 2250K (1977C) and vaporization of AI-Al z0 3 mixture above
T = 2230 K (1957C). (Lamoreaux, R.H., Hildenbrand, D.L. and Brewer, L., 'High temperature behavior
of oxides II. Oxides of Be, Mg, Ca, Sr, Ba, B, AI, Ga, In, TI, Si, Ge, Sn, Pb, Zn, Cd, and Hg,' J. Phys. Chern. Ref.
Data, 16(3), 419-42, 1987. Reprinted with permission of the American Institute of Physics, Woodbury,
NY.)

while for two-dimensional planar growth, and Achar, 1966) geometry:

m ----+ 2. For one-dimensional homogeneous
parabolic growth as the rate limiting step, kt = 1 - (1 - X)l/3 (sphere) (3.18)
1
m ----+'2' kt = 1 - (1 - X)l/2 (cylinder) (3.19)

PHASE BOUNDARY REACTION CONTROL

X = 8~t3 - 12~t2 + 6kt (cube) (3.20)

When diffusion of the mobile reactant through
the product layer is fast compared to reaction,
the kinetics are controlled by chemical
reaction at the phase boundary. Solid-state
reaction models have been developed for
spherical (Jach, 1963), cylindrical (Jach,
1963), and a contracting cube (Sharp, Brindley
These models apply when chemical reaction
is slow compared to diffusion, but rapid
enough to occur in a thin layer near the
interface. The thickness of the reaction zone is
small compared with the dimensions of the
particle. No consideration is given to reaction
of the mobile reactant within the bulk of the
 Kinetics 87

-1 -2

-3

-5 -6
'C'

eas -7 -8
a..
,....
0 o
,....
C> C>
0
--J -9 -10 ..9

-11 -12

-13 o -14

1200 1400 1600 1800

Temperature, T(K)

Figure 3.2(b)

fixed reactant. Equations 3.18 to 3.20 are iden- analyzing experimental data. They are not,
tical to those derived for gas-solid reactions however, derived from physical reaction
involving non-porous solids (Levenspiel, models like those discussed previously.
1972; Szekely, Evans and Sohn, 1976).

DECOMPOSITION
ORDER OF REACTION
Kinetic equations for thermal decomposition
The general rate equation for an nth order of solids have been applied to carbothermal
reaction is given by reduction systems. Those which have been
applied are
kt= (n~1)C1-~t-l-1) (3.21)

For a zero order reaction: dX =k(l-X)a (3.24)

dt
dX=k (3.22)
dt dX =kXb (3.25)
dt
For a first order reaction:
kt = In(l - X) (3.23) (ktY = 1 ~X (3.26)
These simple order expressions for constant
volume conditions are convenient to use in kt d = X (3.27)
88 Thermochemistry and kinetics
-1
-3
-5
-;:-
ectl -7
Q.
0
,...
Ol
0 o
....J -9
-11
-13
1200 1600
Temperature, T(K)
Figure 3.2(c)
IMPORTANCE OF THE GAS PHASE
The fact that many of the overall synthesis
reactions are known to occur through gaseous
intermediates indicates that the gas phase is
very important in the overall mechanism of
numerous carbothermal processes. Some of
the solid reactant metal oxides sublime, have
substantial vapor pressure, dissociate, or
are reacted into volatile species within the
temperature range for reaction. The most
important metal oxide reactants which are
believed to yield substantial volatile species
upon heating in reducing environments are
B2 0 3 (Figure 3.2(a and Si02 (Figure 3.2(b.
There is also particular interest in the volatiles
associated with A12 0 3 (Figure 3.2(c, although
these are considered to be less important than
volatiles in the B2 0 3 and Si02 systems.
-2
-4
-6
-8 Q.
o
,...
Ol
-10 ....J
-12
-14
2000 2400
For carbothermal reduction reactions invol-
ving B20 3 as a precursor, it is clear from the
vaporization equilibria (Figure 3.2(a that
B2 0 2 (g) is important for temperatures above
approximately 1760K (1487 DC). Below this
temperature, vaporization takes place primar-
ily by evolution of B2 0 3 (g). The B2 0 3 (g) has an
increasing vapor pressure with a temperature
above the B2 0 3 melting point (Yoon and Jha,
1995) of 723 K (450 DC). Volatile boron sub-
oxides are believed to play a key role in
carbothermal reduction mechanisms invol-
ving B2 0 3 (Weimer et al., 1992).
Carbothermal reduction reactions involving
Si02 almost always occur through the gaseous
intermediate SiO(g). Vaporization equilibria of
Si02 indicate (Figure 3.2(b that SiO(g) is the
dominant gaseous species under reducing
conditions at temperatures from less than
 Synthesis of carbide and nitride powders 89
1200 K (927C) to well above 2000 K 0727 C).
It is believed that both SiC and Si3N4 are -1
synthesized via carbo thermal reduction
mechanisms which occur through SiO(g). -3
For Al20 3 systems under reducing condi-
tions, the major gaseous aluminum species
above 1500 K 0227C) are Al(g) and AI20(g) -5
(Figure 3.2(c. Volatile aluminum metal, Q)
Al(g), appears to be the dominant species up 1i1
a: -7
to about 2000K 0727C). Above approxi- 0
~

mately 2000 K 0727C), AI20(g) appears to C>

become predominant in the gas phase.
A comparison of the maximum vaporiza-
tion rates (Lamoreaux et al., 1987) for B20 3,
Si02 and Al 20 3 under reducing conditions
(0 2 pressure of 10- 15 bar) is given in Figure
3.3. The rapid volatilization of B20 3 and
Si02, relative to that of A120 3, is an indication
of the significant role played by gaseous sub-
oxides in B20 3 and Si02 containing systems.
The much lower volatilization rate of Al20 3
indicates the much smaller role played by
gaseous aluminum suboxides in Al20 3
systems.
Of course CO, the by-product of all the
carbothermal reduction synthesis reactions,
plays a substantial role in the thermo-
dynamics and reaction kinetics for all of the
reactions. Reduction processes involving CO
are believed to be the primary route by
which certain oxides are reduced, thus produ-
cing intermediate gaseous oxides:
CO(g) + B20 3(1, g)
--4 B20 2(g) + CO2(g) (3.28)
CO(g) + Si02(s) --4 SiO(g) + CO2 (g) (3.29)
2CO(g) + AI203(s)
--4 AI20(g) + 2C02(g) (3.30)
0
...J
-9
-11
-13
800 1200 1600 2000
Temperature, T(K)
Figure 3.3 B2 0 3 , Si02 and Al2 0 3 maximum vapor-
ization rates in 10- 10 Pa (10- 15 bar) O 2 . (Lamoreaux,
R.H., Hildenbrand, D.L. and Brewer, L., 'High
temperature behavior of oxides II. Oxides of Be,
Mg, Ca, Sr, Ba, B, AI, Ga, In, TI, Si, Ge, Sn, Pb, Zn,
Cd, and Hg,' J. Phys. Chern. Ref. Data, 16(3), 419-42,
1987. Reprinted with permission of the American
Institute of Physics, Woodbury, NY.)
The partial pressures of CO, CO2 and O 2 in
the presence of carbon (700 < T < 1800 K;
427 < T < 1527C), when their sum is P =
0.1 MPa 0 atm) (Yamaguchi, 1986), are shown
in Figure 3.4.
SYNTHESIS OF CARBIDE AND NITRIDE
POWDERS

In the presence of carbon at atmospheric BORON CARBIDE

pressure for temperatures T > 1300 K
0027C), any CO2 generated by the above Boron carbide exists in a broad range of com-
reactions is immediately reduced to CO(g) positions (Allen, 1953; Amberger, Druminski
by the reaction and Ploog, 1971; Clark and Hoard, 1943;
Matkovich, 1976; Ploog, 1972) with reported
C(s) + CO 2 (g) --42CO(g) (3.31) molar B/C ratios as high as B51 C. Although
90 Thermochemistry and kinetics
Temperature, T(C)
600 800 1000 1200 1400
101.3

0.8 81.04
P02 @T

E 1000K = 6.08 x 10-22 aIm 6:16 x 10-17 Pa

~
a.
!! 0.6 1200K = 1.06 x 10- 19 aIm 1.07 x 10- 14 Pa 60.78 ~
C\I C\I
0 1400K = 2.86 x 10-18 aIm 2.90 x 10- 13 Pa 0
() ()
a. 1600K = 3.40 x 10- 17 aIm 3.44 x 10- 12 Pa a.
.... 1800K = 2.39 x 10- 16 aIm 2.42 x 10-11 Pa ....
0 0
0
()
0.4 2000K = 1.15 x 10-15 aIm 1.17 x 10-10 Pa 40.52 0
()
a. a.

0.2 20.26

O~~L-~--~~~~~~~ __- L__ L-~ __~~

o
o 800 1000 1200 1400 1600 1800
Temperature, T(K)
Figure 3.4 Change of partial pressures of CO (g), CO2 (g) and O 2 (g) coexisting with carbon, PT = 0.1 MPa
(1 atm). (Yamaguchi, A., 'Effects of oxygen and nitrogen partial pressures on the stability of metals,
carbides, nitrides, and oxides in refractories which contain carbon,' Refractories (Taikabutsu), 38(4), 2-11,
1986. Reprinted with permission of the Technical Association of Refractories (Taikabutsu Gijutso
Kyokai), Tokyo, Japan.)

mechanical applications dictate a maximized promote reaction at a reasonable rate. In

hardness and fracture toughness for stoichio-
metric B4 C (Niihara, Nakahira and Hirai,
1984), specialized semiconductor applications
(Wood, 1984a,b; Wood and Emin, 1984)
require the ability to synthesize boron-
enriched boron carbides. Consequently, it is
essential to control the B/C ratio of the
boron carbide product.
Boron carbide can be synthesized by the
carbothermal reduction of liquid boron oxide
via overall stoichiometric equation 3.3. Equa-
tion 3.3 has a positive standard free energy
change up to about 1834 K (1561C) and so,
unless CO produced is removed from the
process, a higher temperature is needed to
general, equation 3.3 is carried out at higher
temperatures (Lipp, 1965) where the presence
of CO does not inhibit the forward reaction
to B4 C.
The effect of temperature and feed com-
position (Figure 3.5) for a system of 7 mol C
and (a) mol B2 0 3 , according to equation 3.3,
was evaluated at atmospheric pressure over a
wide temperature range (Weimer et al., 1991).
Stoichiometric B4 C is the stable reaction prod-
uct for near stoichiometric feed compositions
(a) = 2) up to the melting temperature
(2743 K; 2470C). On the other hand, excess
B2 0 3 in the feed yields boron-enriched boron
carbides above about 2300 K (2027C). The
 Synthesis of carbide and nitride powders 91
1815 K
5.5

4.5
BORON-ENRICHED
0 '" BORON CARBIDES
N
Cl
1\
4
co
v
+
()
I"'- 3.5
1\
co
v
3

2.5
43K

2
1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800
TEMPERATURE (K)
Figure 3.5 Effect of temperature and feed C-B203 composition on boron carbide product composition
(free energy minimization). (Weimer, A.W., Roach, RP., Haney, CN., Moore, W.G. and Rafaniello, W.,
'Rapid carbothermal reduction of boron oxide in a graphite transport reactor,' AIChE r,
37(5), 759-68.
Reproduced with permission of the American Institute of Chemical Engineers, Copyright 1991
AIChE, New York, NY. All rights reserved.)

composition of the product is highly depen-
dent upon temperature and the initial molar
ratio of C and B2 0 3 (Weimer et al., 1991).
Reactant boron oxide changes phase
throughout the heating process. It softens at
about 600 K (327 DC), melts at about 725 K
(452 DC), in reducing environments yields
volatile suboxide, B20 2(g), at above about
1500 K (1227 DC) (Rentzepis, White and
Walsh, 1960) and boils at about 2133K
(1860 DC). The volatile B20 2(g) provides a
gas-solid mechanism through which boron
carbide can also be synthesized:
C(s) + B203(1) ~ B20 2(g) + CO(g) (3.32)
5C(s) + 2B20 2(g) ~ B4C(S) + 4CO(g) (3.33)
When in contact with carbon, boron oxide
can react in the liquid (equations 3.3 and
3.32) or gas phase (equation 3.33) by nuclea-
tion and subsequent growth. The formation
of boron carbide is highly dependent upon
the phase change of reactant boron oxide
from solid to liquid to gaseous boron sub-
oxide, B20 2(g), and the effect of heating rate
and ultimate temperature on the rate at
which the phase changes occur (Weimer et al.,
1992).
At low temperatures or heating rates, little
nucleation occurs. Reaction proceeds through
the phase transition of liquid boron oxide with
growth processes dominating. Then, larger
crystallites (Figure 3.6(a form.
92 Thermochemistry and kinetics

(a)

(b)

Figure 3.6 Photomicrographs of boron carbide products: T = (a) 1803 K (1530 DC); (b) 1953K (1680 C); (c)
2173 K (1900 C); (d) 2373 K (2100 DC). (Weimer, A.W., Moore, W.G., Roach, R.P., Hitt, J.E., Dixit, R.S. and
Pratsinis, S.E., 'Kinetics of carbothermal reduction synthesis of boron carbide,' J. Am. Ceram. Soc., 75(9),
2509-14, 1992. Reprinted with permission of the American Ceramic Society, Westerville, OH.)
 Synthesis of carbide and nitride powders 93

(e)

(d)

Figures 3.6(c) and (d)

94 Thermochemistry and kinetics
For intermediate to high rapid heating
rates (103 to 105 K/s) from intermediate tem-
peratures up to the boiling point of boron 0
oxide (2133 K; 1860 DC), reaction of carbon
may occur with both liquid B2 0 3 (1) and gas- 1
eous B2 0 2 (g). There is a change in mechanism
at about 1976 K (1703 DC) (Figure 3.7) which is g 2
.!:
believed to be the result of competition
between B2 0 3 (1) and B20 2 (g) reacting with 3
carbon. The liquid phase reaction dominates
at lower temperatures while the gas phase 4
reaction dominates at higher temperatures.
Reaction kinetics are adequately described 5L-~--+--+--4---~~--+--+~~
4.7 4.8 4.9 5.0 5.1 5.2 5.3 5.4 5.5 5.6
by the Erofeyev (1946) equation 3.17 for
1fT (K) x 104
three-dimensional nuclei growth (m = 3):
Figure 3.7 Boron carbide synthesis kinetics.
In(l - X) = _(kt)3 (3.34) (Weimer, A.W., Moore, W.G., Roach, RP., Hitt,
J.E., Dixit, RS. and Pratsinis, S.E., 'Kinetics of
The Arrhenius (equation 3.13) rate equa- carbothermal reduction synthesis of boron carbide,'
tions for B4 C synthesis are (Weimer et al., 1992) J. Am. Ceram. Soc., 75(9), 2509-14, 1992. Reprinted
with permission of the American Ceramic Society,
k = 3.86 X 106 exp( -301 OOOjRgT) Westerville,OH.)
(1803 ~ T ~ 1976K) (3.35)

k = 2.00 X 1020 exp( -820 OOOjRgT)
(1976 ~ T ~ 2123 K) (3.36)
Crystallites formed in the intermediate
region are intermediate in size (Figure 3.6(b)).
High rapid heating rates (> 105 K/ s) to high
ultimate temperatures above the boiling point
of boron oxide (T = 2133 K; 1860 DC) allow the
boron oxide phase change to occur much
faster than any nucleation-growth reaction
mechanism. Formation of boron carbide is
believed to occur entirely via the reaction of
B20 2 (g). It is not known if the reaction
occurs through carbon or CO(g) reacting
with B2 0 2 (g), but the product B4 C is extremely
fine (Figure 3.6(c)) with particles growing by
coagulation and coalescence (Figure 3.6(d.
SILICON CARBIDE
Silicon carbide (SiC) exists in both hexagonal
(a-phase) and cubic (,a-phase) crystal struc-
tures. The a-phase is generally synthesized
by reaction at very high temperatures for
extended reaction times. The ,a-phase is gener-
ally synthesized at lower reaction tempera-
tures and transforms to a-SiC upon high
temperature heating.
There is strong evidence (Weimer et al.,
1993) that ,a-SiC is synthesized through
the gaseous intermediate SiO(g) with the
following reactions being most important:
+ Si02 (s) -4 SiO(g) + CO(g)
C( s) (3.37)
Si02 (s) + CO (g) -4 SiO(g) + CO2 (g) (3.38)
C(s) + CO2 (g) -42CO(g) (3.31)
2C(s) + SiO(g) -4 SiC(s) + CO (g) (3.39)
SiO(g) is initially formed at the contact
points of the carbon and silica according to
reaction 3.37. However, the high rate of
SiO(g) synthesis indicates that the gas/solid
mechanism through reactions 3.38 and 3.31
is the one which makes reaction 3.39 possible
once the C/Si02 contact points are consumed
(Lee, Miller and Cutler, 1976). The free energy

changes for reactions 3.11, 3.31 and 3.37 to 3.39
are shown in Figure 3.8.
The starting carbon source has a substantial
influence on the product SiC morphology and
rate of reaction (Kennedy and North, 1983;
Kevorkijan, Komac and Kolar, 1989, 1992;
Klinger, Strauss and Komarek, 1966; Kuznet-
sova, Dmitrenko and Kokurin, 1980; Wei,
Kennedy and Harris, 1984; Weimer et al.,
1993) with the product SiC crystallites resem-
bling the starting carbon crystallites (Figure
3.9) prior to grain growth. Then, as expected,
SiC crystallites sinter and grow with increas-
ing temperature (Figure 3.10) and reaction
time. Although starting Si02 crystallite size
has little effect on the reaction rate, finer
Synthesis of carbide and nitride powders 95
carbon crystallites react faster than larger
ones. The reduction of SiO(g) with C(s)
according to reaction 3.39 is rate limiting.
All of these reaction characteristics are
consistent with a gas-solid model in which
reaction of SiO(g) proceeds at the surface of
the carbon particles. As the SiC product layer
grows, the reaction surface decreases and
leads to a decrease in the rate of reaction. A
schematic of this mechanistic model for SiC
synthesis according to reactions 3.37 to 3.39 is
shown in Figure 3.11. The synthesis of SiC has
been characterized by an irreversible phase
boundary controlled reaction of spherical
carbon particles for which the thickness of the
reaction zone is small compared with the

300

250

200

150
~Q)
Cl
100
c:
(\l
.s:::.
()
50
>-
e>
Q)
0
c:
w -50
Q)
~
LL
-100

-150

-200

-250

-300L---+----r---+--~----~--~--_r--~----r_~
1500 1700 1900 2100 2300 2500
Temperature (K)

Figure 3.8 Free energy change for SiC synthesis reactions: - ; Si02 (s) + CO(g) ~ SiO(g) + CO2 (g) (eqn
3.38); .-.-.; C(s) + Si02 (s) ~ SiO(g) + CO(g) (eqn 3.37); ---; 3C(s) + Si02 (s) ~ SiC(s) + 2CO(g) (eqn 3.11);
.--.; 2C(s) + SiO(g) ~ SiC(s) +CO(g) (eqn 3.39); ; C(s) + CO2 (g) ~ 2CO(g) (eqn 3.31). (Weimer, A.W.,
Nilsen, K.J., Cochran, G.A. and Roach, RP., 'Kinetics of carbothermal reduction synthesis of beta-silicon
carbide,' AIChE J., 39(3), 493-503. Reproduced with permission of the American Institute of Chemical
Engineers, 1993 AIChE, New York, NY. All rights reserved.)
96 Thermochemistry and kinetics
0.1 8 , . . - - - - - - - - - - - - - - ,
e
(ij ::I. 0.16
ti)..:
~* 0.14
Ue
lij.~ 0.12
.,0
~ VI 0.10
U
Ui~ 0.08
~ 0.06 L-~:.....L_ _..l..__ __1._ _...I.__----l

2000 2100 2200 2300 2400 2500

Reaction Temperature. K

Figure 3.10 Effect of temperature on mean SiC

crystallite size. (Weimer, A.W., Nilsen, KJ.,
Cochran, G.A. and Roach, RP., 'Kinetics of carbo-
thermal reduction synthesis of beta-silicon carbide:
(a)
AIChE J., 39(3), 493-503. Reproduced with permis-
sion of the American Institute of Chemical Engi-
neers, Copyright 1993 AIChE, New York, NY.
All rights reserved.)

by numerous investigators for the synthesis

of SiC by carbothermal reduction of Si02
(Table 3.3). This is most likely due to the
broad range of rate equation forms which
have been used to fit data (Table 3.2). The dif-
ferences in reaction rates are consistent with
differences in carbon source reactivity and

(b)

Figure 3.9 C-Si02 precursor mixture and product

SiC (T = 2323 K; 2050 DC): (a) precursor; (b) product
SiC. (Weimer, A.W., Nilsen, KJ., Cochran, G.A. and
Roach, RP., 'Kinetics of carbothermal reduction
synthesis of beta-silicon carbide: AIChE J., 39(3),
493-503. Reproduced with permission of the Amer-
ican Institute of Chemical Engineers, Copyright
1993 AIChE, New York, NY. All rights reserved.)

dimensions of the particle (Weimer et al., 1993):

C +Si02 --SiO + CO
1- (1_X)1/3
k = ----'---'---
coC+CO.
+ Si0 2 --SiO + C02
__ 2CO
t 2C + SiO - - SiC + CO
_ 27.4 (-383000) (3.40) Figure 3.11 Schematic of SiC synthesis reaction
- d exp R T
g mechanism. (Weimer, A.W., Nilsen, KJ., Cochran,
e.A. and Roach, RP., 'Kinetics of carbothermal
The fit of this model to experimental data
reduction synthesis of beta-silicon carbide: AIChE
for different carbon particle sizes and its J., 39(3), 493-503. Reproduced with permission of
range of applicability are shown in Figure 3.12. the American Institute of Chemical Engineers,
A broad range of activation energies Copyright 1993 AIChE, New York, NY. All
(251 < Ea < 552kJ/moD has been reported rights reserved.)
 Synthesis of carbide and nitride powders 97

-16~----------------------------~
kt = 1 - (1- X)1/3
-17

-"0
~-19
-18

c:
-20 1848 < T < 2273 K
0.14 < X < 0.83
-21 2.5 < t < 4.3 s
0.03 < d < 0.22 f..lm
-22~--~--~--~--~----~--~~
4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6
1fT (K) X 104
Figure 3.12 Reaction kinetics (SiC synthesis) for contracting volume model with phase boundary control.
Carbon crystallite size: e, d = 0.22 J-tm, ., d = 0.03 J-tm. (Weimer, A.W., Nilsen, K.J., Cochran, G.A. and
Roach, RP., 'Kinetics of carbothermal reduction synthesis of beta-silicon carbide: AIChE J., 39(3), 493-
503. Reproduced with permission of the American Institute of Chemical Engineers, Copyright 1993
AIChE, New York, NY. All rights reserved.)

crystallite size. For example, the lower rates
reported by Klinger, Strauss and Komarek
(1966) are expected for the reaction of large,
low reactivity, graphite particles. In addition,
petroleum coke generally contains metal
impurities which are known to increase reac-
tion rates as shown by the data of Kuznetsova,
Dmitrenko and Kokurin (1980) and Viscomi
and Himmel (1978). Carbon from pyrolyzed
polymers is generally very reactive as indi-
cated by the rates reported by Ono and Kura-
chi (1991) and Shimoo, Sugimoto and
Okamura (1990). Likewise, the reaction of
fine carbon black powders (Blumenthal,
Santy and Burns, 1966; Kuznetsova, Dmi-
at temperatures above approximately T =
1960K (1687C) in a closed system at atmo-
spheric pressure (Table 3.1(c. Aluminum
nitride (AlN) is synthesized at lower tem-
peratures by removing CO with flowing N 2.
In this manner, Pco (in atm) is kept below its
equilibrium value which can be calculated
(Cho and Charles, 1991b) for 0.1 MPa (1 atm)
total pressure (CO + N 2) from
(Pea)3 + APea - A=0 (3.42)
where
A = exp ( -~~T ) (3.43)

trenko and Kokurin, 1980; Weimer et ai., ~G (in kJ/mol) = 689.9-0.353T (in K) (3.44)
1993) is fast.
A number of the reaction mechanisms pro- A predominance diagram for phase stability
posed for carbothermal reduction of Si02 to in the Al-O-C-N system is shown in Figure
SiC have recently been reviewed (Metselaar 3.13. The stable phase can be predicted pro-
et ai., 1994). vided that Pco and PN 2 are known. Aluminum
carbide, A14 C3 , will not form at a reaction
temperature of approximately T = 1773 K
ALUMINUM NITRIDE (1500C) since it is not thermodynamically
Aluminum nitride (AlN) can be synthesized stable below T = 2273 K (2000C) at P =
by overall reaction: 0.1 MPa N2 (1 atm N 2).
Although AlON (5AlN 9A120 3 ), A14 0 4 C
A1 20 3 + 3C + N2 --+ 2AlN + 3CO (3.41) and A12 0C should also be included in the
98 Thermochemistry and kinetics
Table 3.3 Comparative reaction rate and activation energy for SiC synthesis by carbothermal reduction

Reference Carbon T(K) k (S-I) E(kJ/mol)

Source d(j-tm)

Blumenthal, Santy and Carbon black 0.017 1573 1.0 x 10-3 287
Burns (1966) 1673 5.7 x 10-3
1773 1.5 x 10- 2

Khalafalla and Graphite 1673 1.4 x 10-3 322

Haas (1972) 1698 1.7 x 10-3
1723 1.9 x 10-3
1788 2.8 x 10-3

Klinger, Strauss and Graphite <44 1818 3.2 x 10- 7 510

Komarek (1966) 1863 4.5 x 10- 7
1913 1.7 x 10-6
1943 2.3 x 10-6
1983 4.5 x 10-6
2038 1.4 x 10-5

Kuznetsova, Dmitrenko and Carbon black 0.187 1773 1.7 x 10-2 251
Kokurin (1980) 1873 5.8 x 10-2
1973 7.6 x 10-2
2073 2.1 x 10-1
Carbon black 0.385 1773 7.8 x 10-3 288
1873 2.8 x 10-2
1973 6.2 x 10-2
2073 1.3 x 10-1
Coke 0.198 1773 9.2 x 10- 3 299
1873 3.1 x 10- 2
1973 6.2 x 10-2
2073 1.6 x 10- 1

Lee and Cutler (1975) Charcoal 70 1623 5.0 x 10-4 544

1643 1.0 x 10-3
1673 1.5 x 10-3
1703 3.9 x 10-3
1713 4.0 x 10-3

Ono and Kurachi (1991) Pyrolyzed polymer 1795 3.2 x 10-3 391
1813 3.5 x 10-3
1821 5.5 x 10-3
1881 1.2 x 10- 2
1962 2.7 x 10-2

Shimoo, Sugimoto and Pyrolyzed polymer 1773 1.5 x 10-2 352

Okamura (1990) 1873 2.7 x 10-2
1973 4.5 x 10-2

Viscomi and Himmel (1978) Coke breeze 1673 1.1 x 10-2 552
1723 1.4 x 10- 2
1773 2.5 x 10- 2
 Synthesis of carbide and nitride powders 99
Table 3.3 Continued

Reference Carbon T(K) k(S-l) E (kJ/mo/)

Source

Weimer et al. (1993) Carbon black 0.030 1848 1.2 x 10-2 382
1898 2.0 x 10- 2
1948 6.2 x 10- 2
1973 8.9 x 10- 2
1998 1.3 x 10- 1
0.218 2173 9.2 x 10- 2
2273 1.5 x 10- 1

Source: Weimer, A.W., Nilsen, K.J., Cochran, G.A. and Roach, R.P., 'Kinetics of carbothermal reduction synthesis of beta
silicon carbide,' AIChE J., 39(3), 493-503. Reproduced with permission of the American Institute of Chemical Engineers,
New York, Copyright 1993. All rights reserved.

predominance diagram, there are no pub-
lished data for these systems. While some
studies (Kosolapova et al., 1984) have indi-
cated the presence of Al4 0 4 C and Al20C in
N2 containing systems at temperatures as
low as T = 1473 K (1200C), other studies
(Hirai et al., 1989; Ish-Shalom, 1982) have not
found evidence of these phases at tempera-
tures as high as T = 2053 K (1780C). On the
other hand, numerous investigations (Cho
and Charles, 1991b; Hirai et al., 1989, 1992;
Hirai and Katayama, 1991; Ish-Shalom, 1982;

L0910 Pee (MPa)

-5 -4 -3 -2 -1 o
0
,,"
:
-1 : -2

-2
AIN /i -3
I','
(ij
E -3 ,," -4 a..
:. ~
C\I
z
C\I
1973 K -5 a..z
a.. -4 -------_ .. ----------------.. ---
0 0

Oi AI203 -6 Oi
0 -5 0
-I 1773 K -I

-6 -7

-7 AI4C3 -8

-8
-5 -4 -3 -2 -1 0 2
L0910 Pee (atm)

Figure 3.13 Phase stability diagram for Al2 0rC-N 2 system; P = 0.1 MPa (1 atm). (Cho, Y.-W. and Charles,
J.A., 'Synthesis of nitrogen ceramic powders by carbothermal reduction and nitridation. Part 3. Aluminum
Nitride,' Mat. Sci. Technol., 7, 495-504, 1991. Reproduced with permission of The Institute of Materials,
London, UK.)
 , lol..\it;, "(t...~. ~ ;'" ."'~:','. :~.;t~ ._, ".,.~.. <-
~ ~~'" '.
' ~ ', . J~ .,.,. 111 .... ~'1 ."1~., .':'-
""." "t... r;.t;~., ,. -,):
'1.'" 'W. ;
..
... ~ ", i\~
.~ .:~:.:.! "I!-'1~~\;--~~f
.' . : ~ " .I' ;.,........ .... .... .... .
.,",,- ,.'.
~'. ,>tr&Vl~ . y:it".<"Z:~Q;: _ ,
'.. . .... .... . . . . . "
. . ' ... ,." . f.i~, ... " ~ C!: . ..,. : . ".. ~ ' .. , , 'lil,. '" , ....... !"'~ .
'1.'_. ~ .:" , ~ < <",~~~1~:~ "wr.-.. ..: . .
. :\~Q" ~""> f'" "I.~' '~."i:
.,,: ~ .~:~ . " .~f.!!. Q~':!:"':;';"!!
.;;-:i ~ ....JJ ..... -. ~:.~.; :. ,~." . ,,.....,,.... ~.~~ . ~'!
. ''f' .'''III . ' ' 1 ....... :.-'.~4
:~ ~~m?~~~~.~)i';. : <. Iifi! --~."" ... --:~ . ('
..' .,~ ,', .~t.; ~'ol~' '''i . ,., ~.,.. -.' '~;' '. , ... ,.~"' ....
~ :;..::.: ',:~ ,~_~~~~~::t~
....1 ....
~! \ -!-.a;.;
~. , ~.
.. .,~~'" ~"'" .. -.,c.r;., .. ,,) . -
, 'i..~~~',~. ~
;,\ ...... e,:: .\' .,~~;.': . .4._-:.~ ....l"' t . . ..-:
'., ~~.~ ,;,. ~'4" . '. ,. .. .:..4 ~ .: .' . .M'.
~ ~~ , ,.~, ," "
',. : .. ' ~'~_~''' 4J.t
........ .. ... . _ :.t'~.;.c.~" _ .. ~ .. ,',
U!.lJ .~_ "..; .. ":' -'c.' ,...-: . "._

,~/........
~\ ,). ,
-.,,-,. ~"'"~~'
'
~
..
'~... '

rD i
..' A . ~"' .. '
"'v ' ~ ,
.)) '\- .'. . ... ' ~fS:.~}; . .-'.:;,. '
-u' ..
... ", . l '......y-: ~ .~, ,
/ ........ . .~ . r-.,'
(;\ . ,,, It "'~
;.,,( ~~(.
r ~. ,.
rm ~~ r:"":,-
Figure 3.14 Photomicrographs of precursor (left) and nitrided AIN product (right): (a-c): from a-A12 0 3 containing precursor; (d-f): AI(OH)3
containing precursor. (Tsuge, A., Inoue, H., Kasori, M. and Shinozaki, K., 'Raw material effect on AIN powder synthesis from Al 2 0 3 carbo-
thermal reduction: J. Mat. Sci., 25, 2359-61, 1990. Reproduced with permission of Chapman & Hall, London, UK.)
 Synthesis of carbide and nitride powders 101
Lefort et al., 1985; Tajika et al., 1991; Willems 1.0 r - - - - - - - - - j . . - - - - - - - - .
et al., 1992a,b) have found the presence of
AION during the carbo thermal nitridation
synthesis of AIN, particularly at temperatures 0.8
x
T> 1913 K (1640 C). From the reported litera- C
0
ture, it appears that oxynitrides may play an .~
Q) 0.6
important intermediate role in the reaction >
c:
0
process under certain conditions. ()

The synthesis of AlN by overall reaction (ij

c: 0.4
n~
0
3.41 is believed to occur primarily by a gas-
solid simultaneous mechanism (Hirai et al., u.
1989; Hirai and Katayama, 1991): 0.2

Al 20 3 + 3CO + N2 -+ 2AIN + 3C02 (3.45)

C + CO 2 -+ 2CO
The reaction proceeds with interdiffusion of
CO with N2 and CO2 through the pores in
the AIN reaction product layer which is
formed surrounding the Al20 3 particles.
Since the Al20 3 particle morphology does
not change during reaction (Baik et al., 1994;
Cho and Charles, 1991b; Hirai et al., 1989;
Hirai and Katayama, 1991; O'Donnell and
Trigg, 1994; Tsuge et al., 1990), it seems that
(3.31) 0.0
0.0 0.5 1.0 1.5 2.0
Time, t(hr)
Figure 3.15 Effect of various additives (3 wt% in C/
Al20 3 = 3.03) on the carbothermal nitridation of
Al20 3 to AIN. (Komeya, K., Mitsuhashi, E. and
Meguro, T., 'Synthesis of AlN powder by carbo-
thermal reduction-nitridation method. Effect of
additives on rate,' J. Ceram. Soc. Japan, 101(4), 377-
82, 1993. Reproduced with permission of The
Ceramic Society of Japan, Tokyo, Japan.)

Time, t(hr)
o 2 4 6 8 10 12

100 1923 K
1873 K

1823 K
c
o
.~

~
50
o
#

o ~--------~--------~--~~--~--------~----~
o 10 20 30 40
Time, t(ks)

Figure 3.16 Effect of temperature on the degree of reaction for AIN synthesis. (Hirai, S. and Katayama, H.G.,
'Mechanism of AlN synthesis by carbothermic reduction of Al20 3 in a flowing N2 atmosphere,' in Ceramics
Today - Tomorrow's Ceramics, Mater. Sci. Monograph (ed. P. Vincenzini), 66B, 615-22, 1991. Reprinted with
kind permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)
102 Thermochemistry and kinetics
Time,l(hr)
o 4 6 8
r----.----.-----r----.-----r~
1923K
0.8
~ 0.6
~
N
+
~~ 0.4
~
0.2
10 20 30
Time,l(ks)
Figure 3.17 Fit of kinetic data for AlN synthesis
(from Figure 3.16) to a diffusion control model.
(Hirai, S. and Katayama, H.G., 'Mechanism of
AIN synthesis by carbothermic reduction of Al2 0 3
in a flowing N2 atmosphere,' in Ceramics Today -
Tomorrow's Ceramics, Mater. Sci. Monograph (ed. P.
Vincenzini), 66B, 615-22, 1991. Reprinted with
kind permission of Elsevier Science - NL, Sara
Burgerhartstraat 25, 1055 KV Amsterdam, The
Netherlands.)
the AlN nucleates on the surface of the alu-
mina and that the reaction front advances
towards the center of the alumina grain
thereby maintaining the original particle mor-
phology (Figure 3.14). The pores are fine, and
the resistance to diffusion through this prod-
uct layer is thought to be enormous and reac-
tion rate controlling (Hirai et al., 1989, 1992).
As expected, an increase in porosity within
the reaction mass results in faster reaction
rates (Chen, Lin and Lee, 1994; Cho and
Charles, 1991b) due to an increase in overall
interdiffusion of gaseous reactants and
products. Although higher N2 flow rates
have an obvious positive impact on diffusion
(Chen, Lin and Lee, 1994), excessive rates
apparently have little impact (Hirai et al.,
1989) on the overall reaction rate. As a
Temperature, T(K)
10
1923 1873 1823 1773
10-1
10-2
10-3 ~_....o.-_--'-_ _L - _ - ' - _ " " " " _ - - '
5.1 5.2 5.3 5.4 5.5 5.6 5.7
I/T(K) x 104
Figure 3.18 Temperature dependence of De. (Hirai,
S., Miwa, T., Iwata, T., Ozawa, M. and Katayama,
H.G., 'Formation of aluminum nitride by carbo-
thermic reduction of alumina in a flowing nitrogen
atmosphere,' J. Jap. Inst. Met., 53(10), 1035-49,
1989. Reproduced with permission of Japan
Institute of Metals, Sendai, Japan.)
minimum, thermodynamic considerations
require a sufficient N2 flow so as to maintain
the amount of CO below its equilibrium value
(equation 3.42) at the reaction sites within the
reaction mass.
In addition to thermodynamic considera-
tions such as temperature and CO concentra-
tion, the size and type of the starting alumina
and carbon also impact the rate. Gamma (-y)-
A120 3 and A120 3 dehydrated from Al(OHh
are more reactive than a-A120 3 (Cho and
Charles, 1991b; Qian and Xiong, 1991; Tsuge
et al., 1990). The reaction rate increases with
finer alumina particle size (Chen, Lin and
Lee, 1994; Cho and Charles, 1991b) and
initially increases for finer carbon particle
size (Chen, Lin and Lee, 1994; Cho and

Charles, 1991b; Lefort et al., 1985), but is
seemingly unaffected thereafter.
It is believed that the faster reaction rates
observed when using dehydrated Al(OHh
are due to the high specific surface areas of
transition aluminas, such as ,-A120 3, which
form during the heating to reaction tempera-
ture. The initial increase in reaction rate with
finer carbon size is believed to be associated
with an increase in the number of direct
contact points between C and A120 3 (Lefort
et al., 1985). From these observations, it
seems that direct solid state reaction between
C and A120 3 is important initially, but once
the contact points are consumed, the reaction
is controlled by interdiffusion of N 2, CO and
CO2 as noted above.
The rate of carbothermal nitridation of
A120 3 can be markedly increased with the
addition of certain catalysts (Komeya, Mitsu-
hashi and Meguro, 1993) such as CaF2, Y20 3
Synthesis of carbide and nitride powders 103
and Yb20 3 (Figure 3.15). It is believed that
with CaF2 or Y203 present, the reaction pro-
ceeds faster through intermediate compounds
like CaF2 . 5A120 3 and Y-aluminates (Y4 Al20 9 ,
Y3Als0 12 and YAI03). These additives also
tend to promote the formation of more spheri-
cal AlN crystallites.
The reaction rate increases dramatically with
rising temperature (Figure 3.16) and can be
modeled according to equation 3.15 for product
layer diffusion control (Hirai et al., 1989, 1992):
kt = 1 - 3(1 - X)2/3 + 2(1 - X) (3.46)
where
k _ 24De(Cco - CCOe)
- 2
d CO2
(3.47)

80

z""'C')" 60
i:i5
~

6.2
0
16
~ 40
.&

3.5
----- Theoretical
20

3 5 7 9 11 13
Nitriding Time, t(hr)

Figure 3.19 Weight percent Si3N4 vs time at T = 1673 K (1400C) for precursors of various C/Si02 ratios:
16,6.2 and 3.5. (Zhang, S.-c. and Cannon, W.R., 'Preparation of silicon nitride from silica,' J. Am. Ceram.
Soc., 67(10), 691-95, 1984. Reproduced with permission of the American Ceramic Society, Westerville,
OH.)
104 Thermochemistry and kinetics
Ceo is the carbon monoxide concentration on
the particle surface; Ceoe is the equilibrium
carbon monoxide concentration; CO2 is the
oxygen concentration; De is the effective
diffusion coefficient inside the particle; D~ is
the apparent effective diffusion coefficient.
The fit of kinetic data to the model is shown
in Figures 3.17 and 3.18.
Although N2 has been used in almost all
studies of carbothermal nitridation AlN
synthesis, there is evidence (Colque and
Grange, 1994) that other nitriding gases such
as NH3 may allow the reaction to occur
quickly and at lower temperatures, relative
to N 2. The formation of HCN and its reaction
with Al20 3 allow the formation of AIN at
1373-1623K (1100-1350C), even when the C
and Al20 3 are physically separated. Some
type of gas phase carbon transport mechanism
such as that through HCN appears to be
important.
SILICON NITRIDE
Silicon nitride (Si3N 4) exists in two hexagonal
polytypes denoted as either a or (3 phase. In
general, a-Si3N4 is considered to be a meta
stable low temperature product which trans-
forms to (3 phase (stable modification) at
higher temperatures. Since control of this trans-
formation is important in the densification pro-
cess to fabricate high quality parts, a-Si3N4 is
considered to be the more desirable modifica-
tion for synthesized powders. In general,
carbothermal nitridation produces a very high
(>95%) a-phase content Si3N4 powder which is
believed to be formed primarily by the reaction
of gaseous species. However, in the presence of
impurities such as Fe, Fe203, CaO and V20 S , (3-
Si3N4 formation is associated with the existence
of low melting eutectics (Bandyopadhyay,
Sanyal and Mukerji, 1994; Peck, Kim and
Choi, 1994).

100
~ IB1 .7 hr
5 hr
80 .A 06.3 hr

~60
.~ .A
C/) .C
#. B2 __ -----------------
40 ~---

AA
20
----
AC
O!~------~--------~--------~--------~------~
o 50 100 150 200
Surface Area of Si02 (m2/g)

Figure 3.20 Weight percent Si3N4 vs surface area of precursor Si02 and C: A (90 m 2 / g Si02 , 55 m 2 / g starch
C); B1 (50 m 2 / g Si02 , 680 m 2 / g activated C); B2 (150 m 2 / g Si02 , 34 m 2 / g lamp black C); C (238 m 2 / g Si02
gel, 34 m 2 / g lamp black C). (Zhang, S.-c. and Cannon, W.R., 'Preparation of silicon nitride from silica,'
J. Am. Ceram. Soc., 67(10), 691-95, 1984. Reproduced with permission of the American Ceramic Society,
Westerville,OH.)
 Synthesis of carbide and nitride powders 105
20~---------------------------'

f\
I \
t, \
16 ~ ~ \
ry\ \
.
\ '\,\
\' \'\
\\'. \
...\ .
12
.....
ou \
\
~ \

8 \ ~"
\, ~\\ ~

\ \\
\ \ \.
4 \ \ \"
Figure 3.21 Photomicrograph of crude product
\. \ ';... :--------
powder synthesized from precursor A (Figure
3.20, C/Si02 =6) reacted for 7h at 1673K o~~ ____ "-'\'\:~~""""'-"''''-''''
-L~~~ ____ -L~ __ ~

(1400 C); bar = 10 Mm. (Zhang, S. -CO and Cannon, o 2 4 6 8

W.R., 'Preparation of silicon nitride from silica:
J. Am. Ceram. Soc., 67(10), 691-95, 1984. Repro-
duced with permission of the American Ceramic
Society, Westerville, OH.)
The overall carbothermal nitridation reac-
tion is described by
3Si02 + 6C + 2N2 ----+ Si3N4 + 6CO (3.48)
Gaseous SiO is generated at C-Si02 contact
points according to equation 3.37 and by gas
phase carbon reduction according to the
combination of equations 3.38 and 3.31. The
gas phase carbon reduction mechanism is
believed to predominate (Zhuang, Wang and
Li, 1991) on the basis of both kinetic and
thermodynamic considerations.
With SiO present, Si3N4 will form according
to one or more of the following reactions:
3C + 3SiO + 2N2 ----+ Si3N4 + 3CO (3.49)
3SiO + 3CO + 2N2 ----+ Si3N4 + 3C02 (3.50)
followed by reaction 3.31, and
3SiO + 2N2 ----+ Si3N4 + 30 (3.51 )
C+O----+CO (3.52)
CO+0----+C02 (3.53)
On the basis of product morphology (single
crystal hexagonal prisms), Zhang and
Time, t(hr)
Figure 3.22 Effect of Si3N4 precursor seed content
on carbothermal nitridation reaction rate (as % CO)
in product gas; fumed silica-acetylene black
precursor; T = 1783K (151OC); wt% seed=O
(-), 5 (----), 10 (..... ) and 20 (.-.-.). (Licko,
T., Figusch, V. and Puchyova, J., 'Synthesis of
silicon nitride by carbothermal reduction and
nitriding of silica: control of kinetics and mor-
phology: J. Eur. Ceram. Soc., 9, 219-30, 1992.
Reprinted with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane,
Kidlington OX5 1GB, UK.)
Cannon (1984) proposed that heterogeneous
nucleation starts according to reaction 3.49,
but that growth proceeds by a gas phase
process according to reaction 3.50. Rahman
and Riley (1989) suggested that Si3N4 is
formed according to reaction 3.51. Thermo-
dynamic calculations (Ekelund and Forslund,
1992a) indicate that atomic oxygen, 0, should
be the dominant oxygen species at high
temperatures and low oxygen partial pres-
sures. The removal of oxygen via reactions
3.52 and 3.53 is thought to be fast enough to
maintain a low oxygen partial pressure, thus
allowing the formation of Si3N4 to proceed
under equilibrium conditions. Although the
 (a) (b)

(c) (d)

Figure 3.23 Photomicrographs of o:-Si3N 4 powder synthesized by carbothermal nitridation: (a) no seed; (b) 10 wt% Si metal (fine grains are {3-
SiC); (c) 10wt% Si3N4 seed; (d) 5wt% Si3N4 seed and controlled Si~ evolution. (Licko, T., Figusch, V. and Puchyova, J., 'Synthesis of silicon
nitride by carbothermal reduction and nitriding of silica: control of kinetics and morphology,' J. Eur. Ceram. Soc., 9, 219-30, 1992. Reprinted

exact reaction mechanism is not defined,
there is general agreement that Si3N4 forms
by a gas phase reaction involving SiO. In
general, the product Si3N4 crystallites bear
no resemblance to either the starting carbon
or silica crystallites.
Nucleation is related to the carbon surface
area (Durham, Shanker and Drew, 1989) and
can be increased by either increasing the
starting C/Si02 ratio (Cho and Charles,
1991a; Figusch and Licko, 1987), increasing
the specific surface area of the carbon source,
increasing the intimacy of contact between the
C and Si02 (Vias ova et ai., 1995), or a combi-
nation of these. The increased carbon surface
area provides greater opportunity for SiO and
N2 adsorption and reaction (i.e. nucleation).
An increase in nucleation (by increasing pre-
cursor C/Si02 ratio (Figure 3.19) or carbon
source surface area (Figure 3.20 increases
the rate of reaction and extent of conversion
(Cho and Charles, 1991a; Durham, Shanker
and Drew, 1991; Figusch and Licko, 1987;
Komeya and Inoue, 1975) of the product
Si3N 4. The additional fine nuclei are believed
to provide added surface for the subsequent
growth reaction(s) to occur. It is also apparent
from the results shown in Figure 3.20 that the
effect of silica surface area on the reaction rate
is minimal compared to that of carbon.
It is believed that the high a-phase content
of the synthesized Si3N4 is related to a high
degree of supersaturation of SiO in the gas
phase (Ekelund and Forslund, 1992a; Hendry
and Jack, 1975) which occurs initially during a
burst of nucleation early in the reaction
(Zhang and Cannon, 1984). Then, as Peo
increases, PSiO and pco/pco2 decrease, thus
making it more difficult to nucleate new
Si3N4 particles. Nucleation may end, though
growth may continue at a lower concentration
of the reactants. The uniform particle size of
the Si3N4 particles (Figure 3.21) supports the
proposal that an initial burst of nucleation is
followed by a slower growth process.
The addition of a small amount of Si3N4
'seed' to the starting C/Si02 precursor has a
Synthesis of carbide and nitride powders 107
substantial effect (Figusch and Licko, 1987;
Inoue, Komeya and Tsuge, 1982; Licko, Figusch
and Puchyova, 1992) on both the reaction rate
(Figure 3.22) and product morphology (Figure
3.23). In addition, 'seeding' makes the reaction
insensitive to the precursor C/Si02 ratio
(Figure 3.24), most likely because the presence
of 'seed' precludes the need for nucleation to
occur. The significant increase in reaction rate
observed with 'seed' addition is believed due
to the fact that the reaction without 'seed'
present is initially controlled by nucleation
(Figusch and Licko, 1987). There is some
indication (Licko, Figusch and Puchyova,
1992) that the intensity of the 'seeding' effect
increases with increasing surface area of seed-
ing powder.
Thermodynamic considerations (Figure 3.25)
dictate an upper reaction temperature limit
for which Si3N4 synthesis is favorable. This
temperature is estimated to be approximately
T = 1708K (1435C) at near atmospheric N2
pressure depending on the data used. Silicon
40,------------------------------,
-
30
20
{ "ISi0 2 -2C
oISi02-4C
1673 K-Sh
10
O~~--~~--~~--~~--~--~~
o O.S 1.0
Si3N4I'Si02 (wt ratio)
Figure 3.24 Effect of precursor Si3N4 seed and C/
Si02 ratio on reaction rate and final degree of nitri-
dation. (Inoue, H., Komeya, K. and Tsuge, A.,
'Synthesis of silicon nitride powder from silica
reduction,' J. Am. Ceram. Soc., 65, C-205, 1982.
Reprinted by permission of the American Ceramic
Society, Westerville, OH.)
 108 Thermochemistry and kinetics
Temperature (0C) and Sasaki, 1986; Tuohino, Laitinen and Tork-
1400 1000 SOD kell, 1990). In addition, Si02 becomes stable
ii' I I I
when the CO partial pressure rises above
+12 Si3N4(S)+C(s) Stable +11 approximately Peo = 34.9 kPa (",,0.345 atm),
even when the temperature is less than
(il 1708 K (1435C).
E +S +7 a..
Kinetically, smaller bulk CO concentrations
:. ~
C\I
z
C\I have a substantial slowing effect on the
z +3 a..
a.. +4 reaction rate and on the product selectivity.
0 0
~

OJ
~

OJ The addition of 1% CO to the N2 gas stream

0
0
...J 0 -1 ...J substantially reduces the degree of conver-
sion, while a 3% CO content effectively
Si02(s)+C(s) quenches the reaction entirely (Ekelund and
-4 SiC(s)+C(s) Stable -5
Stable Forslund, 1992b; Ekelund, Forslund and
Johansson, 1989).
Excess N2 flow above the stoichiometric
0.5 0.6 0.7 O.S 0.9
requirement reduces the CO concentration
1000/T (K-1)
20r-----------------------------~
Figure 3.25 Thermochemical correlation for stabi-
lity of Si3 N4 , SiOz and SiC coexisting with carbon.
(Yamaguchi, A., 'Effects of oxygen and nitrogen
partial pressures on the stability of metals, carbides, 16
nitrides, and oxides in refractories which contain
carbon,' Refractories (Taikabutsu), 38(4), 2-11, !~\
;
1986. Reprinted with permission of the Technical i
i
Association of Refractories (Taikabutsu Gijutso 12 i
i
Kyokai), Tokyo, Japan.) ou
?f. I \
carbide (SiC) is the stable species under co- 8 i! \\, . .

t \' '-'-.'-' ' .

existence with carbon above this temperature
for PN2 = 0.1 MPa (1 atm). In terms of the
reaction rate, it is desirable to operate at as
high a temperature as possible near this
upper thermodynamically imposed limit. One
method for achieving higher rates is to operate
under higher N2 pressures where Si3N4 is the
stable product for higher temperatures. It has
been demonstrated (Ekelund and Forslund,
1990) that a-Si3N 4 can be synthesized at a
temperature as high as T = 1953K (1680C)
when operating under an N2 pressure of
approximately P = 6MPa (",,59atm).
Thermodynamically, CO is detrimental to
the process as the overall reaction 3.48 is rever-
sible and an increased Pco will hinder the
desired forward nitriding reaction. Higher
CO concentrations promote the formation of
,B-Si3N4 and Si2N 20 as well as ,B-SiC (Motoi
4 \
II \'\,.,.'. --=::'. :-... .-. . . . -. . . . .-. . . .- - - -
;:
if
O~ __~if~______~~'~~____~~__~
-2 o 2 4 6 8
Time, t(hr)
Figure 3.26 Effect of impurities and additives on
the carbothermal nitridation reaction rate for
synthesizing Si3 N4 : T = 1783 K (1510 C); fumed
silica-acetylene black (-); fumed silica-pigment
black (.-.-.); and fumed silica-acetylene black-
10wt% Si (..... ). (Licko, T., Figusch, V. and
Puchyova, J., 'Synthesis of silicon nitride by carbo-
thermal reduction and nitriding of silica: control
of kinetics and morphology,' J. Eur. Ceram. Soc., 9,
219-30, 1992. Reprinted with kind permission
from Elsevier Science Ltd, The Boulevard, Langford
Lane, Kidlington OX5 1GB, UK.)

and has been shown to be effective in reducing
the time required to achieve complete con-
version (Hofman et al., 1993) of Si02. Although
high N2 flows are desirable relative to
reducing CO concentrations, too high a flow
may reduce the yield of Si02 to Si3N4 by
promoting the loss of volatile SiO from the
reaction system (Mori, Inoue and Ochiai,
1983). Such SiO losses may present operating
complications such as the deposition of
volatile SiO on cooler surfaces near the exit
of synthesis reactors (Horio, Tsukada and
Naito, 1989). Operation at elevated reaction
pressures reduces the SiO loss (Ekelund and
Forslund, 1990).
The purity of reactants is an important
issue as metal impurities (Cr, Fe, Ni, Si) in
the C/Si02 precursor tend to promote the
synthesis of undesirable ,B-Si3N4 (Bandyo-
padhyay and Mukerji, 1991; Peck, Kim and
Choi, 1994) and ,B-SiC (Siddiqi and Hendry,
1985). In addition, these impurities tend to
catalyze the Si02 reduction reaction as can
be seen (Figure 3.26) by comparing the con-
centration of produced CO for the high
purity fumed Si02-acetylene black precursor
Synthesis of carbide and nitride powders 109
to that for the same precursor with 10%
added Si metal and then to a fumed Si0z-
low purity pigment black precursor. Reduc-
tion of Si02 with low purity pigment black is
much faster than with high purity acetylene
black because of the transition metal impuri-
ties present in the carbon (Licko, Figusch
and Puchyova, 1992).
The carbothermal nitridation of 'seeded'
precursor containing excess carbon can be
modeled using a nucleation-growth rate
expression (equation 3.17). The reaction can
be described by (Weimer et al., 1996)
(kt)o.s = -In(1 - X) (3.54)
k = 2.56 X 1010 exp[( -54968 6615)/T] (3.55)
where precursor 'seed' /Si0 2 = 0.2; 1648 K ~
T~1698K; 3000s~t~18000s; 0~X~1;
X = Si02 conversion.
The reaction rate appears limited by the gas
phase carbon reduction of Si02 according to
reaction 3.38.
Carrying out the carbothermal nitridation
using ammonia (NH3) instead of N2 has
been found to dramatically enhance (Figure
3.27) the nitride formation (Durham, Murtha

100r_----~-------r------,_------~----~r_----~

o Ammonia
80 L::. Nitrogen

"<t
Z
C')
60
Ci5
0~

~ 40

20

0
1548 1573 1598 1623 1648 1673 1698
Temperature, T(K)

Figure 3.27 Effect of ammonia on the carbothermal nitridation reaction rate for synthesizing Si3 N 4 .
(Durham, B.C., Murtha, M.J. and Burnet, G., 'Si3 N 4 by the carbothermal ammonolysis of silica,'
Adv. Ceram. Mat., 3(1), 45-48, 1988. Reprinted with permission of the American Ceramic Society,
Westerville,OH.)
110 Thermochemistry and kinetics
and Burnet, 1988). It is believed that the
dissociation of NH3 to active molecular nitro-
gen and hydrogen with smaller amounts of
NH, NH2 and N2 increased the reaction rate.
The addition of H2 to reactant N 2 has also been
found to accelerate nitride formation (Rahman
and Riley, 1989), although its addition at
higher reaction temperatures may promote
the formation of SiC (Li et al., 1983).
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ACHESON PROCESS
Philip J. Guichelaar
INTRODUCTION, HISTORY
Silicon carbide (SiC) is not uncommonly
referred to as 'carborundum'. This vernacular
term commemorates a word coined by
Edward G. Acheson in 1892 to describe
crystals that he made in an experiment
which had the real goal of making a dia-
mond-like crystal from carbon and alundum
(Acheson, 1893). Using a primitive electric
furnace of his own design, he in fact made
SiC. Acheson immediately designed a more
efficient electric furnace and soon a profitable
business with the jewelry trade was estab-
lished. A century later, the furnaces used to
make almost all SiC world-wide follow his
original design concept.
As is common in technological develop-
ment, Acheson was not the first person to
make SiC and he was not the first person to
propose and demonstrate a direct resistance
smelting furnace. Naturally occurring SiC
was known (moissanite) and small quantities
had previously been made on a laboratory
scale but not always recognized (Despretz,
1849; Marsden, 1880; Colson, 1882). The
Cowles furnace, patented in 1885 and intended
for refining zinc ores (Cowles and Cowles,
1885), is very similar to Acheson's design of
1893; a patent infringement suit, however,
was unsuccessful (Vanderbilt, 1974). Acheson,
to his credit, quickly recognized the commer-
cial potential of his invention and his legacy
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
4
is the world-wide electrominerals industry
which developed from these efforts.
An examination of Acheson's original
furnace is instructive for our purposes since
his basic design principles have remained
unchanged as furnace design has evolved
toward larger sizes and better efficiency.
Figure 4.1, copied directly from his patent,
shows electrodes which connect to a graphite
core laid within a surrounding mixture of
reactant carbon, salt and sand. When an elec-
tric current is passed through the graphite
core, it heats the surrounding reactants, result-
ing in the formation of a hollow cylinder of
SiC and the expulsion of carbon monoxide
(CO) gas. The final SiC cylinder has graphite
in its interior and partially reacted charge
materials in an annular zone on its periphery.
Acheson described the principal manufactur-
ing process control parameters in his first
paper:
. .. the extent of the [crystalline silicon
carbide] zone and the character of the crys-
talline material depend upon many things,
such as the strength of the current, the time
of operation, the character of the material
used, and other conditions (Acheson, 1895).
These parameters continue to be the key oper-
ating concerns in contemporary operations.
Silicon carbide (SiC) was far superior to all
other abrasives of the time and sales grew
quickly to the jewelry and grinding wheel
116 Acheson process
. 'f ' -,
I significantly larger, far more mechanized and
I environmentally friendlier over the past two
I decades. But they continue to be called Ache-
!I
.L. _ ._ ._._ ._ .~_
_ ~._ _ . _ .. .. _. ~I
Figure 4.1 Cross-sectional view of a direct resis-
tance furnace for manufacturing silicon carbide,
adapted from Acheson's original patent. (Adapted
from Acheson, 1895.)
trades. To meet this demand, Acheson built
the first commercial plant in 1896 in Niagara
Falls, New York. Abundant, low-cost hydro-
electric power was available, a necessity for
his power-intensive manufacturing process.
Other companies followed and Niagara Falls
became the focus of the SiC industry for
many decades (Cheape, 1985). The industry
grew quickly as manufacturers of abrasives
and refractories took advantage of the func-
tional and productivity benefits of the
material. Thirty-five years later, the tech-
nology had matured. Furnace lengths had
increased to 15.2 m (49.2 ft) and power inputs
were commonly 1.5 MW, but the basic furnace
design, according to a detailed contemporary
account, was unchanged (Eardley-Wilmot,
1929). Salt was still included as a reactant
to remove iron (Fe) as a volatile chloride and
coarse sawdust was mixed in to vent the
escaping gases and minimize the danger of
' ... the whole mass exploding ... '.
In the industrial expansion that followed
World War II, somewhat larger and higher-
powered furnace plants were built, but again
the basic design did not change. Additions of
salt were discontinued after about 1960 when
furnace plant managers decided that the puri-
fying advantage was minimal in contrast to
the rapid corrosion that it caused to the struc-
tural steel that supported plant roofs (Walker,
personal communication, 1991). Sawdust is
still in use in many plants. Others have discon-
tinued its use in an effort to reduce visible
plant emissions. Furnace plants have become
I son furnace plants because the fundamental
. principles are unchanged from his 1892
design.
BASIC SILICON CARBIDE PROCESS
DESCRIPTION
The chemical reaction for the manufacture of
SiC from silica (Si0 2 ) and carbon is written as
Si02 + 3C ---; SiC + 2CO (4.1)
Most of the early process descriptions (Ache-
son, 1893) and even a few more current
descriptions (Margrave and Mamantov, 1967)
mistakenly assume that SiC results solely from
a condensed phase reaction between Si02 and
carbon. Even if one assumes that such a direct
reaction will occur more efficiently above
the fusion point of Si02 , ",2000 K (1727 C),
extensive diffusion still must occur to bring
silicon (Si) atoms into proximity to carbon
atoms. This is not reasonable for the large
particle sizes used in commercial SiC manu-
facture.
Instead, SiC forms as a result of four sub-
reactions, each of which provides mass trans-
fer in the vapor phase (Weimer et al., 1993):
C + Si02 ---; SiO(g) + CO(g) (4.2)
Si02 + CO (g) ---; SiO + CO2 (g) (4.3)
C + CO2 (g) ---; 2CO(g) (4.4)
2C + SiO ---; SiC + CO(g) (4.5)
These reactions provide a more reasonable
path from the Si02 and coke reactants to the
SiC and CO products. First, the Si02 particles
react with adjacent coke particles, liberating
silicon monoxide (SiO) and CO. The CO
reacts with other Si02 sites to liberate addi-
tional SiO and carbon dioxide (C0 2 ), which
is reduced by carbon to CO. The SiO reacts

Figure 4.2 Cylinder of silicon carbide produced in an Acheson furnace. (Photo courtesy of Arendal
Smelteverk a.s., Eydehavn, Norway.)
directly with carbon, at the carbon particles,
to form SiC. Most of the SiC in a cylinder
is made through this series of reactions at
temperatures above 1970 K (1697C). How-
ever, at lower temperatures, between 1800 K
(1527C) and 1970K (1697C), SiO will react
directly at carbon particle surfaces to form
SiC (Poch and Dietzel, 1962).
The product form in Acheson furnaces is a
large hollow cylinder, as shown in Figures 4.2
and 4.3. Additional SiC is formed only on the
outer periphery. In practice, one finds a mix-
ture of carbon particles, sand particles and SiC
in an outer annular zone at the end of a furna-
cing run. The other product of the reaction,
CO, is formed in substantial volumes that
flow outward from this peripheral reaction
zone through unconverted reactants.
Basic silicon carbide process description 117
All SiC is initially formed as small crystals
of the cubic beta form (Jepps and Page, 1983).
Beta silicon carbide (B-SiC) can be formed at
temperatures as low as 798 K (525C) (Bau-
mann, 1952). In Acheson furnaces, however,
Pure Silicon Carbide
Reaction Zone
U--7li~'- Center Cavity
with Graphite
Condensed Metal
Oxides
Figure 4.3 Cross-sectional view of a typical cylin-
der, showing the interior cavity in which graphite
is formed, the pure silicon carbide body and the less
pure material in the reactant zone.
118 Acheson process
the reaction takes place at temperatures above
1800K (1527C) (Poch and Dietzel, 1962). The
transformation of relatively pure j1-SiC to the
alpha crystalline form (a-SiC), specifically the
6H crystalline polytype, occurs at temperatures
above 2173 K (1900 0c) (Kistler-De Coppi and
Richarz, 1986). Further crystal growth occurs
by a vapor transport mechanism; the activation
energy is similar to the value for the heat of
sublimation of solid SiC. Drowart and De
Maria (1960) noted that the vapor pressures
of Si, disilicon carbide (Si2 C) and silicon dicar-
bide (SiC2) are sufficiently high at these
temperatures that crystal growth can occur by
transport of their respective vapor phase
species. Porter (1967) found that the molecular
structure of the vapor phase over solid SiC at
these temperatures is a stable polyatomic
species SixCy similar to that for carbon vapor.
As these vapor species are formed and migrate
to colder regions, graphite is left behind with a
pseudomorphology corresponding to the origi-
nal SiC crystals. Silicon carbide totally decom-
poses to graphite and Si at 3103 K (2830C)
(Scace and Slack, 1960).
Pure SiC is colorless and transparent
(Hamilton, 1960). However, such pure SiC
cannot be made on a commercial scale because
nitrogen from air is soluble in SiC, causing the
crystals to take on a green color. Additions of
aluminum (AI) into the structure result in a
blue color shading to a black color at higher
concentrations. The maximum solubility of
Al is 2.0% (Kistler-De Coppi and Richarz,
1986). Boron (B) solution causes brown crys-
tals to form, shading to black at amounts up
to 0.2%. The maximum B solubility is about
0.5%. Iron (Fe) is commonly present as an
impurity in Si02 raw materials. It catalyzes
the formation of SiC formation by affecting
the reaction (equation 4.4) between carbon
and CO2 (Lee and Cutler, 1975). However, it
is not soluble in the SiC lattice and is instead
distilled to the outer edges of the peripheral
reaction zone.
Additions of Al and B affect the crystal
growth rate and the dominant crystal structure
that is produced (Kistler-De Coppi and
Richarz, 1986). Pure SiC that has been heated
above 2373 K (2100C) has a 6H structure,
shown in practice by the presence of well
formed hexagonal-shaped platelets. Alumi-
num (AI) additions result in the formation of
the 4H polytype at the expense of the 6H
polytype. The rate of formation of a-SiC from
the low temperature beta structure is also
enhanced. Particle shapes tend to remain hex-
agonal as Al is dissolved into the lattice but
growth in the thickness direction is augmented
at the expense of growth in the hexagonal
plane. This is a desirable feature for abrasive
use since the particles will be mechanically
stronger. However, Moser (1980) has proposed
that the increased fraction of the lower micro-
hardness 4H polytype that is attributed to the
presence of Al may result in inferior abrasive
performance. Conversely, as B is dissolved
into the structure, particle growth is favored
in the hexagonal plane and shapes become
thinner and extended, producing mechani-
cally weaker shapes, an undesirable outcome.
RAW MATERIALS PREPARATION
A furnace mix prepared to strict stoichiometry
for the overall reaction will state that
1.5 x 105 kg (150 t; 330 000 lb) of Si02 are to
be mixed with 9 x 104 kg (90t; 198 000 lb)
of carbon to produce 1 x 105 kg (100 t;
220000lb) of SiC and 1.4 x 105 kg (140t;
308000lb) of co. In practice, though, there
are three factors which alter the mix formula-
tions. First, some of the carbon is lost to
oxidation with air and moisture and therefore
it cannot be counted towards reaction to SiC.
Second, the ingredients used in the mix
formula are most commonly petroleum coke
and sand, not carbon and Si02 . Adjustments
to the formulation must be made to reflect
impurities in these materials. Third, dust
losses are inevitable for both Si02 sand and
coke.
The Si02 source for SiC manufacture can be
Si02 sand, quartzite or crystalline rock quartz.

Only the purest quartz can be used if a clear
green SiC is to be made from the furnace mix.
If the mix is to be used for making black SiC,
Fe contents up to 0.30% and Al contents up to
0.50% are acceptable as impurities. Calcia and
magnesia must be limited to 0.25% total; addi-
tional amounts will cause an excessively thick
peripheral reaction zone which will have to be
discarded. Size is not critical; particles as large
as 0.64 cm (! in) can be used without affecting
electrical and raw material productivity.
However, the size distribution should be
narrow with minimal fines so that the final
furnace mix is permeable to the CO gases
which must leave the reaction zone.
The most common carbon source is petro-
leum coke, the final residue from crude oil
refining. It typically contains 10-14% volatile
carbonaceous matter, 1-7% sulfur, 0.5-3.0%
ash and up to 3% moisture. The fraction of
carbon available for reaction to SiC thus
ranges from 80% to 90%. The sulfur content
of the coke is in direct proportion to the
sulfur content of the original crude oil.
During furnacing, this sulfur is vaporized at
the reaction site, burned inefficiently at the
surface of the furnace and then emitted from
the plant as various sulfur compounds which
have a characteristic and unpleasant odor.
Total sulfur emissions for a 2.5 x 107 kg
(25000 t; 55 MM lb) per year plant can
approach 5 x 105 kg (SOOt; 1.lMMlb). As a
result, environmental authorities are increas-
ingly restricting sulfur emissions from SiC
manufacturing operations and operators are
therefore purchasing low sulfur petroleum
coke. Some petroleum cokes contain vana-
dium (V) and nickel (NO. These elements
will be distilled into the peripheral reaction
zone as the SiC cylinder is produced. Since
there is an energy cost associated with this
distillation process, the use of purer cokes is
preferable. The particle size of the coke
should preferably be minus 0.95cm (iin)
for good reactivity. The fines portion of the
size distribution should be as low as possible
to maintain final mix permeability, as with
Basic silicon carbide process description 119
sand, and also to minimize dust losses which
can be as high as 2-4% of purchased totals,
particularly for outside storage.
Anthracite coal was used as the carbon
source for SiC for many years. Petroleum
coke is less expensive to use per unit of
carbon and contains less ash and therefore
has become the favored carbon source. It
has a low index of reactivity with CO2 and
SiO but this is counterbalanced by the surface
disintegration effect that occurs when the
larger mole volume SiC that is formed on the
carbon surface flakes off, exposing fresh
carbon for reaction (Tuset and Raaness, 1976).
Bituminous coal contains too much volatile
carbonaceous material for use in the Acheson
furnace.
Furnace mixes are calculated to obtain a
specified Si02 /C ratio, usually about 1.70. It
is therefore very important that each ingre-
dient be accurately analyzed for Si02 and
free carbon. This is an easy task for new
sand and petroleum coke. However, all oper-
ating plants recycle huge quantities of furnace
mix. Typically, recycled mix will constitute
from 40% to 70% of each mix formulation in
a large plant running at steady state, the
exact fraction being variable with furnace
size and total power input. This creates mix
composition control problems. First, the com-
position of revert mixes can vary over a wide
range:
Free carbon 15-30%
Si02 40-60%
SiC 10-30%
Ash 1-5%
This composition variability is com-
pounded by an inherent segregation problem.
Recycled mix from the top of a furnace has a
lower carbon content in comparison to mix
that was located under the cylinder (McMul-
len, 1957). For this reason, operating plants
develop sampling plans and storage proce-
dures to ensure that raw material and recycled
material stocks are well characterized. Wide
swings in final mix composition must be
120 Acheson process
avoided since they negatively affect plant
electrical and labor productivity.
If the furnace mix is low in carbon, Si metal
will form (Butler, 1952). Chemical analysis of
the finished grain will show excessive surface
Si and particle surfaces may be contaminated
with a layer of Si02 (Wei, 1983). In the worst
scenario, superheated Si will flow downward
into the floor of the furnace until it forms a
continuous layer below the bottom of the fur-
nace mix, such that an electrical short circuit
results (Nagamori, Malinsky and Claveau,
1986). When this happens, the apparent fur-
nace resistance is lower than normal and the
furnace yield of acceptable product drops
sharply since a proportion of the power is
being dissipated into heating the earth under
the floor of the furnace. Conversely, if the Si02
to carbon ratio of the mix is too low, the SiC
will form in long, splintery crystals which
break into fine particles during crushing,
reducing the yield of coarse grits. Chemical
analysis of the grain will show excessive free
carbon. Note that both conditions can apply
on a local basis within a furnace. Mix homo-
geneity is therefore fully as important as over-
all formulation. Mixing is therefore preferably
accomplished in large batches.
To make green SiC, the furnace mixes must
be made from high purity sand and low
metals content petroleum cokes. Revert
furnace mix from prior green SiC furnaces
may be used in limited quantities to partially
recover the SiC content. Excess quantities of
revert mix can be blended into furnace mixes
to make green-black SiC, an intermediate
purity final product, or they can be used to
make conventional black SiC by adding
alumina (AI2 0 3 ). Such Al2 0 3 additions are
commonly made to black SiC mixes to
ensure a consistent crystal color. The Al2 0 3
may also be added directly to a furnace by
sprinkling it on top of the graphite core
before adding the top mix.
Porosity agents are traditionally incorpo-
rated into SiC furnace mixes to make them
permeable to the escaping CO. Sawdust,
bagasse and rice hulls are commonly used.
Liquid adhesives such as lignin sulfonates
have also been successfully used to prevent
settling of mixes and the consequent decrease
in open porosity. All of these porosity agents
are organic materials. As the cylinder forms
and heats the surrounding mix, they are
pyrolyzed and the gaseous products of the
process are carried along with the CO to
furnace surfaces where they are burned with
insufficient oxygen for complete combustion.
The resulting effluent gases cause visible air
pollution. For this reason, many operations
have eliminated porosity agents by controlling
the fines content of mix ingredients, especially
the revert mix, to a maximum of 5% finer than
297 ji,m (48 mesh) particles. This may require
briquetting of fines that are scalped from
material flows in order to maintain acceptable
raw material productivity levels.
Sodium chloride (NaCl) was used as a mix
ingredient for several decades in the belief
that the volatile chlorides resulting from the
dissociation of the salt and their subsequent
reaction with metal contaminants such as Fe
and Al were necessary for the production of
high quality green SiC. Plant-scale investiga-
tions have shown that control of raw material
purity is a more efficient way to ensure that
high quality green SiC is consistently manu-
factured (Mehrwald, 1967).
Rice hulls can be used as an SiC raw
material. After coking at 1623 K (1350C), the
rice hulls have a composition of 47% Si02 and
53% C (Lee and Cutler, 1975). When heated to
temperatures of 1623 K (1350C) to 1793 K
(1470 C), cubic SiC is formed in shorter times
than is required for samples of sand and char-
coal, presumably due to the more intimate
mixture of the reactants. The low bulk density
and the extra coking step combine to preclude
commercial use in Acheson furnaces.
FURNACE DESIGN AND OPERATION
Acheson furnaces use electrical resistance heat-
ing to make SiC. Their productivity is therefore

directly dependent on furnace length and rate
of power input. The technological evolution
of Acheson furnace technology over the past
century can therefore be traced by examining
these key parameters.
The first commercial SiC furnace was about
2 m (6.6 ft) long and had a power input rate of
58kW (Acheson, 1893), resulting in a power
intensity of 29 kW I m. Thirty-five years later,
the technology had reached a maturity plateau
and Acheson furnaces were typically 15 m
(49.2 ft) long with a power input rate of
1.5MW (Eardley-Wilmot, 1929) such that
power intensity had reached 100kW 1m.
Furnaces built subsequent to World War II
utilized transformers that could supply
about 3 MW to furnaces that were about 18 m
(59.1 ft) long (Parche, 1964), a power intensity
of 166 kW 1m. More recent furnace designs
employ power intensities approaching
260kW 1m (Exolon-ESK, 1990).
This increase in power intensity over the
past century refutes any considerations that
the cylinder temperature is controlled or that
one can 'overpower' a furnace. Heat transfer is
not a rate-limiting step with vapor phase reac-
tions. Production experience at high power
intensities indicates that even higher power
intensities could be used. The technological
limit to furnace size and power intensity has
been and continues to be the available electri-
cal power supply technology.
Acheson furnace plants are conventionally
designed in three units of three to five fur-
naces per unit. In this configuration, one
furnace in each of the three units is powered
at any given time, thus presenting a balanced
three-phase load to the power company
(Butler, 1952). The other furnaces in each
unit are in the stages of cooling, cylinder
removal and new furnace preparation. Trans-
former capacities for these plants range from
2.5MW to 10MW output.
In most plants, the cylinders are heated by
alternating current. However, the reaction of
sand and coke to SiC is insensitive to the
type of current used. In 1979, the first direct
Basic silicon carbide process description 121
current plant was built in Jaltipan, Mexico.
In this plant, and a few subsequent installa-
tions, three-phase alternating current is
converted by solid-state rectifiers to a single,
direct-current power source. Capital costs
are stated to be lower, reactive power losses
are significantly reduced and power rates
may be lower because the power company
always sees a balanced load.
Most Acheson furnaces are shaped like a
trough, with fixed ends and movable sides
made from steel frames lined with firebricks.
Graphite electrodes are situated in the
masonry head that is situated at each end of
the furnace. The electrodes are connected on
the outside of the head to copper bus bars
that bring in electrical power from the trans-
former or rectifier. At the start of a new
furnacing run, the movable side frames are
positioned between the heads. The furnace
cavity is then filled with the first layer of mix
to the level of the electrodes. This mix formu-
lation is generally richer in Si02 than the mix
formulations used in the upper portions of the
furnace. The filling may be done with lateral
trip conveyors fed by a main delivery belt,
with front-end loaders or with dump hoppers
carried by overhead cranes. Next, the graphite
core that constitutes the initial electrical path
is installed by cutting a shallow channel in the
mix bed and filling it with tamped graphite
recovered from previous furnace runs, mixed
as needed with coke particles. The width-to-
thickness ratio of the graphite core determines
the ovality of the final cylinder. Finally, the
furnace is filled with mix, usually carbon
rich, to the top of the side frames and
heaped to a maximum angle of repose. The
total mix weight for a 12 m (39.4 ft) long
furnace that will yield about 7200 kg
('" 16000 lb) of SiC is typically 32 000 kg
(",70000Ib) (Koehler, 1943). A typical furnace
ready for firing is shown in Figure 4.4.
In a newer design, permanent masonry
head structures and movable side frames are
not used (Wiebke et al., 1979). Instead, elec-
trodes extend up from an underground
122 Acheson process
Figure 4.4 Typical silicon carbide furnace fully loaded just prior to the application of electrical current.
(Photo courtesy of Arendal Smelteverk a.s., Eydehavn, Norway.)
electrical supply. Furnace mix is piled over
these electrodes and away from them forming
an extended U shape such that the effective
length of the furnace is 47.6 m (156 ft)
(Exolon-ESK, 1990; Friesen, 1994). The mix
pile is higher than is used for conventional
furnaces and the sides are allowed to reach
the natural angle of repose for the mix. Overall
furnace dimensions are 36.6 m (120 ft) long
by 15.2 m (50 ft) wide by 6.1 m (20 ft) high.
Total mix weight is about 3 x 106 kg (3000 t;
6.6MMlb) to produce a final cylinder that
weighs about 9 x 105 kg (900 t; 1.98 MM lb).
The entire pile is covered with a plastic sheet
and extra mix is placed along the edges as a
seal. When the furnace power is turned on
and CO is produced, it is confined by the
plastic sheet such that it can only flow out
through vent pipes situated under the plastic
sheet or through underground ducts. The
effluent gas is directed to a central point
where it is flared. Pollution control is thus
enhanced over conventional Acheson fur-
naces. The off-gases could be used for power
generation or as a chemical feed stock, thus
improving the overall cost structure. The
plastic sheet cannot be allowed to become
hot and therefore there is more mix in the
furnace per 1000 kg (1 t; 2200 lb) of SiC product
than there would be in conventional furnaces.
This results in better insulation such that over-
all energy productivity is improved.
At start-up of an Acheson furnace, the elec-
trical power must be supplied at a relatively
high voltage to develop as high a power
input as possible, given the initially high

resistance of the graphite core. The core
quickly becomes hot from joule heating and
in turn heats adjacent mix above 1850 K
(1577C) and the reaction to ,a-SiC and CO is
initiated. Continued heating results in the
formation of more beta crystals and the con-
version of the inner layer of ,a-SiC to a-SiC.
The a-SiC layer is electrically continuous and
therefore it becomes a parallel electrical path
and an efficient joule heating source. As the
cylinder grows and the current path develops
a larger cross-section, the total resistance of
the furnace decreases but at a continuously
diminishing rate. Since most power supplies
and bus bar systems are current limited, the
voltage level is therefore lowered throughout
a furnace run to prevent excessive currents
(Koehler, 1943). The usual operating strategy
is to maintain a constant power input rate
throughout a furnace run consistent with the
design of the electrical power supply and to
end a furnace run at a predetermined total
power input.
The effluent CO is a significant operating
problem. It is produced in volumes ranging
from 25 to 40m3 /h (rv 15-24scfm) along each
meter of furnace length, depending on power
intensity. In conventional open furnaces, it
diffuses through the covering mix until it
can flare at the upper mix surface or at
cracks in the side walls. The combustion pro-
cess associated with this flaring is usually
incomplete. Furthermore, the exiting gas is
not pure CO; it also may include volatile
tars and gases from the coke, pyrolyzed
organic porosity agents and various sulfur
compounds, including hydrogen sulfide. The
potential for producing visual haze and objec-
tionable odors is thus very high. The plastic-
sheet-covered furnace discussed above was
specifically designed to prevent this problem
(Exolon-ESK, 1990: Friesen, 1994). Another
furnace design employs geodesic domes
made from Al to cover a furnace which has
the shape of an almost complete circle. The
effluent gases are collected from the open
space between the top of the furnace and
Basic silicon carbide process description 123
the dome and piped to a high efficiency
burner.
Astute managers have been fascinated with
the potential economic benefits of recovering
the energy content of the CO since the early
days of the process (Tone, 1908). In theory
this could replace about one-third of the
input power (McMullen, 1957). Operating
problems such as explosive hazard and tar
build-up in flues appear to have frustrated
any significant acceptance of the practice
until environmental pressures mandated
solutions such as the domed furnace and the
covering plastic sheet.
Since all heating is resistive, the normal
operation of an Acheson furnace is essentially
silent. However, a distinctively noisy condi-
tion known as a 'blow' occurs infrequently.
A blow is typically a vertical fountain of hot
gases and sparks that erupts from the top of
the furnace with a roaring sound. The inten-
sity varies and visible flaring can reach a
height of 5 m (16.4 ft). Furnace operators
extinguish blows by shutting off the power
for 10-15min and spilling loose furnace mix
into the blow as it subsides in intensity. The
origin of the phenomenon is not documented
in the literature but it is thought to be related
to local electrical conduction faults which
allow arcing to occur. The channels through
which the hot gases flow during a blow are
lined with exceptionally large SiC crystals as
shown in Figure 4.5. Local temperatures may
exceed 2700 K (2427C) as indicated by the
rounded, fire-polished morphology of the
crystal aggregates shown in Figure 4.6.
The upper surface of the furnace mix gradu-
ally sinks over the course of a furnacing run
because the cylinder is more dense than the
original mix and because a considerable
weight of CO leaves the system. The end of a
furnace run in smaller furnaces is therefore
usually determined by penetration of the
upper surface of the cylinder through the
covering mix. When this hot surface is
exposed to ambient conditions, the attendant
heat losses become so high that further power
124 Acheson process

Figure 4.5 Large, well formed silicon carbide crystals formed by condensation of silicon carbide vapors in
a 'blow' channel.

Figure 4.6 Silicon carbide crystal aggregates that have been fire polished at temperatures exceeding 2700 K
(2427 C).

input is wasted unless the additional mix is
placed onto the top surface. The other limiting
condition for a furnace run is the current-
carrying capacity of the transformers and
bus bars. Since the cylinder in larger furnaces
will be heated for a longer time, the minimum
width and depth of insulating mix cover are
larger. At the center of these larger cylinders,
the average crystal size is larger and the final
grain is less friable.
Furnace cooling time is variously stated in
the literature to extend up to several days.
The practical dilemma facing operators is the
necessity to make the furnace available for the
next run, balanced against the intense heat
that will be radiated from a newly-made
cylinder. This dilemma is compounded by
the insulating nature of the fine particulate
matter covering the cylinder. When stirred
up, for example by removal of furnace side
frames, these fine particulates are carried up
by convective air currents into an impres-
sively opaque and filthy dust cloud. In addi-
tion, hot coke particles may burn, resulting in
lower raw material productivity. Cylinder
cooling can be facilitated by stripping away
horizontal layers of mix with a crane or a
vacuum system until the cylinder is exposed.
Water sprays are also used for cooling and for
dust suppression, creating the inconvenience
of a muddy plant.
After the mix is removed from the furnace
top and sides, the upper half of a cylinder is
taken away in large chunks after being
broken by a hydraulic grab mounted on
portable equipment. The graphite core is
recovered for use in subsequent furnaces.
Finally, the lower half is removed in chunks.
SILICON CARBIDE SEPARATION
The large chunks of cylinder removed from
furnaces are by no means homogeneous.
Graphite powder may adhere to the inner sur-
faces. The generally thick annular layer a-SiC
crystals toward the inside of the cylinder may
be contaminated with Si and carbon but it
Basic silicon carbide process description 125
represents the purest product. Contaminant
elements that were present in the reactant
sand and coke, such as Fe, AI, calcium (Ca)
and V, are reduced to their elemental form
by the high CO/C02 ratios that prevail in
the central regions of the cylinder. Further,
these elements have significant vapor pres-
sures at the prevailing temperatures, which
are typically 2300 K (2027C). These elements
are therefore convected radially outward in
the flow of SiC sub-species. They recondense
in the lower temperature primary reaction
layer where ,a-SiC is being formed or in the
adjacent layer of mix (Butler, 1952). The loca-
tion and characteristically different color and
texture of this region result in the popular
designation 'crust'.
The crust is preferably scraped from the
chunks of cylinder and discarded since it can
contain up to 10% metal oxides, primarily of
Fe, Ca, Al and V.
The highest tonnage application for SiC is a
product termed metallurgical SiC, a silicon
and carbon source for the iron casting indus-
try. Purity is not important to its function.
Therefore, the chunks of cylinder may be
crushed in their entirety to make this product,
often without removing the crust. The crushed
mixture will contain from 90% to 92% SiC.
More pure SiC for abrasive, refractory and
other applications must be cut away from
the cylinder chunks. The process is typically
manual. Large pieces of SiC cylinder are
dumped onto a cleaning floor where workers
use pneumatic chipping hammers to cut
away the less pure outer layer. The division
is done solely by visual appearance. The
two separated materials are manually moved
onto conveyors or into hoppers for crushing
into metallurgical grade (80-90% SiC) or to
No. 1 SiC (+97% SiC). Inevitably, some of
the first grade SiC is lost to less pure grades
and the overall plant efficiency is thus
compromised. The manual cleaning of green
SiC uses the same practice except that the
outer layer is less thick and is easier to
remove.
126 Acheson process
Table 4.1 Commercial purities of silicon carbide
SiC, Surface Si Free C
min. (%) (%) (%)
No.1 black 97.0 0.85 (max.) 0.25 (max.)
Green-black 96.5 0.75 (max.) 0.50 (max.)
No.1 green 97.2 0.60 0.50
a Si02 , coke and partially converted coke.
Mechanized methods for separation of the
two grades of SiC have been proposed. Since
impurities such as iron distill into the lower
purity zone, magnetic separation can be used
if the Fe content of the initial mix is increased
slightly (Seider, Guichelaar and Anderson,
1987a). A similar method is based on mixing
fine magnetic powders with the crushed frag-
ments of an entire cylinder. The magnetic
powders are concentrated into the pores and
voids that are more prevalent on the surfaces
of particles derived from the lower purity
reaction zone. Conversely, a-SiC particles are
smooth and dense such that the powders do
not adhere. The two types of particles can be
readily separated by a high intensity magnetic
field. Separation efficiencies of greater than
95% are possible (Seider, Guichelaar and
Anderson, 1987b). Separation on the basis of
particle shape has also been shown to be
feasible (Versteegen and Dalmijn, 1990).
CRUSHING AND GRADING
The crushing and screening of SiC into various
final products is a mature technology. Crusher
design affects particle shape with rolls produ-
cing high aspect ratio particles suitable for
certain abrasive products and impact crushers
producing blocky particles which have a
higher bulk density. Similarly, various screen-
ing devices are chosen for their high through-
put or their ability to separate into closely
spaced fractions. Depending on its end use,
the finished product may be magnetically treat-
ed to remove Fe particles worn from crushing
Total Fe, Total AI, Color Contamination,
max. (%) max. (%) (% crystals) max. (%)a
0.25 0.25 90 (min.) black 2
10-40 black 1
10 (max.) black,
35 (min.)
light green
machinery, washed to remove adhering
graphite and acid-treated to remove surface
Si. Froth flotation can be used to recover SiC
after wet processing (Smith, Llewellyn and
Sullivan, 1995). Powders are made from dust
collector fines, by ball-milling coarse fractions
and by attrition milling. Separation into size
fractions is done by elutriation or settling.
Powders intended for structural ceramics are
often treated with hydrofluoric acid (HF) or
reducing gases to remove surface oxides
(Rahaman, Boiteux and De Jonghe, 1986).
Silicon carbide (SiC) is graded by color,
chemical composition and contaminant
particle content, as shown in Table 4.1.
MANUFACTURING COST FACTORS
In comparison to other manufactured
materials, SiC manufacturing is electrical
power intensive. Most plants are therefore
located in areas where power is relatively
inexpensive, typically because it derives
from hydroelectric installations. A few SiC
crude plants have low power costs as a
result of government concessions. The specific
power requirement is normally in the range of
6.5 kW . h to 8.0 kW . h/kg, the theoretical
requirement being 5.74 kW . h/kg (Finlay,
1952). Small furnaces have proportionally
higher thermal losses than large furnaces
and their electrical usage is greater per kilo-
gram of SiC produced. Parche (1964) states
that the manufacture of green SiC requires
12 kW . h/kg; such high energy usage may
not include SiC losses to metallurgical product

and recycled mix, a common energy account-
ing error. Green SiC has the same electrical
power requirement as black SiC
The two raw materials, sand and petroleum
coke, are commodity materials. Differences in
delivered costs from plant to plant are primar-
ily due to transportation and composition.
Each kilogram of SiC product may use 110-
120 kg of coke. Sand usage tends to be close
to the stoichiometric amount if a reasonably
dry and calcia-free sand is used.
Overall plant costs for the manufacture of
SiC, before administrative overhead, are typi-
cally 30% electrical power, 30% raw materials,
20% labor, 10% maintenance and 10% miscel-
laneous.
The cost structure for the conversion of
crude SiC to grain and powder products
reflects labor intensity. Equipment wears
quickly so labor costs for maintenance are
usually the most significant item. Many of
the crushing and grading operations are
done in batches and labor costs are corre-
spondingly higher per kilogram of output.
Quality control costs increase significantly as
particle size decreases toward powder sizes.
Power requirements are about 1.5 kW . h/kg
(Smoak et al., 1978).
Approximately 49% of the SiC produced
world-wide by the Acheson process is the
lower purity metallurgical grade and 39% is
abrasive grade. The remainder is sold into
the refractory and specialty markets (Austin,
1989).
SUMMARY
It would be presumptuous to believe that one
could improve on the summary written by
McMullen (1957):
The art of furnacing SiC has not departed
radically from the method originated by
Acheson. Today's furnaces are much
larger but they still use his principle of heat-
ing from within, with the charge acting as
a refractory container as well as a thermal
Summary 127
insulator for the ingot being formed.
Improvements in furnace design have facili-
tated loading and unloading operations.
Large scale collection and utilization of
waste gases have not yet been achieved.
Changes in core composition and geometry
have resulted in a moderate improvement
in over-all efficiency of the operation.
Better physical and chemical properties of
the product have been attained by control-
ling mix composition and power input.
Several starts have been made toward a con-
tinuous process for making SiC [McMullen,
J.C, 'A review of patents on silicon carbide
furnacing,' J. Electrochem. Soc., 104, 464,
1957. Reproduced with permission of the
Electrochemical Society, Pennington, NJ.]
Since McMullen wrote this summary, furnaces
have grown much larger, power supplies have
changed to take advantage of solid-state
electronics and specific electrical power usage
has decreased. Pollution control is greatly
improved in the newer installations. The
product, however, forms from its raw materials
in essentially the same static reactor used by
Dr Acheson over a century ago.
The disadvantages of this reactor are the
variable product chemistry, the coarse crystal
size and the practical necessity to manufacture
on a large scale. They are far overbalanced by
the many advantages that have sustained the
use of the Acheson furnace concept:
the inherent thermal efficiency derived from
internal joule heating;
the ease with which extreme temperatures
can be attained;
the static reaction zone with attendant
considerations of no reactant mix feeding
mechanisms;
the composition gradient that results from
the radial temperature gradient and effluent
gas flow direction;
the inherent control stability.
It is thus not unreasonable to predict that
McMullen's summary (except for the waste
128 Acheson process
gas recycling proviso) will apply through the
next century.
REFERENCES
Acheson, E.G. (1893) Carborundum: its history,
manufacture and uses. J. Franklin Inst., 136, 194-
214.
Acheson, E.G. (1895) Production of artificial crystal-
line carbonaceous materials. US Patent Reissue
No. 11,473.
Austin, G.T. (1989) Abrasive materials, in Minerals
Yearbook, US Bureau of Mines, pp. 77-96.
Baumann, H.N. (1952) The relationship of alpha
and beta silicon carbide. J. Electrochem. Soc., 99,
109-14.
Butler, G.M. (1952) Electric furnace silicon carbide
production. J. Electrochem. Soc., 99, 51C-54C
Cheape, CW. (1985) Family Firm to Modern Multina-
tional, Norton Company, a New England Enterprise,
Harvard University Press, Cambridge, MA.
Colson, A. (1882) Some new carbosilicic com-
pounds. c.R. Acad. Sci., 94,1316--18.
Cowles, E.H. and Cowles, A.H. (1885) Electric
smelting furnace. US Patent 319,945.
Despretz, CM. (1849) Fourth note on the fusion
and volatilization of bodies. c.R. Acad. Sci., 29,
709-24.
Drowart, J. and De Maria, G. (1960) Thermo-
dynamic study of the binary system carbon-
silicon using a mass spectrometer, in Silicon
Carbide, A High Temperature Semiconductor (eds
J.R O'Connor and J. Smiltens), Pergamon, New
York, pp. 16--23.
Eardley-Wilmot, V.L. (1929) Artificial Abrasives and
Manufactured Abrasive Products and their Uses,
F.A. Acland, Ottawa, pp. 6--14.
Exolon-ESK (1990) Carbolon, July, 1-2, Exolon-ESK
Company, Hennepin, IL.
Exolon-ESK (1991) Carbolon, March, 1-2, Exolon-
ESK Company, Hennepin, IL.
Finlay, G.R (1952) Calculated energy requirements
of electric furnace products. Chem. Canada, 14(2),
25-28.
Friesen, L. (1994) A century of SiC Ceram. Indust.,
Feb., 41-44.
Hamilton, D.R (1960) Preparation and properties of
pure silicon carbide, in Silicon Carbide, A High
Temperature Semiconductor (eds J.R O'Connor
and J. Smiltens), Pergamon, New York, pp. 43-52.
Jepps, N.w. and Page, T.F. (1983) Polytypic trans-
formations in silicon carbide. J. Cryst. Growth
Character., 7, 259-307.
Kistler-De Coppi, P.A. and Richarz, W. (1986) Phase
transformations and grain growth in silicon
carbide powders. Int. J. High Technol. Ceram., 2,
99-113.
Koehler, W.A. (1943) Principles and Applications of
Electrochemistry, Vol. 2, Applications, Wiley, New
York, pp. 443-47.
Lee, J.G. and Cutler, LB. (1975) Formation of silicon
carbide from rice hulls. Ceram. Bull., 54(2), 195-98.
Margrave, J.L. and Mamantov, G. (1967) High-
temperature reactions, in High Temperature
Materials and Technology (eds I.E. Campbell and
E.M. Sherwood), Wiley, New York, p. 88.
Marsden, RS. (1880) Crystallization of silica from
fused metals. Proc. R. Soc. Edinb., 11, 37-4l.
McMullen, J.C (1957) A review of patents on silicon
carbide furnacing. J. Electrochem. Soc., 104, 462--65.
Mehrwald, K.H. (1967) Die Rolle von NaCl bei der
Technischen SiC-Herstellung. Ber. Dtsch. Keram.
Ges., 44, 148-55.
Moser, M. (1980) Microstructures of Ceramics, Struc-
ture and Properties of Grinding Tools, Akademiai
Kiado, Budapest, pp. 119-39.
Nagamori, M., Malinsky, I. and Claveau, A. (1986)
Thermodynamics of the Si-C-O system for the
production of silicon carbide and metallic
silicon. Met. Trans. B, 17, 503-14.
Parche, C (1964) Silicon carbide, in Encyclopedia of
Chemical Technology, 2nd edn, Wiley, New York,
pp.114-32.
Poch, W. and Dietzel, A. (1962) The formation of
silicon carbide from silicon dioxide and carbon.
Ber. Deut. Keram. Ges., 39, 413-26.
Porter, RF. (1967) High-temperature vapor species,
in High Temperature Materials and Technology (eds
I.E. Campbell and E.M. Sherwood), Wiley, New
York, p. 74.
Rahaman, M.N., Boiteux, Y. and De Jonghe, L.C
(1986) Surface characterization of silicon nitride
and silicon carbide powders. Ceram. Bull., 65(8),
1171-76.
Scace, R.I. and Slack, G.A. (1960) The Si-C and
Ge-C phase diagrams, in Silicon Carbide, A High
Temperature Semiconductor (eds J.R O'Connor
and J. Smiltens), Pergamon, New York, pp. 24-30.
Seider, RJ., Guichelaar, P.J. and Anderson, RO.
(1987a) Production of silicon carbide with auto-
matic separation of a high grade fraction. US
Patent 4,659,022.
Seider, RJ., Guichelaar, P.J. and Anderson, RO.
(1987b) Automatic method for separating and
cleaning silicon carbide furnace materials. US
Patent 4,686,032.

Smith, C.W., Llewellyn, T.O. and Sullivan, G.V.
(1995) Silicon carbide, flotation recovery, in Ency-
clopedia of Chemical Processing and Design (ed. J.J.
McKetta), Vol. 50, Wiley, New York, pp. 172-78.
Smoak, R.H., Korzekwa, T.M., Kunz, S.M. and
Howell, E.D. (1978) Silicon carbide, in Kirk-
Othmer: Encyclopedia of Chemical Technology, Vol.
4, The Minerals, Metals and Materials Society,
Warrendale, PA, pp. 520-35.
Tone, FJ. (1908) Use of waste gases. US Patent
908,357.
Tuset, J. Kr. and Raaness, O. (1976) Reactivity of
reduction materials for the production of silicon,
silicon-rich ferroalloys and silicon carbide, in
34th Electric Furnace Conference Proceedings, 1SS-
A1ME, Warrendale, PA, pp. 101-07.
References 129
Vanderbilt, B.M. (1974) Inventing: How the Masters
Did It, Moore Publishing, Durham, NC, p. 187.
Versteegen, J.M. and Dalmijn, W.L. (1990) Concen-
tration of silicon carbide with a density process.
Min. Metall. Process., 8, 136-40.
Wei, G.c. (1983) Beta SiC powders produced by
carbothermic reduction of silica in a high-tem-
perature rotary furnace. Comm. Am. Ceram. Soc.,
C-l11-13.
Weimer, AW., Nilsen, K.J., Cochran, G.A and
Roach, R.P. (1993) Kinetics of carbothermal
reduction synthesis of beta-silicon carbide.
AIChE J., 39(3), 493-503.
Wiebke, G., Korsten, A, Benecke, T. and Petersen, F.
(1979) Collector apparatus for gaseous reaction
products. Canadian Patent 1,066,019.
ELECTRIC ARC FURNACE PROCESSES
William S. Wilson and Philip J. Guichelaar
INTRODUCTION
The electric arc furnace processing of oxide
ceramics is a well-established and widely-
used industrial technology. Raw materials
are readily melted together by joule and
radiant heating to form substantially large
liquid volumes. These are refined if necessary
with carbon and additions of metal scaven-
ging agents such as iron, and the product is
then poured into molds for solidification.
The castings can be used directly as fused
cast refractories or, more commonly, are
crushed down to fine sizes for use in a wide
variety of applications.
Arc furnaces are less commonly used for
manufacturing non-oxide ceramics. The melt-
ing points of most of these materials are well
over 2273 K (2000C) and thermal conductiv-
ities are high, resulting in a condition where
reaction products are more likely to freeze
just outside of the arc zone than to flow
away and form a surrounding liquid pool.
Production is therefore limited to relatively
small batch quantities. Furthermore, useful
shapes cannot be directly made by the arc fur-
nace process and downstream processing and
consolidation are always necessary.
The patent and technical literature describe
many attempts at developing arc-based
manufacturing processes for non-oxide cer-
amics (Lipp, 1965). Successes exist, notably
boron carbide (B4 C) for which production
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
5
quantities are about 500000 kg (1.1 MM lb)
per year (Schwetz and Lipp, 1985). We will
therefore discuss the manufacturing tech-
nology for this material in detail and then
enumerate similar processes used for other
commercial non-oxide ceramics.
BORON CARBIDE MANUFACTURING
Boron carbide (B 4 C) is manufactured in elec-
tric arc furnaces by heating anhydrous boric
acid (i.e. B20 3 ) together with graphite par-
ticles. The electric arc supplies sufficient
thermal energy to melt the boric oxide
(B 2 0 3 ) and to react it with the graphite to
produce B4 C:
2B20 3 + 7C ----> B4C + 6CO (5.1)
The reaction occurs at temperatures slightly
above the melting point of B4 C, 3036 K
(2763C) (Thevenot, 1990). While the forma-
tion of B4 C is in theory easy to accomplish,
the enormous volume of carbon monoxide
(CO) that is liberated makes practical opera-
tions troublesome at best. Total energy
productivity is quite low since 70-95 MW . s
are required per kg of gross product (20-
26 kW . h/kg) in comparison to the theoretical
energy requirements of 14.7MW s/kg. How-
ever, arc furnace manufacture is almost twice
as efficient as Acheson resistance furnace
production of B4 C (Scott, 1964b).
132 Electric arc furnace processes
RAW MATERIALS PREPARAnON
Anhydrous boric oxide (B20 3 ), produced by
the dehydration of boric acid (H3 B03 ), is read-
ily available in the desired purity of 99.0%
B2 0 3 Coarse sizes such as 4.76 mm (4 mesh)
are preferred to minimize dust collector
losses. Boric oxide should be purchased and
stored in bags that have a moisture-resistant
barrier since it is very hygroscopic and any
hydration creates furnacing problems. For
best results, the loss-on-ignition must be
maintained below 1.5%.
Most final product specifications for boron
carbide require purity in excess of 99% and
therefore the preferred source of reactant
graphite is machining chips from electrode
turning operations. These are usually pur-
chased as 2.38 mm (8 mesh) and finer particles.
Purity exceeds 99.9% carbon.
A furnace mix formulated on a stoichio-
metric basis would contain 62.4% by weight
anhydrous boric acid (Le. B20 3 ) and 37.6% of
graphite particles in order to yield a product
which contains 78.3% boron. This proportion
will vary depending on the molar ratio of
carbon to boron that is specified for the final
product; typically boron-rich B4 C is specified.
However, a substantial portion of the graphite
will be lost to oxidation with air and therefore
mix formulations for stoichiometric B4 C are
carbon-rich, typically in a ratio of 71 % boron
to 29% carbon. Each mix batch also contains
from 20% to 40% 'old' mix reverted from pre-
vious furnace runs. Since the addition of the
partially deoxidized revert requires less
energy input for a given volume of mix and
will result in less fume production, batches
of mix that are designated for the bottom of
the furnace charge will preferably contain up
to 40% revert. Dust collector fines from crush-
ing operations involving recycled mix and
B4 C grain are also included in the mix in
amounts up to 10% of the total to improve
raw material productivity. Excess grits from
crushing operations can also be included but
it is usually more profitable to sell them as fine
powders after milling, elutriation and acid
leaching.
The total carbon, total boron and free B2 0 3
concentrations should be known for all of the
raw materials to be used in each mix batch.
The components for each batch are then
weighed in proportions that will achieve the
desired boron-to-carbon ratio. Mixing follows,
typically in a ribbon blender, with the addi-
tion of sufficient kerosene to suppress dust
losses, typically about 1%.
FURNACE DESIGN AND OPERAnON
Boron carbide is made in open-top arc
furnaces. The conventional three-electrode,
three-phase power arrangement is preferred
for energy productivity but single-phase fur-
naces have been successfully used. Electrode
circles are small. Typically, the 0.30-0.35 m
01.8-13.8 in) diameter graphite electrodes
used in a 1.8 m (5.9 ft) diameter, 2000 kVA
furnace, are spaced from 0.30-0.35 m 01.8-
13.8 in) apart. Their closeness is usually
dictated by electrode holder configurations.
The spacing will be less for lower power
furnaces (Scott, 1964b). A three-phase trans-
former provides an output voltage to the
electrodes that can be stepped from about
80V to about 140V.
The furnace structure is designed for easy
disassembly. The slightly conical steel shell
is set on a carbon base as shown in Figure
5.1. The assembly may be supported by a
mold cart so that it can be pulled away from
the electrodes. The shell is continuously water
cooled on its outside walls.
A furnace run begins by lining the inside
bottom surface of the furnace shell with a
layer of petroleum coke. A layer of bottom
mix, containing 40% revert, is spread over
the petroleum coke and banked up around
the periphery. A cavity matching the electrode
configuration is scooped out from under the
electrodes to a depth of about 0.1 m (3.9 in).
This cavity is filled with 2.38 mm (8 mesh) gra-
phite chips. The electrodes are then energized
 Boron carbide manufacturing 133

Electrode Electrode

Arc Area

Water Cooled
Furnace Shell

""
Start-Up - - _......_ - - During Process

Figure 5.1 Cross-sectional views through a typical furnace, (1) at the beginning of a boron carbide furna-
cing run showing the preparation of the furnace bottom (left side) and (2) midway through a run showing
the formation of the ingot (right side).

and lowered until contact is made with the
graphite. Mix is lightly fed at this time until
a stable power input is established.
During a run, additional furnace mix is
added manually by operators as the arc
under the electrodes becomes more visible.
This mix should be added slowly at a rate of
about 50-60kg (1l0-132lb) each 10 min. A
typical furnace run will thus take about 18-
20 h. Sufficient mix must be present to
minimize radiative heat losses and operators
will usually maintain a mix cover that is
excessively deep to minimize the dangers
associated with the spitting out of molten
globules. This spitting is an annoying trait of
B4 C furnacing attributed to the strong CO
currents, the conductivity of the product and
the magnetic forces from the arc current.
However, if the mix cover is over 0.15 m
(5.9 in) thick, excessive quantities will be
carried away into the dust collector by the
large volumes of CO that must diffuse away
from the reaction site. In addition, excessive
feed rates may cause limiting reaction condi-
tions and reduce energy productivity.
As a furnacing run progresses, B4 C product
is formed according to reaction 5.1 above. The
local composition across a furnace ingot will
vary with operating conditions such as feed
rate, arc length, spitting tendencies and tem-
perature gradients. The product immediately
outside of the arc zone is at a lower tem-
perature and solidifies quickly, such that
pillars of boron carbide are formed under
each electrode as shown in Figure 5.1. These
pillars may connect together, forming one
134 Electric arc furnace processes
Table 5.1 Typical grades of boron carbide powders

Grade Total B, B2 0 3 , Total Fe, Total B + C,

min. (%) max.(%) max.(%) min. (%)

Technical 70 3 2 94
Industrial 73 0.5 1 96
High purity 76.5 0.2 0.1 98

three-lobed ingot, or they may be singular for
the case of a wider electrode spacing. The fur-
nace electrodes are gradually lifted away from
the advancing pillars by the power control
system until their tips approach the top of
the water-cooled area of the furnace shell.
The power is then turned off, the electrodes
are withdrawn and the top of the furnace is
covered with additional mix while it cools.
If desired, the furnace shell can be removed
and another run initiated in a second furnace
shell.
The enormous quantities of fume that are
spewed from the furnace must be removed
from the furnace area by an adequate venti-
lation system such that no CO poisoning
hazard exists for personnel in the area and
all fugitive dusts are contained. This requires
a hood, connecting ductwork and a fan which
provides a flow rate of about 2.5 m 3 / s
(",5300 scfm) for each square meter of furnace
surface area. The H 3 B03 and coke particles
are fine and well dispersed and therefore an
adequate bag house collector must be pro-
vided. The system will be over-designed in
comparison to other similar installations
since it must have a capacity of about 10% of
each furnace charge. The shakedown mechan-
ism and bag materials must anticipate a fine,
sticky dust that quickly blocks air flow. Fume
control is also important for environmental
reasons. Boron is a plant nutrient which can
cause gigantism if in abundance in soils
(Massey and Kane, 1972). Excessive quantities
will kill many forms of vegetation.
CRUSHING AND GRADING
After cooling, the furnace shell is lifted to a
breaking floor and the contents are dumped

Figure 5.2 Traditional boron carbide powders. (Weimer, A.W., Roach, R.P., Haney, CN., Moore, W.G. and
Rafaniello, W., 'Rapid carbothermal reduction of boron oxide in a graphite transport reactor,' AIChE J.,
37(5), 759-68. Reproduced by permission of the American Institute of Chemical Engineers, 1991
AIChE. All rights reserved.)

Table 5.2 Properties of boron carbide powders (Weimer et al., 1991)
Powder B C
(wt%) (wt%)
Tetrabor 800 78.0 19.6
Tetrabor 1500 76.6 20.8
out. The solid portion under the electrodes
will form about 900 kg (,....,2000 lb) of the total.
It will be surrounded by about 2300 kg
(,....,5100 lb) of unreacted mix, assuming that
7000 kg (,....,15000 lb) of mix was added to the
furnace during the run of which 500 kg
(I 100 lb) was lost to the dust collector. The
ingot is broken into chunks that are hand
sorted by comparing their color, density and
texture with standard samples. The crude is
then crushed to 2.38 mm (8 mesh) and finer.
Each crude lot is designated to be technical,
industrial or high purity grade based on a
representative chemical analysis. A typical
specification for each is given in Table 5.l.
Subsequent processing into grains and
powders for all of these applications follows
conventional practice. Since boron carbide
causes extraordinary wear of crusher parts,
finish graded product is always washed in a
sulfuric acid bath to remove iron and free B2 0 3
High purity fine powder is normally sold on
the basis of particle size and the fixed B/ C
ratio. Two grades of powder sold by Elekto-
schmelzwerk Kempten GmbH (Munich) as
Tetrabor 800 and 1500 are shown in
Figure 5.2 and their properties are shown in
Table 5.2. Final product particle morphology
is characterized by fractured surfaces (Figure
5.2) (Weimer et ai., 1991).
OTHER NON-OXIDE CERAMICS
The arc furnace process has been used in
essentially the same manner to produce
other non-oxide ceramic materials, such as
zirconium carbide and titanium carbide
(Scott, 1964a,c), aluminum boride and boron
References 135
0 Fe Fixed Surface area
(wt%) (ppm) B/C (m 2 /g)
0.65 530 4.37 3.2
1.82 390 4.04 11.7
silicide (Vogt and Wiebke, 1965) and tungsten
carbide (Kobayashi, 1972). The process
descriptions usually indicate that the final
product chemistry will vary with raw material
balance. This is particularly true for oxygen
purity and carbon uniformity (Storms, 1967).
Titanium carbide and B4 C may be contami-
nated by nitrides if air enters the reaction
area (Ridgway, 1940). Arc furnace processing
of non-oxide ceramics is economical but
limited to products that can tolerate a
variable final chemistry, coarse grains and
particle shapes that result from crushing
processes.
REFERENCES
Kobayashi, Y. (1972) Method for manufacturing
tungsten carbide. Japanese Patent 47-51000.
Lipp, A (1965) Boron carbide: production, proper-
ties, applications. Techn. Rundsch. 14,5; 28, 19; 33,
5; (1966) 7,3.
Massey, AG. and Kane, J. (1972) Boron, Mills &
Boon, London, p. 15.
Ridgway, RR (1940) Method of producing the
abrasive metal carbides. US Patent 2,285,837.
Schwetz, K.A and Lipp, A (1985) Boron carbide,
boron nitride, and metal borides, in Ullman's
Encyclopedia of Industrial Chemistry, 5th edn, A4,
Weinheim, pp. 295-307.
Scott, J.J. (1964a) Arc furnace process for the
production of zirconium carbide. US Patent
3,161,470.
Scott, J.J. (1964b) Arc furnace process for the
production of boron carbide. US Patent 3,161,471.
Scott, J.J. (1964c) Arc furnace process for the
production of titanium carbide. US Patent
3,161,472.
Storms, E.K. (1967) The Refractory Carbides, Aca-
demic Press, pp. 226-27.
136 Electric arc furnace processes
Thevenot, F. (1990) Boron carbide - a comprehen-
sive review. J. Eur. Ceram. Soc., 6, 205.
Vogt, A. and Wiebke, G. (1965) Process for the
production of carbides, borides and silicides of
the IIIrd and IVth main groups of the periodic
system, whose vapor phase in the arc conducts
electrical current poorly. FRG Patent No. DE
191343.
Weimer, A.W., Roach, R.P., Haney, CN., Moore,
W.G. and Rafaniello, W. (1991) Rapid carbo-
thermal reduction of boron oxide in a graphite
transport reactor. AIChE ,., 37(5), 759-68.
TUBE/PUSHER/MOVING BED FURNACE
PROCESSES
William E. Hollar Jr and Jonathan
INTRODUCTION
Tube or pusher furnaces, hereafter called
pusher furnaces, and moving bed furnaces
have been used for the continuous production
of ceramic powders. The present work will
focus on the use of these furnaces as reactors
for non-oxide ceramic powder synthesis at
high temperatures (i.e. above 1773 K (1500 C)).
Pusher furnace characteristics as a reactor
include:
continuous operation;
plug flow of solids having a uniform resi-
dence time;
gas-solid contacting whereby the gas is
supplied as a reactant or as a purge to
remove by-products such as carbon mon-
oxide;
a static bed (i.e. gas flow above the solids,
with no directed flow through the bed) or
packed bed (i.e. purge or reactant gas flow
directed through the solid bed) (Reh, 1978;
Dunn et ai., 1991) operation. The static bed
configuration appears to be typical.
Each of these characteristics affects the
product characteristics, the process scale-
ability, and the reactor performance. A
schematic of a pusher furnace including typi-
cal hardware features is shown in Figure 6.1.
Major reactor design advantages of a pusher
furnace system are summarized in Table 6.1.
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
6
J. Kim
Moving bed furnaces have several features in
common with pusher furnaces. Moving bed
reactors are continuous, plug flow reactors.
They are always operated with a purge or
process gas flowing though the bed; gas-
solid contact can be either co- or counter-
current but is typically counter-current. A
typical moving bed furnace configuration is
shown in Figure 6.2.
The furnace process step represents only
one step of a typical non-oxide ceramic
powder manufacturing process (Kim and
McMurtry, 1985). Other steps include feed
preparation, crude product purification and
post-processing such as milling. Reviews of
some of these other processing steps can be
found in Part Seven of this text. The synthesis
step typically presents the most challenging
technical difficulties; therefore, a detailed eva-
luation of the pusher furnace and moving bed
furnace is warranted.
ADVANTAGES OF PUSHER FURNACE
SYNTHESIS PROCESSES
The use of a pusher furnace for non-oxide
ceramic powder synthesis imposes the condi-
tion of plug flow on the reacting solids. This
impacts reactor design, operating conditions
and production costs. The design and operat-
ing conditions include residence time and
138 Tube/pusher/moving bed furnace processes

Crucibles
Pre- or Boats
Pusher Cooling
Mechanism Heat Zone
Zone Hot Zone

Crucible
Feed
Mechanism

+ +
Airlock Airlock

Water Insulation
Cooled
Channels

Figure 6.1 Common features of pusher furnaces.

reactor volume which control furnace size and should be better than the product of a mixed
throughput. Reacting solids in plug flow have flow reactor (Dunn et al., 1991).
a uniform residence time distribution. In the A plug flow reactor can lead to other advan-
absence of transport limitations, the entire tages relative to a mixed flow reactor such as a
feed experiences the same thermal and continuous fluid bed. The reactor volume to
chemical environment for the same length of produce fully reacted powder is smaller for a
time. Theoretically, the uniformity of the plug flow reactor (Levenspiel, 1972). This mini-
product produced in a plug flow reactor mizes the hot zone dimensions and will reduce
operating and capital costs. For reactions which
are sensitive to residence time due to phenom-
Table 6.1 Potential reactor design and economic ena like grain growth, a plug flow reactor
advantages of a pusher furnace synthesis process
minimizes the residence time necessary to
Reactor characteristic Potential advantages achieve full reactant conversion.
Pusher furnaces can offer flexibility in their
Reactants in plug Minimum reactor volume to physical configuration. Horizontal configura-
flow achieve complete conversion tions are typical, but pusher furnaces with cru-
Uniform reactant residence cibles moving vertically have been reported
time
(Hayashi, Mochizuki and Ozawa, 1986;
Static/packed bed Optimum for slow reactions Wilkening, 1988). The furnace purge gas can
Flexibility in reactant particle be directed co-current or counter-current
size
relative to the solid reactant flow. The gas-
Continuous Efficient energy utilization solid contacting scheme will be critical when
Reduced manpower gaseous by-products adversely impact prod-
requirements uct quality or inhibit reaction rates. The
Product uniformity
High potential for flexibility of the gas-solid contacting concept
automation can be used to enhance performance in pusher
furnace synthesis operations.

Raw Material Feed 1 Ir-------~) Purge Gas + Reaction By-products
Gas Solids
Product Discharge
1rPu~eG~
Figure 6.2 Schematic of moving bed furnace.
Pusher furnaces have flexible residence
time ranges. This can be an important advan-
tage for slow reactions (Reh, 1978). The ability
to vary residence time over a wide range can
be a distinct advantage over transport type
reactors which typically have short residence
times and minimal flexibility in adjusting
these times.
Pusher furnaces have been used in
metallurgical processing for heat treating
and gas-solid reactor operations (Danninger
et al., 1985; Zhangyuan et al., 1990). The large
Introduction 139
Pre-heat Zone
Reaction Zone
Cooling Zone
scale use of a pusher furnace in the metallur-
gical industry illustrates its potential for a
non-oxide ceramic powder manufacturing-
scale operation.
DISADVANTAGES OF PUSHER FURNACE
SYNTHESIS PROCESSES
As mentioned earlier, pusher furnace syn-
thesis operations typically use a static bed
configuration. The uniformity of reaction
rates and product properties can be adversely
140 Tube/pusher/moving bed furnace processes
impacted by wide variations in the thermal
and chemical conditions with position. Spatial
variations in aluminum nitride (AIN) powder
characteristics have been reported in a static
bed pusher furnace (Dunn et ai., 1991). There
are several potential causes for this type of
behavior including: (1) carbothermal reduc-
tion reactions form by-product carbon mon-
oxide (CO), which can adversely impact the
powder quality (mass transport limitations),
and (2) carbothermal reduction reactions are
endothermic, which can produce temperature
gradients within the reacting bed (heat trans-
port limitations). Ceramic powder properties
tend to be sensitive to the synthesis tempera-
ture and chemical conditions (Venkateswaran
et ai., 1992). Variable product characteristics
can result from these limitations.
Mass transfer processes such as the trans-
port of gaseous reaction by-products away
from the reacting solids can impact powder
characteristics. Inadequate heat and mass
transfer rates have been reported as possible
causes for undesirable product quality fea-
tures, such as incomplete conversion of raw
materials and wide variations in powder
properties (Dunn et ai., 1991). These limita-
tions have been reported by others (Van der
Pyl, 1970); large scale SiC synthesis in a
pusher furnace proceeded more rapidly in a
crucible designed for enhanced CO removal.
The modified configuration also impacted
the average crystallite size. Full conversion
of the reactants was impossible without this
modification. Others (Wilkening, 1988) have
proposed similar hardware modifications to
improve CO removal rates.
The inherent limitations of the static bed
configuration have been recognized by
others (Dunn et ai., 1991); various hardware
modifications to direct gas flow through the
crucible have been proposed. These modifica-
tions effectively convert the static bed to a
packed bed. Hardware designs with gas dis-
tribution holes which direct gas through the
reacting bed have been developed. Others
(Nakano et ai., 1991) maintained the static
bed configuration, but modified the gas flow
path to direct flow over multiple static beds.
This modification was chosen to reduce mass
transfer limitations observed in a single,
thicker bed of reactants.
The potential for product and process non-
uniformity from transport limitations can
limit the scaleability of pusher furnace syn-
thesis processes. The TiB2 pusher furnace
described by Kim and McMurtry (1985) was
reported to be near its maximum scale of
effective operation. The calculations included
later in this chapter will analyze the potential
difficulties which arise with increasing thick-
ness of the bed.
Pusher furnaces are complex mechanical
systems that operate at much higher tempera-
tures than typical mechanical systems. This
results in a potential for operating difficulties
and higher capital costs. The complexity and
higher capital costs can result in higher
powder production costs.
ADVANTAGES OF MOVING BED FURNACE
SYNTHESIS PROCESSES
Moving bed reactors have advantages similar
to pusher furnaces. They offer flexibility in the
reactant residence times with residence times
of hours possible in these units. This is impor-
tant considering the relatively slow kinetics
exhibited by many carbothermal reactions.
They can be operated over a range of gas
flow rates; this is especially important for
carbothermal nitridation processes where the
process gas is also a reactant. There are upper
limits on the process gas flow rates. These will
be discussed as disadvantages.
The plug flow imposed on both the reacting
solids and the process gas is another advan-
tage of the moving bed furnace. As discussed
above, plug flow minimizes the reactor size
and can promote uniform product characteris-
tics. The packed bed flow configuration of the
gas relative to the solid can be advantageous
in promoting effective heat and mass transfer
between the solid and the gas.

Moving bed reactors are a well-established
unit operation in the metallurgical and
chemical process industries (Szekely and
Themelis, 1971; Perry and Green, 1984). The
potential for large scale, economical process-
ing in a moving bed reactor is indicated by
this widespread usage.
DISADVANTAGES OF MOVING BED
FURNACE SYNTHESIS PROCESSES
There are several potential disadvantages
associated with moving bed reactors. An
important one is the tendency towards poor
operability if not operated under very specific
conditions. One example is the tendency of
the bed to freeze or sinter. Several of the
references focus on this operating difficulty.
The potential for bed freezing can be reduced
by controlling the thermal history of the feed
material (Enomoto, Yoshioka and Yokoyama,
1981; Henley et al., 1994).
The moving bed reactor places limitations
on the reactant characteristics and the process
gas flow rates. For example, small diameter
feed materials are difficult to use due to
Introduction 141
their poor flowability and their tendency to
fluidize. Even large feed particles place maxi-
mum limits on the gas flow rate based on their
minimum fluidization velocity. Finally, the
feed must remain flowable and cannot
become friable during heating and reaction.
Particle attrition can lead to fluidization and
a transition from moving bed to fluidized
bed behavior (Henley et al., 1994).
As with pusher furnaces, there is the poten-
tial for non-uniform reaction environment as
the reactor size is increased. Significant tem-
perature variations with position eventually
limit reactor size. A maximum bed thickness
of around O.3-O.4m (",12-16 in) has been
reported (Enomoto, Yoshioka and Yokoyama,
1981).
INDUSTRIAL PUSHER FURNACE POWDER
SYNTHESIS PROCESSES
Pusher furnaces have been used to produce a
wide range of non-oxide ceramic powders.
This section summarizes industrial powder
synthesis processes reported in the literature;
a general summary is contained in Table 6.2.

Table 6.2 Summary of pusher furnace synthesis processes from the literature

Material Reference Temperature (K) Atmosphere Calculated furnace

(ac) production capacity
(kg/yr)

SiC Van der Pyl (1970) 2823 Ar Up to 227000

(2550)
,B-SiC Kurachi et al. (1987) 2023-2373 He, Ar or CO
(1750-2100)
,B-SiC whiskers Hayashi, Mochizuki 1773-2273 Ar or CO 4500-9100
and Ozawa (1986) (1500-2000)
WC Kieffer and Benesovsky (1978) 1673-1873 H2
(1400-1600)
TiC Kieffer and Benesovsky (1978) Not listed H2 or CO
zrC Kieffer and Benesovsky (1978) 2673 H2
(2400)
TiB2 Kim and McMurtry (1985) 2273 Ar 45 500-90 900
(2000)
AIN Dunn et al. (1991) 2023 N2 9100-13600
(1850)
142 Tube/pusher/moving bed furnace processes
Boron carbide
Moore (1990) described a boron carbide (B4 C)
synthesis process which combines a continu-
ous transport reactor with a pusher furnace
system. The pusher furnace crucibles were
used to collect the reacted product exiting
the transport reactor. The process targeted
full conversion of the reactants in the trans-
port reactor section. The reacted product can
be maintained at an elevated temperature in
the pusher furnace, potentially allowing for
reactant conversion within this zone.
Smudski (1968) described the preparation of
small batches of B4 C in a pusher furnace. The
patent focused on demonstrating an improved
process for the preparation of process feed
materials.
Silicon carbide
Van der Pyl (1970) synthesized silicon carbide
(SiC) from silicon-carbon (Si-C) or silica-
carbon (Si02-C) reactant mixtures in a
pusher furnace. Gas purge holes through the
center of the crucible were developed as a
means of improving by-product gas removal.
The reported throughput of the pusher fur-
nace was quite high. Based on furnace dimen-
sions and maximum production rates on
scale-up, throughputs up to 227000 kg/yr
(500000 lb/yr) were reported as feasible.
Kurachi et al. (1987) discussed the impact of
the pusher furnace configuration on the
product purity of ,B-SiC Furnace configura-
tions with separate removal of by-product
gases and SiC products were developed.
They claim an improved synthesis process
by this approach due to improved handling
of condensable species such as Si and silicon
monoxide (SiO). Both species are gaseous
intermediates or by-products of the synthesis
process and condense to form solid deposits
upon cooling. A series of furnace configura-
tions was proposed for separate cooling
and removal of the by-products from the SiC
product.
Hayashi, Mochizuki and Ozawa (1986)
developed a vertical pusher furnace for the
production of ,B-SiC whiskers by the reaction
of Si02 and C Their patent focused on the con-
trol of the feed packing density to achieve high
whisker yields and desirable product aspect
ratio. Their furnace had a production capacity
of 4500-9100kg/yr (rv10000-20000Ib/yr) of
SiC whisker product.
Wilkening (1988) synthesized SiC in a
vertical pusher furnace system. The vertical
orientation was chosen to allow gravity to
transport the crucibles through the furnace.
Other carbothermal powders were produced
in this furnace, including nitrides (boron
nitride (BN), aluminum nitride (AIN), silicon
nitride (Si3 N 4 ), titanium nitride (TiN) and
zirconium nitride (ZrN, carbides (boron
carbide (B4 C), aluminum carbide (AI4 C3 ), tita-
nium carbide (TiC), zirconium carbide (ZrC)
and tungsten carbide (WC and titanium
diboride (TiB 2 ).
Tungsten carbide
Kimmel et al. (1987) described a pusher fur-
nace process for the production of WC This
patent described an approach to resolve non-
uniformity in the product composition caused
by differences in the chemical environment
within the static bed. They proposed and
demonstrated a two-step furnacing process
which included an intermediate feed com-
position modification. The process concept is
shown in Figure 6.3. The reported advantages
of their process include increased throughput
of WC powder, and reduced hazards asso-
ciated with pyrophoric tungsten (W) powder
by-products.
Kieffer and Benesovsky (1978) reported that
WC production furnaces include both alumina
(AI2 0 3 ) and carbon tube furnaces, heated with
either molybdenum or graphite heating
elements. The synthesis reaction takes place
in a hydrogen atmosphere at temperatures of
1673-1873K (1400-1600C). Tungsten carbide
is formed by the reaction between a tungsten

CO CO2
wo3 Initial W.WC.W~
Reduction
c Step
Figure 6.3 Modified pusher furnace process for
source and carbon black. The W source can be
a number of starting compounds, including
tungsten trioxide (W03 ), tungstic acid
(H2W04 ) or ammonium para tungstate
(5(NH4 h . 0.12W03 5H20). Product charac-
teristics such as particle size, particle shape
and product purity are determined by the
starting raw material characteristics.
Titanium carbide
The world-wide production capacity for TiC is
also substantial (Kieffer and Benesovsky,
1978). The starting raw material is formed by
mixing titanium oxide (Ti02) with carbon in
the form of carbon black or low ash carbon.
Feed material is heated in a pusher furnace
under a hydrogen (H2) or CO atmosphere.
The resulting product is broken up by jaw
crushing and ball milling. The TiC product
contains the following impurities: 0.5-1.5% C
(free), 0.5-1.0% and Nand 0.1 % impurities.
Introduction 143
CO CO2
Final
Reduction wc
Step
(After C Addition)
we powder synthesis.
Zirconium carbide
Zirconium carbide (ZrC) is formed in a gra-
phite tube furnace under an H2 atmosphere
at 2673 K (2400C) (Kieffer and Benesovsky,
1978). The product composition is as follows:
88.3% Zr, 11.3% C (total), O/N 0.3% and a
trace of free C.
Titanium diboride
Kim and McMurtry (1985) evaluated the pro-
cess economics and technical feasibility of
TiB2 production in a pusher furnace. Titanium
diboride (TiB2) was produced by the carbo-
thermal reduction of Ti02 by B4 C and C. The
process had an annual production capacity of
45000-91000 kglyr (",100000-200000 lb/yr).
It was reported that the furnace used in their
work was near its upper scale-up limit. Further
furnace scale-up was impractical due to
heat transfer limitations which resulted in
144 Tube/pusher/moving bed furnace processes
Figure 6.4 TiB2 powder produced by a carbothermal pusher furnace process.
incomplete reactant conversion. The as-
synthesized product size distribution was
broad, ranging from 1 to 160 Mm with an aver-
age grain size of 31 Mm. The product contained
less than 1% residual carbon and oxygen, and
less than 1% residual nitrogen in the form of
nitrides. A photomicrograph of as-synthesized
TiB2 product is shown in Figure 6.4. The as-
synthesized crystal dimensions could be
modified by changing the synthesis tempera-
ture (McMurtry, personal communication,
1992).
There are other reports of TiB2 production
by carbothermal reduction of Ti0 2 by B4 C-C
in a pusher furnace (Van der Pyl, 1970).
Product characteristics were not reported.
Aluminum nitride
Dunn et al. (1991) described a pusher furnace
system for the production of AlN powder by
carbothermal nitridation. They showed the
limitation of the static bed configuration in a
series of experiments where the bed depth
was increased from 0.013 m to 0.038 m (0.5-
1.5 in) for a fixed reaction time. These changes
resulted in large spatial variations in the
oxygen content. The variations in the oxygen
content indicated significant variations in the
chemical synthesis conditions with position
for the thicker beds of solids. To resolve this
issue, they developed a modified crucible
design which directed gas flow through the
reactant bed and converted the reactor con-
figuration to a packed bed. The resulting
improvements in heat and mass transfer led
to improved product uniformity and reaction
rates and increased the process throughput.
The furnace operating capacity was 4500-
18000 kg/yr ('" 10000-40000 lb/yr).
INDUSTRIAL MOVING BED FURNACE
POWDER SYNTHESIS PROCESSES
There are a limited number of references
describing the use of moving beds to produce

Table 6.3 Summary of moving bed furnace synthesis processes from the literature
Material Reference
AIN Henley et al. (1994)
AlN Ravenel and Bachelard (1994)
Ravenel et al. (1994)
,6-SiC Enomoto, Yoshioka and
Yokoyama (1981)
non-oxide ceramic powders. Applications of
moving bed furnaces to produce nitrides and
carbides are summarized in Table 6.3. In gen-
eral, process conditions such as temperature
and process gas atmosphere for moving bed
reactors are similar to pusher furnace process
conditions.
Van Dijen, Metselaar and Siskens (1985)
reviewed the advantages of a moving bed
reactor relative to other gas-solid reactors;
for example, they mentioned the inherent
advantages of using a plug flow reactor to
promote more uniform powder properties.
They also listed important feed and reactor
operating factors. Their reactor was used to
synthesize a range of non-oxide ceramic pow-
ders including TiN, Si3N 4, SiC and AlN-SiC
and AlN-Si3N4 composites. Reactor through-
puts of 100000-1000000kg/yr.m2 (220000-
2.2MMlb/yr m 2 ) of furnace were claimed.
o
Assuming a maximum furnace diameter of
around 0.3-0.4m (",12-16 in), throughputs
of 10000-100000 kg/yr (22000-220000 lb/yr)
would be feasible. This range agrees well
with maximum throughputs reported by
Enomoto, Yoshioka and Yokoyama (1981).
Aluminum nitride
The synthesis of AIN in a pilot scale moving
bed reactor was described by Henley et al.
(1994), Ravenel and Bachelard (1994) and
Ravenel et al. (1994). Henley et al. (1994)
focused on the importance of feed charac-
teristics, reactor temperature profile and gas
Introduction 145
Temperature (K) Atmosphere Calculated furnace
(DC) production capacity
(kg/yr)
1873-1973 Nz 5000
(1600-1700)
1723-1773 Nz 20000
(1450-1500)
1923-2173 500000 max.
(1650-1900)
dynamics for the successful operation of a
moving bed reactor. The patent lists the reac-
tor operating parameters in substantial detail,
making it a good data source for moving bed
synthesis processes. The synthesis process
described in the patent had a potential
throughput of 5000kg/yr (11 OOOlb/yr).
The AlN product had properties typical of
commercial AlN powders produced by carbo-
thermal nitridation. Some typical properties
included:
surface area: 2.4-2.8 m 2 / g;
oxygen content: 0.7-1.2%.
Ravenel and Bachelard (1994) and Ravenel
et al. (1994) emphasize the importance of
process uniformity in which each particle of
reactant participates in the reaction and all
particles of reactant participate equally. A
preferred length to internal diameter ratio is
identified as being between approximately 8
and 15. In their process, uncalcined feed
pellets of carbon, alumina and a binder are
fed in the top of the reactor and calcined as
their first step in the process. Some typical
properties of the AlN produced in this process
included:
surface area: 2-5 m 2 / g;
oxygen content: <0.5 wt% O.
Silicon carbide
Enomoto, Yoshioka and Yokoyama (1981)
described a moving bed furnace for the
146 Tube/pusher/moving bed furnace processes
production of ,B-SiC powder. Their most
interesting contribution was a reactor design
capable of a very high throughput. They
demonstrated an annular reactor design
which maximized reactor volume for a fixed
bed thickness. For a bed thickness of 0.35 m
(",14in), they demonstrated a reactor design
with a potential throughput of approximately
500000kg/yr (1.1 million (MM)lb/yr). This
represents a five- to tenfold increase in the
process throughput relative to a standard
cylindrical furnace of equivalent bed thickness.
FUNDAMENTAL PHYSIO-CHEMICAL
CONSIDERAnONS
The kinetics of carbothermal reactions have
been evaluated for several non-oxide ceramic
powders (van Dijen and Metselaar, 1991;
Lefort and Billy, 1993; Weimer et al., 1993).
The reaction kinetics of carbothermal reduction
reactions are described in detail in Chapter 3.
There are several general features of these
reactions which impact the design, operation
and performance of pusher furnaces. First,
carbothermal reduction reactions are relatively
slow in a static or packed bed reactor con-
figuration. Reaction times as long as 6 h
(Kuramoto and Taniguchi, 1986; Lefort and
Billy, 1993) are sometimes required to achieve
full reactant conversion in a lab-scale reactor.
These reactions frequently exhibit a narrow
acceptable temperature operating window
(Kuramoto and Taniguchi, 1986). This range
is determined by two limits of behavior. The
lower limit is the lowest temperature which
produces acceptable reaction rates based on
process economic considerations. The upper
limit is determined by the onset of unaccept-
able grain growth of the product and is
dependent on the required product character-
istics. This temperature range can be as small
as several hundred degrees.
Furthermore, the carbothermal reduction
reactions typically exhibit high activation
energies. Activation energies of 300-400 kJ /
mol have been reported, indicating reaction
rates that change significantly with tempera-
ture. This temperature dependence can
adversely impact reactors which exhibit
large temperature variations as a function of
position.
Finally, these reactions often exhibit a sharp
reaction rate decrease as complete reactant
conversion is approached (Lefort and Billy,
1993). This behavior can result in long
residence times to achieve complete reactant
conversion. This can be an important consid-
eration for products which are adversely
impacted by the presence of small amounts
of unreacted raw materials. The increased
residence times necessary to achieve the com-
plete conversion of reactants directly impacts
furnace size and throughput.
The performance of a gas-solid reactor
can be strongly influenced by transport
processes (Levenspiel, 1972). These processes
include:
gas-solid mass transport processes (reactant
and by-product transport);
heat transport processes (replacement of the
heat of reaction).
Carbothermal reduction reactions are endo-
thermic and require heat transfer to maintain
a constant reaction temperature. Enthalpies of
formation for carbothermal synthesis reac-
tions are discussed elsewhere in this volume;
several values of enthalpy of formation for
nitrides, borides and carbides by carbo-
thermal reduction are summarized in Table
6.4 (Chase et al., 1985). The necessity of
replacing the heat of reaction can limit the
maximum allowable thickness of the bed
since the powdered raw materials (ceramic
powders and carbon) typically have a low
thermal conductivity and therefore conduct
heat poorly.
As shown by the examples in Table 6.4, CO
is the gaseous by-product of carbothermal
synthesis reactions. It can retard the reaction
kinetics, limit conversion levels and adversely
impact product characteristics. The ability to
remove CO depends on mass transfer rates

Table 6.4 Typical enthalpies of reaction for carbothermal synthesis reactions
Reaction
(1527C) (klima/)
Al20 3 + 3C + N2 --t 2AIN + 3CO
2Ti02 + B4 C + 3C --t 2TiB2 + 4CO
Si02 + 3C --t SiC + 2CO
across the gas-solid interface and through the
bed; therefore, the bed thickness may have an
upper limit. The implications of the mass
transfer processes are discussed in more
detail later in this chapter.
Carbothermal nitridation reactions repre-
sent a special case. In nitriding reactors, the
nitrogen process gas is a reactant. Transport
of N2 into the reacting bed is required in addi-
tion to removal of the by-product CO. The
nitrogen transport dynamics can therefore
affect the reactor performance.
An understanding of the relevant heat and
mass transport processes is necessary to prop-
erly evaluate the limitations caused by these
mechanisms. A number of texts contain
detailed descriptions of these processes
(Bird, Stewart and Lightfoot, 1960; Szekely
and Themelis, 1971; Perry and Green, 1984).
Chemical engineering analysis of metallur-
gical processes can provide useful insights
into the transport and kinetic processes
which affect ceramic powder synthesis pro-
cesses. Taylor (1971) and Taylor et al. (1971)
provide a comprehensive review of high
temperature chemical engineering as applied
to the metallurgical industry. These references
provide valuable insights into the effects of
transport phenomena and reaction kinetics
on the performance of high temperature
reactors.
Most of the considerations discussed for
pusher furnaces are applicable to moving
bed furnaces. The references on moving bed
furnaces describe the major engineering and
design considerations for these units. The
furnace temperature profile and heating
Fundamental physio-chemical considerations 147
~at 1800K Energy requirement
(kW hlkg product)
674.1 2.28
898.1 1.79
590.6 4.09
zone dimensions are important factors and
have been evaluated (Enomoto, Yoshioka
and Yokoyama, 1981; Henley et al., 1994).
These design parameters affect the process
throughput, furnace operability and product
characteristics.
The importance of proper feed characteris-
tics is a major emphasis in the moving bed
process patents. The feed properties affect
both furnace operability and product charac-
teristics. The patents describing AIN and SiC
moving bed processes (Enomoto, Yoshioka
and Yokoyama, 1981; Henley et al., 1994) list
the important aspects of the feed design
including:
raw material characteristics;
binder characteristics;
feed composition;
feed pretreatment;
pellet strength;
particle size;
powder flowability.
These factors tend to strongly impact the
reactor performance.
Non-oxide powders for electronic and high
temperature structural applications can be
adversely impacted by trace impurities.
Starting raw materials used for non-oxide
ceramic powder synthesis often contain
trace impurities which are undesirable in
the product powder. High synthesis tempera-
tures can volatilize the impurities and can
result in improved product purity. However,
this behavior can lead to product contamina-
tion by the condensation of impurity-rich
deposits in cool areas of the furnace. This
148 Tube/pusher/moving bed furnace processes
phenomenon is not limited to trace impuri-
ties; vapor phase reaction intermediates
such as Si and SiO can degrade the quality
of the SiC by contaminating the product
with free Si and Si02 (Kurachi et ai., 1987).
To summarize, the unique features of carbo-
thermal synthesis reactions can place con-
straints on the design and operation of
pusher and moving bed furnace synthesis
processes. The supply and removal of gaseous
species require mass transfer through the
reacting bed. This may limit its allowable
thickness. Similar constraints can result from
the need to transfer heat to maintain uniform
synthesis temperatures. Heat transfer rates in
the bed can become a critical constraint; the
low thermal conductivity of the solid reactant
bed may lead to excessive temperature gradi-
ents in the bed. Control of the exhaust gas
composition necessitates careful engineering
of the gas contacting scheme (co- vs counter-
current) and exhaust gas handling to prevent
product contamination and reaction rate
inhibition.
MASS TRANSFER BEHAVIOR
Simple mass transfer models have been used
to evaluate potential rate limitations caused
by the transport of N2 and CO in a static
Wall
co
Figure 6.5 Important mass transfer processes in a pusher furnace synthesis process.
bed. There are two mass transfer processes
occurring in series:
laminar mass transfer to/from the N2 pro-
cess gas stream to the static bed surface;
mass transfer within the static bed.
Mass transfer effects in the reacting pellet
have been ignored for these calculations.
Figure 6.5 shows a schematic diagram of the
mass transfer processes.
The model calculations have been used to
evaluate maximum gas flux rates; such simpli-
fied models are useful for identifying potential
rate limitations in high temperature synthesis
processes (Biernacki, 1987; Hollar and Kim,
1991). The key assumptions are:
Temperature = 1773 K (1500 DC);
LlPi = 0.01 MPa (,....,1.5 psi);
Average pore diameter = average pellet
diameter;
Atmosphere: mixture of CO and N 2 .
The model equations are, for laminar mass
transfer from the free stream (Biernacki, 1987):
i = kc(LlC i )
kc(LlP i )
(i = N2 or CO)
RgT
k _ 0.664v
c - SCO.67 Reo.s
 Fundamental physio-chemical considerations 149
and for mass transfer through the packed section). For the calculations, a mole fraction
bed: of 0.1 has been assumed as a typical driving
force. The calculations have been used to
relate trends between mass transfer rates and
key geometrical and transport parameters.
The calculated N2 flux rates are compared
D = 1 in Table 6.5. The mass transfer from the gas
e (l/D) + (l/Dk )
to the packed bed does not appear to be a

Dk = 48.5d p ( M
T )0.5
where:
Ci concentration of species i (mol/m3 or
kgmol/m3)
D molecular diffusivity (m2Is)
De effective diffusivity in a porous body
(m2 Is)
Dk Knudsen diffusivity (m2I s)
dp particle diameter (m)
kc mass transfer coefficient (ml s)
I bed thickness (m)
M molecular weight (g/mol or kg/kgmol)
Pi partial pressure of species i (Pa or MPa)
Rg gas constant (8.314 JImol K)
Re Reynolds number
Sc Schmidt number
T temperature (K)
v velocity (ml s)
> flux (mol/m2. s or kgmol/m2. s)
Effective pore diameters for packed bed
diffusion behavior have been assumed equal
to the feed particle size. Process conditions
are assumed typical of a 120 000 kg/yr
(",250000 lb/yr) plant (described in the next
rate-limiting step since the calculated flux is
greater than the assumed reaction rates. The
calculated flux is sensitive to the assumed
gas flow rate; however, further decreases in
the assumed flow rate would not be feasible
in a production reactor due to the resulting
excessive CO concentrations.
Mass transfer within the static bed could
represent a rate-limiting step. The predicted
molar flux decreases linearly with increasing
bed depth. A depth of 0.05 m (",2 in) produces
a flux similar to that required to sustain the
assumed reaction rate. This indicates that
mass transfer through the bed could be a
rate-controlling step; increasing the bed
thickness would increase the probability of
diffusion through the bed becoming the rate-
controlling step.
The feed particle size only becomes impor-
tant for very fine (i.e. micron-sized) particles.
These effects are summarized in Table 6.6. A
static bed with an average pore diameter of
l/.Lm produces a diffusion flux one-half the
value for a packed bed with 100/.Lm average
pore diameter. Beyond 100/.Lm, there is no
change in the flux with increasing pore
diameter. This result could indicate that

Table 6.5 Order of magnitude comparison of N2 flux rates in a pusher fur-

nace synthesis process

Mass transfer mode Mass transfer flux

(kg mol/m2 s x 106 )

Calculated flux (average requirement) 7.5

Laminar flow mass transfer (High N2 flow rate) 22.3
Laminar flow mass transfer (Low N2 flow rate) 15.8
Packed bed (0.01 m (rvO.4in) deep) 14.6-32.5
Packed bed (0.05m (rv2in) deep) 2.9-6.5
150 Tube/pusher/moving bed furnace processes
Table 6.6 Effect of pore size on calculated mass to the fourth order temperature dependence of
transfer flux rates radiation heat transfer (Bird, Stewart and
Lightfoot, 1960). The presence of solid bodies
Pore diameter (m) Calculated flux rate
blocking radiative heat transfer by the
for a 0.05 m static bed
(kg mol/rrt . s x 106 ) shielding effect can reduce heat transfer rates
(Bird, Stewart and Lightfoot, 1960). This
1 X 10- 6 2.9 shielding effect can seriously limit the ability
1 X 10-4 6.4 to rapidly heat a charge (Kim, Dover and
1 X 10-3 6.5 Venkateswaran, 1986). Under the laminar
flow conditions typical of pusher furnaces,
convective heat transfer rates are not signi-
pelletization of feed materials (Dunn et ai.,
ficant. Conduction is an important heat
1991) may be beneficial in reducing the static
transfer mechanism under these conditions.
bed mass transfer resistance. The relatively high thermal conductivity of
graphite (the most commonly used structural
HEAT TRANSFER BEHAVIOR material) helps maintain high conduction heat
transfer rates.
There are four primary mechanisms for heat The heat flux for each of the major heat
transfer in a pusher furnace: transfer mechanisms is compared in Table
6.7. A static temperature driving force of 1 K
radiative heat transfer from the heating
source or crucible; at a temperature of 1773 K (1500 0c) has been
assumed. The heat flux per unit area over a
conduction through structural materials
(crucible, muffle); distance of 0.0254 m (1 in) has been deter-
convective heat transfer from the process mined for a flat or parallel plate geometry.
gas; The calculations are sensitive to the
conduction and radiation within the static assumed heat transfer parameters; therefore,
bed. values typical for a high temperature pusher
furnace were assumed. Graphite has been
A schematic diagram of the important heat chosen as a typical material of construction.
transfer mechanisms is shown in Figure 6.6. The emissivity of graphite is quite high, 0.9-
At high temperatures, radiation tends to be 1 (Touloukian and DeWitt, 1972). Thermal
the dominant mechanism for heat transfer due conductivity of graphite materials used for

k(graphite) Temperature

Conduction

Radiation
e >-
Convection Process Gas Flow z

Conduction

k(bed)
Figure 6.6 Important heat transfer processes in a pusher furnace synthesis process.

Table 6.7 Heat flux values for high temperature heat transfer mechanisms
Mechanism
Radiation
Conduction (graphite)
Conduction (static bed)
Convection (laminar flow)
a 10, emissivity; k, thermal conductivity (WI m K); h, conductive heat transfer
coefficient (W 1m2 K).
furnace construction typically range from 30-
100 WI m . K. Convective heat transfer co-
efficients are small for the typical laminar
flow conditions 10 W 1m2 K). The thermal
conductivity of a packed bed is lower than the
starting materials (Laubitz, 1959) and depends
on the packing density and temperature. The
assumed thermal conductivity value is typical
of ceramic powders (Laubitz, 1959).
The calculations indicate that conduction
through graphite and radiation heat transfer
are rapid and are unlikely to limit heat trans-
fer. Convection is slow, but acts in parallel to
radiation; it is therefore not a critical factor.
Heat transfer through the static bed is the
slowest process and is most likely the limiting
heat transfer step.
Another simple calculation can be used to
identify important variables in the steady-
state conduction of heat into a solid body
with an internal heat generation source
(Welty, Wicks and Wilson, 1976). In this
analysis, the temperature gradient through a
cylinder at steady state is related to three
critical parameters - the radius of the cylinder,
the heat of reaction (rate of heat generation)
and the solid thermal conductivity. The
gradient between the surface and center tem-
perature is directly proportional to the rate of
heat generation and inversely proportional to
the thermal conductivity. The temperature
gradient is proportional to the radius squared.
By analogy, this analysis can be used to
estimate the temperature gradient in a tube
furnace full of reacting powder at steady
Fundamental physio-chemical considerations 151
Assumed parameter a
c=l 1263
k=40W/mK 1575
k=O.4 W/mK 16
h = 5 W/m2 .K 5
state. Increases in the diameter of the pusher
furnace for a cylindrical geometry can lead
to significant increases in the temperature
gradient. Manifestation of this behavior
could include an unreacted core region similar
to that reported by Rafaniello and Moore
(1989) and McMurtry (personal communica-
tion, 1992).
The same considerations affect the perfor-
mance of moving bed reactors. Enomoto,
Yoshioka and Yokoyama (1981) propose a
maximum bed thickness of 0.35m (rv 14 in).
This limit is similar to the maximum size pro-
posed for pusher furnace beds (Kim and
McMurtry, 1985).
Based on these analyses, heat transfer
through the reacting bed appears to be the
primary limitation in the replacement of the
endothermic heat of reaction. For certain
processing conditions (highly endothermic
reaction, low bed thermal conductivity, large
diameter), temperature gradients up to
several hundred degrees can result. Since
carbothermal reaction rates are temperature
sensitive (Lefort and Billy, 1993), the static
bed reaction rate at specific locations can
differ by at least an order of magnitude. This
can lead to product non-uniformity in
manufacturing-scale equipment.
MATERIAL AND ENERGY BALANCE
A material and energy balance has been calcu-
lated for a manufacturing-scale carbothermal
synthesis process. The calculations are based
152 Tube/pusher/moving bed furnace processes
on a lOt/month AlN synthesis operation
using the following process assumptions.
1. Plant operations:
yearly throughput = 120000 kg/ yr
(264 000 lb/yr);
operating factor = 95%;
post-processing yield = 95%.
2. Furnace parameters:
hot zone length = 14.0m (",,46 ft);
hot zone characteristic thickness = 0.3 m
(",,12 in).
3. Reaction conditions:
feed: 30% excess C;
feed density=1000kg/m3 (62.4lb/ft3 );
average synthesis temperature = 1800 K
(1527C);
reactant residence time = 4.32 x 104 s
(12 h).
The material balance is summarized in Figure
6.7. There are several features of interest. Even
with a modest excess nitrogen supply (i.e. ten
times the stoichiometric requirement), supply
and control of large process gas flow rates
become a necessity. Despite the presence of
excess nitrogen, high partial pressures of by-
product CO are indicated by the material
balance. The exhaust gas will contain
25 mol% CO for the assumed N2 flow. The
modification of the chemical environment
through CO overpressure can become a
major problem at this scale of operation and
effective CO removal becomes critical.
Exhaust Gas
47.2 kg/h (37.8 scmh) N2
15.7 kg/h (12.6 scmh) CO
Solid Reactants ,-----'-------, Solid Product
19.1 kg/h A120 3 15.4 kg/h AIN
8.7 kg/h C 2.0 kg/h C
Feed Gas
52.5 kg/h (42 scmh) N2
Figure 6.7 Hypothetical AIN manufacturing plant
materials balance.
The energy balance is summarized in
Table 6.8. The total power requirement for
heating the reactants, kiln furniture and
replacing the heat of reaction is 125 kW;
this requirement increases to 150 kW when
a furnace purge rate equal to the reactant
N2 flow rate is included. This power require-
ment does not take into account energy
losses at the terminals or through the
insulation; the minimum expected total
energy requirement including such losses
will be at least twice this value (Orfeuil,
1987), and probably closer to three times
this value (Kim and McMurtry, 1985). The
process energy requirement per unit mass
of product has been estimated as 10 kW . h/
kg; actual energy requirements would be 20-
30kW.h/kg.

Table 6.8 Energy requirements for AIN synthesis in a pusher furnace

Energy requirement Fraction of the total

(kW h/kg) energy requirement
Heat reactants to 1800 K (1527 DC) 1.02 0.10
Heat crucibles to 1800 K (1527 DC) 3.22 0.33
Heat N2 (reactant) to 1800 K (1527 DC) 1.66 0.17
Heat N2 (purge) to 1800 K (1527 DC) 1.66 0.17
Replace heat of reaction 2.28 0.23
Total 9.83 1.00

SYSTEM DESIGN CONSIDERATIONS
PUSHER FURNACES
All pusher furnace configurations contain
similar hardware features which are not a
function of the process chemistry. Some of
the more important features are discussed
below.
Crucibles or boats and a mechanism for
charging and discharging them from the
furnace are typical pusher furnace features.
The crucibles transport the solid reactants
through the furnace. Proper crucible design
requires that heat and mass transfer require-
ments be met. Powder handling operations
can be incorporated at each end of the
system to automate the transport of the feed
material and as-synthesized product. Air
lock systems are required to maintain low
oxygen partial pressure within the furnace.
In addition, the furnace is typically operated
at a slight positive pressure to limit leakage
of ambient air. Air leakage into a graphite
furnace at temperature will lead to rapid
consumption of structural parts and insula-
tion. In addition, most carbothermal reactions
will not proceed at excessive oxygen partial
pressures.
Two crucible geometries are reported in the
literature: trays or flat plates and cylindrical
crucibles. The crucible geometry corresponds
to the geometry of the furnace muffle struc-
ture. In several cases, the design has been
chosen to improve gas dynamics and improve
mass transfer rates (Dunn et al., 1991; Nakano
et al., 1991). Graphite is a common material
of construction for non-oxide synthesis
operations. Cylindrical geometries are advan-
tageous in promoting a symmetrical and gas-
tight environment. Rectangular geometries
are typically available in larger sizes, but this
geometry has the potential for non-uniform
heating and unusable hot zone volume. In
addition, gas-tight construction becomes
more difficult to achieve in a rectangular
geometry. The Harper sales brochure
System design considerations 153
(Harper, 1988) lists maximum dimensions for
each geometry: cylindrical furnaces up to
0.254 m (10 in) inner diameter and rectangular
furnaces up to 1.63 m (5.4 ft) wide.
Both induction and resistance heating have
been used in pusher furnaces. Induction
heating can directly heat the furnace muffle.
Resistance heating uses electrically conduct-
ing elements to generate heat which is then
radiated to the muffle. Wilkening (1988)
reported a novel method of resistance heating;
electrical current was passed through the
crucibles via a layer of coke concentric to the
crucibles. The Wilkening patent was unique in
another respect; the coke was fed through the
furnace counter-current to the crucibles to
transfer heat between incoming and cool out-
going crucibles to improve energy utilization.
The advantages and disadvantages of
resistance and induction heating, and operat-
ing details, design considerations and numer-
ous industrial examples, have been compiled
elsewhere (Orfeuil, 1987).
Insulation design of the furnace is an impor-
tant consideration in minimizing energy
consumption. Several types of insulation
can be used. Carbon black has been used
in older furnace designs (Kim, Dover and
Venkateswaran, 1986). There are potential
hazards associated with carbon black as an
insulation due to its flammability and reactiv-
ity at elevated temperatures. Carbon black can
also contaminate the non-oxide powder
product if care is not taken to prevent contact
between the powders. Carbon and graphite
fiber insulation materials are currently popu-
lar. These materials have the advantages of
decreased thermal mass and increased
cleanliness. For a continuous pusher furnace,
minimization of furnace heat losses is the
primary insulation design criterion.
The deposition of condensable compounds is
periodically encountered in high temperature
furnaces. It is common in synthesiS processes
where gaseous intermediates and by-products
can form. The generation of condensable
species and subsequent condensation in the
154 Tube/pusher/moving bed furnace processes
cool zones of the furnace can occur by a wide
variety of physical and chemical mechanisms.
Some synthesis reactions proceed via the
vaporization of condensable species like SiO.
Polymeric binders, used to pelletize feed
materials, can cause deposition of carbon-
aceous pyrolysis products. Trace impurities
can vaporize at high temperatures in a
number of forms. Each source of condensable
species can lead to solid deposition. Product
contamination can result if the deposition
products mix with the product powder.
Reduced furnace operability can also result if
the condensed layer becomes thick enough
to interfere with the motion of the crucibles.
Contamination of the product can seriously
degrade powder properties; interruptions of
the furnace operation seriously impacts the
throughput and can raise the production cost.
Both problems need to be addressed for
effective utilization of the pusher furnace for
powder synthesis. Proper hardware design
can prevent or reduce the severity of these
problems (Kurachi et al., 1987).
MOVING BED FURNACES
Many of the furnace design considerations for
moving bed furnaces are similar to those for
pusher furnaces. The major difference in
these furnace types is the feed and product
handling. Powder transport. tends to be
mechanically simpler for the moving bed
reactor. The reactant residence time in the
reactor is controlled by the rate of feed input
and product withdrawal. No mechanical
devices for the handling of crucibles are
required.
The temperature profile of the moving bed
is a crucial design consideration (Henley
et al., 1994). The profile must be controlled
to prevent condensable species such as
reaction intermediates and volatile impurities
from condensing in cool areas of the
furnace. Condensation deposits can cause
the bed to freeze and terminate furnace
operation.
PROCESS SCALE-UP CONSIDERATIONS
Szekely and Themelis (1971) discuss the four
conditions of similarity which are important
for successful scale-up of a process. These
similarity conditions include:
geometric;
mechanical (dynamic);
thermal;
chemical.
The maintenance of these similarity conditions
can be crucial to attain laboratory-scale reactor
performance and product characteristics at
increasing production levels. The conditions
for achieving similarity in high temperature
metallurgical processes and several examples
are described in detail by Szekely and
Themelis (1971).
The difficulty in maintaining similarity in a
pusher furnace process results from the trade-
offs between keeping similarity conditions
constant while producing powder at the
lowest possible cost. As with metallurgical
processes, similarity for non-oxide ceramic
powder synthesis processes can only be
maintained if the temperature and chemical
conditions are exactly the same at each
scale of operation. If the thermal and
chemical characteristics change during scale-
up, the desired reactor performance may be
impossible to achieve.
As shown earlier, transport limitations can
prevent the attainment of thermal and
chemical similarity within the reacting bed.
For example, thicker beds can contain larger
temperature gradients. These limitations
become more significant with increasing bed
thickness. As a consequence, limits on the
bed thickness may be required to maintain
reaction conditions which produce acceptable
product quality and uniformity.
The transition from the laboratory to the
manufacturing plant can be complicated by
other changes during scale-up. For example,
static bed synthesis experiments at the lab
scale are typically conducted in a batch mode

(Kuramoto and Taniguchi, 1986), since con-
tinuous pusher furnaces for the production
of gram quantities of powder are uncommon.
As a result, the scale-up of the process
may involve a simultaneous increase in
scale and change from a batch to continuous
reactor.
In order to explore challenges posed by
scale-up, the changes in important geometric,
thermal and chemical characteristic param-
eters have been computed for two scales of
operation. At the laboratory scale, a muffle fur-
nace capable of producing 10-100 g batches of
powder was assumed. At the other extreme, a
manufacturing-scale pusher furnace with a
production capacity of thousands of kilograms
per year was postulated. For each case, impor-
tant operating/ characteristic parameters were
computed.
The variations in parameters during scale-
up are summarized in Table 6.9. Geometric
similarity becomes difficult to maintain with
increasing reactor size. The controlling vari-
able is the bed thickness. Production costs
are minimized by maximizing furnace loading
and furnace throughput. Decreases in the
production cost would therefore result from
an increased bed thickness; however, this
increase creates difficulties in maintaining
chemical and thermal similarity. Trade-offs
between product characteristics and produc-
tion costs can result.
There are substantial differences in the
chemical environments of the laboratory and
manufacturing reactors. A characteristic par-
ameter which highlights these differences is
the gas to solid mass ratio, which compares
the relative concentrations of process gas and
Table 6.9 Effect of reactor scale-up on parameters that affect similarity
Scale Bed Surface areal
thickness volume
(m) (m- 1)
Laboratory 0.005 200
Manufacturing 0.025 40
Process scale-up considerations 155
solid reactants. The laboratory reactor is
typically operated with a large excess of N 2
This is not the case in the manufacturing
pusher furnace, where excessive flow rates
can be uneconomical and may lead to solids
entrainment. The lab-scale process has CO
concentrations one order of magnitude lower
than the manufacturing-scale furnace, as
shown in Table 6.9.
The thermal similarity behavior is also
affected by the necessity of increasing the
bed depth. The required heat flux doubled
during scale-up as shown in Table 6.9. This
results from (1) increased bed thickness and
(2) increased volume to surface area ratio.
Surface area to volume ratios represent a
fundamental difficulty in the scale-up of all
processes involving heat transfer (Bisio and
Kabel, 1985). Both conditions increase the
temperature drop through the bed for a
given reaction rate. This calculation indicates
the potential difficulties in achieving thermal
similarity between the laboratory and the
manufacturing-scale reactors. At the manu-
facturing scale, there is a high probability of
significant temperature gradients within the
bed which would not be observed in the lab
reactor. This can adversely impact product
characteristics, either through incomplete
conversion or product grain growth. At the
manufacturing scale, the reactor may require
higher operating temperatures to achieve
acceptable kinetics within the coolest volume
element of the static bed.
The changes in physical and chemical par-
ameters during process scale-up indicate that
their impact needs to be addressed as early as
possible in the process development cycle. The
Gas/solid CO Average N2 Average heat Reynolds
mass (mole flux flux number
ratio fraction) (kgmol/m 2 . s) (W/m2)
29 0.02 1.9 x 10-6 1258 22
2 0.25 3.9 x 10-6 2629 589
156 Tube/pusher/moving bed furnace processes
process sensitivity to processing conditions
expected in the manufacturing-scale furnace
can be simulated by a careful choice of experi-
mental conditions. These experiments can
provide useful information on the feasibility
of different reactor concepts and may identify
important scale-up issues. In addition, issues
associated with the product characteristics
that could result in a manufacturing-scale
reactor may be detected. Well-designed lab-
scale experiments can prevent an expensive
mistake in choosing the manufacturing-scale
reactor concept.
To summarize, simple order of magnitude
calculations of the parameters which influence
thermal and chemical similarity at the labora-
tory and manufacturing scale indicate that full
similarity can be difficult to achieve during
scale-up of a pusher furnace. This is primarily
the result of increasing bed thickness and
decreasing gas to solid ratio.
CONCLUSIONS
Pusher furnaces are used or have been
evaluated for the synthesis of a wide variety
of non-oxide ceramic powders including
carbides, nitrides and borides. They have
several desirable features including flexibility
of operation, insensitivity to feed particle size
and minimization of residence time require-
ments to achieve full reactant conversion.
They can be operated continuously, which
can reduce manpower and energy require-
ments. When used to produce non-oxide
powders in a static bed configuration, pusher
furnaces can produce significant powder
throughputs (up to 100000kg/yr (220000Ib/
yr with acceptable uniformity and properties.
Moving bed reactors have many features in
common with pusher furnace reactors, includ-
ing similar advantages and limitations. The
maximum production capacity of moving
bed reactors and pusher furnace reactors
are similar. Moving bed reactor production
capacity can be increased by clever furnace
design. There are fewer applications reported
in the literature; this may be due to the
criticality of suitable physio-chemical feed
properties and careful temperature control
for trouble-free reactor operation.
Pusher furnace and moving bed furnace
processes can be constrained by mass and
energy transport processes and require a
careful engineering design that takes into
account critical scale-up parameters. Simple
engineering calculations have been used to
demonstrate that the static bed reactant con-
figuration typically used in pusher furnace
synthesis operations can result in performance
issues caused by heat and mass transfer
limitations. Heat transfer appears to be the
critical limitation for the moving bed reactor.
A number of examples in the literature have
demonstrated that these limitations can lead
to variable product quality. These limitations
eventually constrain the maximum dimen-
sions of the furnaces and fix the maximum
process throughput. This limit appears to
be around 50 000-100 000 kg/yr (110000-
220000Ib/yr) based on the literature refer-
ences.
For pusher furnaces, mass transfer rates
appear to be limited by diffusion through the
static bed of reactants. This process can limit
the maximum reaction rate and affect the pro-
cess throughput. Heat transfer is limited by
conduction through the bed. Relatively high
synthesis energy requirements result from
the endothermic energy requirements for
carbothermal synthesis reactions. The tem-
perature gradients in a reacting bed can
become large as the bed thickness is increased.
The scale-up behavior of pusher furnaces
has been examined with a special focus on
the problems in moving from the laboratory
scale to the manufacturing scale. There are
difficulties in simultaneously maintaining
geometric, thermal and chemical similarity
due to geometric and transport limitations.
These difficulties require careful evaluation
of the tradeoffs between reactor design, pro-
cess throughput, product characteristics and
process economics.

ACKNOWLEDGMENTS
The authors gratefully acknowledge the con-
tributions of M. Wolf, who performed several
of the calculations used in this chapter. The
contributions of everyone who provided
critiques of this manuscript are gratefully
acknowledged. Finally, W. Hollar would like
to thank the Carborundum Company for
supporting his efforts on this project.
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158 Tube/pusher/moving bed furnace processes
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ROTARY TUBE REACTOR PROCESSES
Peter T.B. Shaffer
INTRODUCTION
The goal of engineers in the development of
practically every process is to make the opera-
tion continuous. Such a process can consist of
either automated or repetitive operations, but
the ideal solution is to find a way to make
operation truly continuous and to as great an
extent as possible, hands-off. The synthesis of
refractory materials is no exception. Rotary
kilns and furnaces represent the goal which,
with the exception of the cement industry,
has rarely been achieved.
The history of the manufacture of silicon
carbide (SiC) provides an excellent example,
not only of the attempts to develop such a con-
tinuous as well as rotary furnace process, but
also of the problems and frustrations that have
been encountered in trying to do so. Almost
immediately after Acheson (1893) discovered
SiC and described the furnace (Acheson, 1895)
which today still bears his name (Chapter 4),
investigators started the search for a better,
preferably continuous, furnace with which to
carry out his process. Some of the derivations
consisted of moving containers (Benner,
Melton and Boyer, 1939), of the transfer of
reaction mix via belts (Roberts, 1897; Tone,
1910), via gravity (Tone, 1909), an up-feed
arrangement (Cox, 1937a,b), even a screw-
type conveyor (Suzuki and Hase, 1983) and
ultimately via rotary furnaces (Wei, 1983;
Shaffer, 1985). It has been found that any
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
7
process which involves the physical transfer
of an abrasive material, especially one which
has become coarsely crystalline, relative to
fixed parts of a furnace, suffers from extreme
wear problems. The only acceptable means of
moving abrasive material through a furnace
appears to be by gravity and with a tumbling
action under which conditions wear problems
are at least minimized. A review of the differ-
ent approaches to the furnacing of SiC has
been published by McMullen (1957).
In the synthesis of most refractory materials
by the so-called carbothermal processes there
are several parallel, as well as competing,
reactions and processes that are taking place
(Chapter 3). These carbothermal reactions are
often highly endothermic. Therefore, heat
transfer into the reaction zone is usually one,
if not the major, rate controlling factor. In
order for heat to be transferred at as high a
rate as possible, it is necessary to establish as
high a temperature gradient as practical,
commensurate with the prevention of other
undesirable side reactions and processes. It
is desirable to have as high a thermal con-
ductivity as possible to maximize this heat
transfer.
Several counter-productive forces are com-
peting with these desirable factors. Too high a
temperature leads to sintering, crystal growth
and, in the worst case, melting or decomposi-
tion of the product. Freshly prepared fine
powders of many refractory materials, such
160 Rotary tube reactor processes
as SiC, have a very low thermal conductivity. ROTARY FURNACE DESIGN
In spite of the fact that the intrinsic thermal CONFIGURA nONS
conductivity of SiC is high, the heat transfer
A rotary furnace consists of an open-ended
through freshly prepared fine SiC is low, com-
cylinder, revolving about its axis while at
parable to that of lamp black carbon. A thir.d
least a portion of it is maintained at a tempera-
factor, especially in any fixed bed process, IS
ture sufficient to bring about certain desired
the counter-current flow of the by-product
reactions. Reactant materials are introduced
gases and the associated cooling effects.
into the rotating cylinder, agitated and
These by-product gases act essentially as
exposed to the reaction temperature by
transpiration coolants. How serious these
means of the rotation of the cylinder and the
different effects can be is best demonstrated
associated stirring or tumbling action of the
by an example given later in this chapter.
materials within it. After a suitable time of
Clearly, the only way to produce refractory
exposure limited in large part by the size of
non-oxide powders derived from a carbo-
the reactant particles or by the size of the
thermal reaction without the unacceptable
agglomerates of reactants and controlled by
crystallization and sintering must involve a
the rate of rotation and the pitch of the tube,
means of continuously exposing the unreacted
the product is discharged from the tube into a
materials to modest reaction temperatures
cooling and collection system.
while minimizing the insulating effects of the
A familiar example of the production-scale
already formed powder, as well as minimiz-
rotary kiln is the cement kiln. In this appara-
ing the cooling effects of the counter-current
tus, reactants are fed into the upper end and
by-product gas flow. How best can a reactor
traverse counter to the heat flow from the
at temperatures of the order of 1998K
internal flame. Entering the cooler upper end
(1725 0c) be stirred to insure this near iso-
of the kiln the reactants are first dried, then
thermal state?
calcined and finally converted as they reach
A multitude of methods have been investi-
the hotter regions within the kiln.
gated, and alternatives to the Acheson furnace
It is not as simple a matter to heat the high
(Acheson, 1895) devised. None of these has
temperature rotary furnaces for carbothermic
been completely successful, especially for the
reactions. Flames and their associated by-
coarser abrasive grades of the carbides. Diffi-
products are incomparable with. the car~o
culties associated with maintaining electrical
thermal reaction sequence. Heatmg a hIgh
continuity to the resistance heater, and with
temperature rotary furnace has been su.cc~ss
wear and abrasion by the hard refractory
fully carried out by locating the heater ~nsld.e
materials have proved many of these concepts
the reaction tube as well as by havmg It
unworkable.
surround the reaction muffle, supplying heat
Two exceptions to this are the fluidized bed
from the exterior, or by heating the reactant
(Chapter 8), and variations on it, and the high
muffle itself.
temperature rotary kiln. Their successful
designs all seem to be related to the design
based on stationary heat sources, and elimina-
INDIRECT, INTERNALLY HEATED DESIGN
tion of the abrasion and wear by the preven-
tion of the formation of a coarsely crystalline In order to heat from the interior, an electrical
product. resistor, such as a graphite rod, or an electric
This chapter will address only the latter arc is arranged axially within the reactant
system, the high temperature rotary furnace muffle. Such a system is shown schematically
or high temperature rotary kiln (HTRK) as it in Figure 7.1. Such arrangements have been
is sometimes called. demonstrated not only to be a feasible, but to

Reaction Muffle _ _ _ _...
. ::..:..:.::..:..;;.:..;.
Heater ------~~+I:..:.:
Outer Mufflee-
Insulation ~=====~.~~~~~~~~~~~~~~
Figure 7.1 Internally heated rotary furnace configuration.
be energetically the most efficient option.
Since both the heater and muffle are typically
graphite, they can become part of the reaction
system. Reaction of both the heater and the
muffle with reactants within the muffle
remains a problem.
On the basis of engineering, this heater loca-
tion within the muffle is nearly ideal. Heat is
generated within the reactant muffle and, as
such, provides the most thermally efficient
system. The only moving parts are those asso-
ciated with the material feed, discharge and
the muffle itself. Encrustations on the heater
as well as on the muffle remain problems, as
they are for all rotary furnace designs.
INDIRECT, EXTERNALLY HEATED DESIGN
A second option is to arrange the heater as a
larger cylinder, axially oriented around the
reaction muffle, and separate from it (Figure
7.2). Within this heater is located the reaction
muffle. This muffle contains the reactants and
reaction products. It prevents, or at least mini-
mizes, the reactants and reaction products
contacting and altering the geometry and elec-
trical behavior of the heater. On the exterior,
the heater is provided with yet an additional
muffle. The purposes of this outer muffle
Heater
Reaction- --
Muffle
Retainer Muffle
-----.....
_ ___~
_ . _ . _ . __.
(Black -
Insulation BO)dd~Y)~_==::::~~~~~~~~~~~~~~~
Figure 7.2 Single element externally heated rotary furnace configuration.
Rotary furnace design configurations 161
jllllllllll~I~:
. ;;.,.;..;
._;;.;...;;..;......:-. - .- .- . - . - .-....... _._ .- -1
are twofold. It prevents the insulation from
contacting the heater and affecting the
electrical flow within the system, and it also
prevents the movement of the insulation
during the replacement of the heater. The
second purpose, and from a practical point
perhaps more important, is to provide a
radiation chamber, effectively a black body,
in which the temperature is made more
nearly constant throughout its length. This
provides a longer, more uniform hot zone
in which the muffle is suspended, and as a
consequence a longer uniform hot zone in
which the reaction can take place.
A modification of this external heater
arrangement involves the use of several
smaller diameter heaters located within the
outer gua~d muffle, and surrounding the reac-
tion muffle (Figure 7.3). The outer muffle
again acts as a black body to produce a more
uniform, extended hot zone.
DIRECTLY HEATED DESIGN
A third option is simply to apply power to the
muffle and to heat the reaction muffle directly.
While certain advantages seem apparent,
operation of such a configuration soon
shows the near impossibility of maintaining
'!!!!!!!!!!!!r:
. _. _. _. _.- . _. _. _ . _. _. _. _. _
_.. _ . -
162 Rotary tube reactor processes
Furnace Shell
~:::;;::.......-\\_ _- Outer Muffle
Inner Muffle
Heaters
Figure 7.3 Multiple element externally heated
rotary furnace configuration.
a controlled hot zone configuration as the
muffle reacts and is eroded by the reactants.
In addition, since the heater/muffle is rotat-
ing, the problem of maintaining high current
contacts to the moving reactor becomes yet
another engineering problem.
COMPARISON OF INDIRECTLY HEATED
DESIGN OPTIONS
Both of the first two furnace arrangements
offer advantages as well as weaknesses. The
first, having the heater within the reactor, pro-
vides greater thermal efficiency. The heater is
smaller and requires less power to operate. It
also requires a smaller, less expensive piece of
graphite from which it is machined. It does
provide somewhat reduced total power to
the reactants, at the same surface loadings.
On the negative side, it complicates the feed
mechanism which delivers reactants into the
hot zone. We will discuss this delivery of reac-
tants at more length later. It also reduces the
reactor volume, thus reducing the throughput
over a given period of time. When it comes to
rodding out blockages, encrustations and
build-ups within the muffle, the presence of
an electrically 'hot' structure offers a serious
potential safety hazard.
The externally heated rotary muffle pro-
vides an unobstructed reactor. On the other
hand, it requires significantly larger diameters
not only for the heater but especially for the
outer guard muffle. In order to make such
large heaters, it is necessary to increase their
resistance length and reduce their cross-
sections. Otherwise, the currents required
to heat such a massive heater become un-
manageably large. In order to achieve this
increased length to cross-section ratio, heaters
are typically machined in the form of helices
to increase their resistance. This makes them
more expensive as well as fragile. There is a
hidden advantage to the helix structure, how-
ever. There is a certain degree of flexibility
associated with the helical arrangement, one
not found in simple cylinders. This flexibility
reduces to some extent the possibilities of
fracture due to slight misalignment. It also
reduces the problems associated with thermal
expansion of the heater and maintaining
electrical contact via 'floating' electrode
contacts.
PROCESS CONSIDERATIONS
Delivering large currents to a high tempera-
ture apparatus is in itself a challenge. Heat
transfer from the hot zone toward the in-
coming electrical conductors leads to signifi-
cant heat losses from the reactor, as well as
limiting the materials which are available for
construction. Rotating the reactor provides
similar mechanical difficulties.
The author's experience has been that revol-
ving the reactor on rollers or trunnions is the
simplest, least troublesome arrangement.
Forces to operate this rotation are best deliv-
ered mechanically through atmosphere seals
from an outside drive mechanism through
the furnace shell which provides atmosphere
isolation for the furnace. Atmosphere controls
are' provided at these mechanical lead-
throughs, and all other mechanics are carried
out within the atmosphere chamber. The
overall arrangement of an operational high
temperature rotary furnace system is shown
schematically in Figure 7.4.

Feed Hopper ---+-
----->;~~~~~;;;;;;;;;;;;;;;;;;;;;;;...
i--
Feed Screw
Pitch -+-
Pitch Adjustment
Reaction Muffle - - - - - - /
Heater
Outer Muffle _ _ _ _ _ _..J
Drive Trunions
Figure 7.4 Rotary tube furnace.
REACTANT FEEDING
Reactants are best delivered by a screw feed
from a closed, inert gas purged feed system
through another entrance port into the
muffle. A supply of reactants acts as a stopper
to mlmmlze atmospheric contamination.
Large rotary isolation valves (shown as 'R' in
Figure 7.4) above and below the powder feed
storage provide the most effective atmosphere
isolation.
Attempts to deliver reactants by other
means such as vibratory feeders have been
found to be less effective for at least two
reasons. The positive feed of a screw conveyor
obviously provides a more certain rate of
delivery than a vibratory one. Of even
greater importance are the difficulties asso-
ciated with vibratory feeding at high tem-
peratures. Many of the oxides begin to sinter,
even melt as the reaction temperatures are
approached. This causes them to adhere to
the feed mechanism, and to act to dampen
the vibratory feed process. One option which
has been found at least partially successful
is to encase the powder delivery system
within a water-cooled jacket insulated from
the high temperatures within the reaction
muffle.
Process considerations 163
To Exhaust
~ Product Hopper
~R
REACTION
Carbothermic reactions, especially in produc-
tion scale, generate large volumes of by-
product gases, principally carbon monoxide
(CO), but also including numerous volatile
oxides and suboxides of the reactants. The
large volumes of gas, exiting through a
rather small diameter discharge pipe, mini-
mize the amount of back diffusion and atmo-
sphere contamination. Where discharged, this
gas is passed through a woven metal screen
which acts as a flame arrestor, and is burned
to carbon dioxide prior to discharge to the
outside atmosphere. The flare is maintained
against possible extinguishment by means of
a pilot flame. Experience with such flares,
located within a fully enclosed manufacturing
facility has shown that the release of CO is
effectively eliminated.
PRODUCT DISCHARGE
The product, which will be discharged from the
muffle as a thin incandescent stream, must be
collected and cooled in a water-cooled chamber
before it can be safely discharged and exposed
to the ambient atmosphere. An effective way of
doing this is to discharge the stream first onto
164 Rotary tube reactor processes
an agitated water-cooled chiller or water-
cooled rotary valve ('R' in Figure 7.4), then to
a water-cooled collection chamber, capable of
being isolated from the first by means such as
a gate valve or rotary isolation valve arrange-
ment, and finally discharged from the holding
chamber through a second valve into product
containers.
OPERATING DIFFICULTIES
Several operating difficulties are associated
with any rotary furnace. Not only do the
desired reactions take place, but at least to
some extent a number of especially undesirable
side reactions, for want of a better definition,
occur. Consider some of these.
WALL BUILD-UP AND TUBE PLUGGING
Silica (SiO z) and carbon react in a matter of
seconds at temperatures over 1873 K
(1600 DC). However, SiOz begins to sinter at
temperatures somewhat below 1273 K
(1000 DC). Thus, if a mixture of SiOz and
carbon is allowed to enter a rotary furnace
in the cold zone of the muffle, and to mix as
it is heated, the SiOz soon reaches this sinter-
ing temperature and develops larger sintered
agglomerates as well as a glassy ring near the
entrance of the furnace. The material which
passes the SiOz ring becomes carbon rich.
Far worse, however, the muffle soon becomes
totally plugged by the glassy siliceous ring.
No fully acceptable method has, to the writer's
knowledge, been found to completely prevent
such build-ups.
Two methods of circumventing, or at least
minimizing, this difficulty are to introduce
the silica-carbon mixture along with a layer
of carbon which prevents, or at least mini-
mizes, contact with the muffle until reaction
has begun, or to introduce the reactants
directly into the hotter zones of the rotary
tube, at temperatures above those at which
reaction is essentially instantaneous. Feeding
the raw materials in a comparatively thick
layer, or as a pelletized feed stock, are also
effective in reducing these build-ups.
Over a period of time, all rotary furnaces
and kilns develop such build-ups, clinkers
and dams. In the cement kiln these are
removed by shooting them with a kiln gun
and a projectile. From time to time, even
under the best operating conditions, it
becomes necessary to dislodge these build-
ups by loosening them ('rodding') with a
graphite rod. An effective approach to this
is through water-cooled sight ports axially
located at the entrance and discharge ends of
the muffle. Access through these brings with it
furnace interruptions, thermal instabilities,
introduction of atmospheric contamination
and personal hazards associated with manip-
ulation of incandescent graphite rods. No way
has been found to eliminate this problem
completely.
In most cases, not only do these build-ups
occur near the feed end of the reaction
muffle, but they also develop near the dis-
charge end. One of the reaction intermediates
in many carbothermic reactions is a volatile
suboxide, such as silicon monoxide (SiO)
vapor. This material is unstable except in the
vapor state. On reaching the cooler zone near
the discharge, the SiO vapor cools and dispro-
portionates. In the process, a glassy ring is
deposited at the discharge end. The presence
of SiO as a discharge species can be minimized
by operation of the furnace in a carbon-rich
regime. To the author's knowledge, these
problems have not yet been completely
solved in the operation of rotary furnaces.
While SiO has been cited, it is certainly not
the most troublesome oxide. In the production
of boron carbide, for example, not only are
volatile oxides of boron encountered, but a
special problem is encountered. In the pres-
ence of even traces of water, boron oxides
become increasingly volatile through the
process of steam distillation. Even at tem-
peratures of a few hundred degrees, solid
encrustations of boric oxide form. Also, in
the presence of even small amounts of water,
 Applications to non-oxide powder synthesis 165
boric oxide melts to a viscous glassy material Heat transfer under these conditions would
far below the reaction temperatures. This not be a constraint. The inside surface area of
sticky material becomes an extreme problem such a reactor would be about 0.84 m 2 (9 ft2).
unless the system is completely anhydrous. Based on an enthalpy of reaction of 604 kJ / mol
Since boric oxide readily absorbs water from (van Dijen and Metselaar, 1989) and a furnace
the atmosphere, maintaining anhydrous con- throughput of 6.5 kg/h (14.3lb/h), one can
ditions is extremely difficult. calculate a total required energy input of
27 kW, a very modest load for such a massive
furnace.
REACTOR SIZE LIMITATIONS
There are practical limitations of the sizes of
APPLICA nONS TO NON-OXIDE
graphite which can be obtained without the
POWDER SYNTHESIS
expense of special order. Sizes up to 0.7m
(2.3 ft) in diameter and up to 2.8 m (9.2 ft) The author has had first-hand experience in
in length are available in electrode grade the production of SiC, not only with the exter-
graphite. Standard sizes are more typically nally heated rotating graphite muffle reactor,
0.35m (,....,14 in) diameter and 1.8m (,....,6ft) but with internally heated rotary retorts as
long. The problem is not so much the actual well. Some personal observations are germane
sizes, but the aspect ratio for standard large to this discussion.
graphite. An aspect ratio of 5 (0.35 m The use of the externally heated rotary
dia. x 1.8 m long), after subtracting end- muffle reactor likely provides the best overall
cooling effects, provides a comparatively control of the reaction system, temperature,
short reaction zone, of the order of a meter at atmosphere, agitation rate, dwell time etc.
best. The external atmosphere shell can be pro-
In addition to simple sizes, the weight of the vided with suitable vacuum for atmosphere
material that must be supported and rotated at control, with gas-swept, water-cooled obser-
high temperatures offers serious engineering vation and access ports. It is highly desirable
difficulties. The heat transferred by these to be able to observe the goings-on in one of
massive pieces of graphite must be dissipated . these furnaces. Likewise, it is necessary to
in order to protect electrodes, etc. For access the interior from time to time to take
example, assume a 0.15 m (,....,6 in) inside dia- care of problems such as build-ups when
meter by 1.8m (,....,6ft) long muffle with a they occur.
0.013 m <! in) wall, a space of 0.025 m (1 in)
between the 0.013 m <! in) thick heater and
FEED PREPARA TION
the muffle, and similarly a 0.025 m (1 in)
spacing between the heater and the outside It has been learned that best results with the
0.013 m <! in) thick muffle. This arrangement externally heated rotary reactor could be
would provide a reactor volume of 1 m achieved using a small diameter pelletized
(,....,39 in) in length and 0.15 m (,....,6 in) diameter, reactant feed. The reaction when using the
or approximately 0.018 m 3 (0.64 fe). At a powder feed system could be observed to
volume loading of 15%, a powder density of occur to completion in a matter of seconds.
0.5g/cm3 (31.2Ib/ft3 ), a residence time of 5h The particles would be seen to react, and to
and a yield of 40%, this would yield approxi- generate a quantity of some gaseous product
mately 6.5kg/h (14.3lb/h) of SiC product. when they first entered the reactor. Within a
The graphite parts, only the heater, reactor matter of seconds, certainly much less than a
muffle and outer muffle, would weigh about minute, all evidence of reaction would cease.
68 kg (,....,150lb). The particles would become invisible in and
166 Rotary tube reactor processes
isothermal with the muffle interior. Larger
pelletized feed, however, would exhibit a
dark interior suggesting incomplete reaction
on discharging even after several minutes'
exposure. Thus, it becomes obvious that
pelletized feed should be as small as possible,
commensurate with proper, sustainable
furnace operation.
The thermal transfer through a pelletized
reactant mix during a carbothermal reaction
is complicated. The as-synthesized powders
are excellent thermal insulators. Many of the
typical advanced materials are either metallic
in appearance, and opaque, or they have high
refractive indices and as such scatter rather
than transmit thermal radiation. Thus, the
heat transfer through the as-formed powder
is poor at best. Couple this with the fact that
the by-product gases typically evolved by
these reactions are flowing from a zone at
the reaction temperature outward through
the already formed product. These act as
transpiration coolants, absorbing heat from
the hotter outer zones and carrying this
energy away from the unreacted interior. A
dramatic demonstration of this effect was
demonstrated earlier during an attempt to
scale-up a process for the manufacture of
fine SiC powder.
SILICON CARBIDE
Experiments were conducted at The Carbor-
undum Company, the goal of which was the
development of a process for the production
of fine abrasive SiC lapping powders. Initial
experiments with a small scale 9 cm (3.5 in)
diameter laboratory tube furnace were quite
encouraging in both the rate of conversion
and final powder size. The reaction was
shown to take place in a matter of a few
seconds at temperatures above perhaps
1873 K (1600C). Attempts to scale-up the
reaction were another matter entirely. In the
scale-up experiments, large crucibles 0.23 m
(rv9 in) in diameter by 1.2 m (rv4 ft) long
were loaded with various mixtures of Si02
and carbon and passed through a continuous
0.25 m (rv 10 in) diameter tube furnace approxi-
mately 23 m (rv75 ft) long. Heater and muffle
temperatures ranged from about 1698 to
2748 K (1425-2475C).
The results were enlightening as well as
discouraging. All products, no matter how
rapidly they were pushed through the fur-
nace, contained a cylindrical zone of fine
beta SiC powder, immediately outside the
zone of unreacted starting materials. Even in
the most drastic case involving an 8 h
exposure at 2748 K (2475 0c), there remained
this unreacted zone along the axis of the
crucible. However, the outer regions on the
crucible exposed to temperatures above
perhaps 2373 K (2100C) were crystallized to
the point that in extreme cases individual
crystallites approaching 0.006 m (0.25 in) were
the norm.
Further, side-by-side studies showed that
the thermal insulating capacity of the initially
formed SiC powder was at least equivalent to
that of lamp black carbon, at that time a gen-
erally accepted high temperature insulating
material. It became obvious that this process
and geometry would not be economically
capable of being scaled to production.
TUNGSTEN CARBIDE AND MIXED METAL
CARBIDES
Hara and his co-workers have explored the use
of high temperature rotary furnaces for the
production of tungsten carbide and mixed
metal carbide powders (Hara and Miyake,
1974). Their choice of systems appears to
offer advantages since tungsten oxides in
their partially reduced state can sublime
rather than sintering to form the usual sintered
deposits which have been the limiting factor in
the use of rotary furnaces.
A pilot-scale two-stage system of rotary
furnaces (Miyake and Hara, 1979; Miyake,
Hara and Sho, 1979) has been addressed, the
first to carry out the carburization of the oxide
in an N2 atmosphere, the second using an H2
 Applications to non-oxide powder synthesis 167

C / W03 pellets (6.5 kg/h)

10cmI.D.x1.5m
T=1773K

9cm I.D.x2.4m
T=1923K
.... WCpowder
Figure 7.5 Two-stage rotary tube furnace process for manufacturing fine tungsten carbide powder.
(Miyake, M., Hara, A. and Sho, T., 'The direct production of WC from W03 powder by means of a two-
stage rotary carburization furnace,' Funtai oyobi Funmatsu Yakin (Powder and Powder Metallurgy), 26(3),
90-95, 1979. Reproduced by permission of Funtai Funmatsu Yakin Kyokai, Kyoto, Japan.}

atmosphere to adjust and control metal carbon
stoichiometric ratios (Figure 7.5). The first
rotary furnace had an inside diameter of
lOcm (3.9in) and a length of l.5m (4.9ft).
The second rotary furnace had an inside
diameter of 9 em (3.5 in) and a length of
2.4 m (7.9 ft). Both rotating tubes were inclined
at an angle 6 from the horizontal. In this pro-
cess, a mixture of W03 and carbon was pelle-
tized having an extruded diameter of 1 mm.
The aggregates were heated continuously as
they moved from the first to the second
rotary furnace. Total residence time through
both furnaces was 25 min. The first upper
furnace was heated to 1773 K (1500C) and
supplied with 3m3 /h (1.8scfm) of N 2 . An H2
atmosphere for carburizing was maintained in
the second furnace with a 1 m 3 /h (0.6 scfm) H2
flow. The second furnace was operated at a
higher temperature of 1923K (1650C). The
carbon content and grain size of the product
WC could be controlled closely by adjusting
the initial ratio of C/W03 as well as the atmo-
sphere and temperature of the two rotary tube
reactors. Approximately 6.5 kg/h (14.3Ib/h)
of pelletized precursor could be processed
while maintaining a 1 em (0.39 in) layer thick-
ness in the rotating tubes.
SCALE-UP ISSUES AND OTHER SYSTEMS
To the author's knowledge, there are no
applications in which high temperature
rotary furnaces are being used for the large
scale production of fine powders. A number
of patents have been issued, but the scale of
any commercial application is most likely
developmental. Many of the descriptions of
rotary furnace procedures have addressed
only small scale operations (Wei, 1983), or
have focused on theoretical aspects such as
heat transfer (Sass, 1967; Pearce, 1972; van
Dijen and Metselaar, 1989), or on material
transport phenomena (Taylor and Jenkins,
168 Rotary tube reactor processes
1968; Hehl et ai., 1978; Helmrich and Schugerl,
1980; Ferron and Singh, 1991; Das Gupta,
Khakhar and Bhatia, 1991; Rao, Bhatia and
Khakhar, 1991; Lebas et ai., 1995).
Once perfected, the production of non-
oxide powders by way of the high tempera-
ture rotary furnace should yield an excellent,
consistent, reproducible, economical powder,
possibly superior to any presently being
produced.
REFERENCES
Acheson, E.G. (1893) Carborundum: its history,
manufacture, and uses. J. Franklin Inst., 136,
194-214.
Acheson, E.G. (1895) Production of artificial crystal-
line carbonaceous materials. US Patent Reissue
No. 11,473.
Benner, M.R, Melton, RC and Boyer, J.A. (1939)
Silicon carbide and the manufacture thereof. US
Patent 2,178,773.
Cox, G.C (1937a) Continuous high temperature
electrothermal furnace. US Patent 2,068,447.
Cox, G.C (1937b) Continuous high temperature
electrothermal furnace. US Patent 2,068,448.
Das Gupta, S., Khakhar, D.V. and Bhatia, S.K. (1991)
Axial transport of granular solids in horizontal
rotating cylinders. Part 1: Theory. Powd.
Technol., 67, 145-5I.
Ferron, J.R and Singh, D.K. (1991) Rotary kiln
transport processes. AIChE J., 37(5), 747-58.
Hara, A. and Miyake, M. (1974) Rotary furnace for
carburization. US Patent 3,802,847.
Hehl, M., Kroger, H., Helmrich, H. and Schugerl, K
(1978) Longitudinal mixing in horizontal rotary
drum reactors. Powd. Techno!., 20, 29-37.
Helmrich, H. and Schugerl, K (1980) Rotary kiln
reactors in the chemical industry. Ger. Chem.
Eng., 3, 194-202.
Lebas, E., Hanrot, F., Ablitzer, D. and Houzelot,
J.-L. (1995) Experimental study of residence
time, particle movement and bed depth
profile in rotary kilns. Can. J. Chern. Eng., 73,
173-80.
McMullen, J.C (1957) A review of patents on SiC
furnacing. J. Electrochem. Soc., 104(7), 462-65.
Miyake, M. and Hara, A. (1979) On the carbon
reductions and carburization of W03 with trial
rotary carburization furnace. Funtai oyobi Fun-
matsu Yakin, 26(2), 72-77.
Miyake, M., Hara, A. and Sho, T. (1979) The
direct production of WC from W03 powder
by means of a two-stage rotary carburization
furnace. Funtai oyobi Funmatsu Yakin, 26(3),
90-95.
Pearce, KW. (1972) A heat transfer model for rotary
kilns, in 4th Symposium on Flames and Industry,
British Flame Research Committee and Institute
of Fuel, Imperial College, London, Paper No.7.
Rao, S.J., Bhatia, S.K. and Khakhar, D.V. (1991)
Axial transport of granular solids in rotating
cylinders. Part 2: Experiments in a non-flow
system. Powd. Technol., 67, 153-62.
Roberts, LL. (1897) Process of and apparatus for
manufacturing metallic carbides. US Patent
587,138.
Sass, A. (1967) Simulation of the heat transfer
phenomena in a rotary kiln. I&EC Proc. Des.
Dev., 6(4), 532-35.
Shaffer, P.T.B. (1985) Fine SiC powders for high
performance ceramics, their production and
characterization, in Adv. Eng. Ceram., Proc. Conf.
Raw Mater. Adv. Ceram. Mater., U. Alabama,
Tuscaloosa, AL, Feb. 11-12, pp. 1289-95.
Suzuki, H. and Hase, T. (1983) Method of produ-
cing beta silicon carbide. US Patent 4,368,18I.
Taylor, RF. and Jenkins, T.R (1968) A review of
some aspects of continuous solids-gas flow
behavior in tubular reactors. 1. Chem. Eng. Ser.,
No. 27, 101-1I.
Tone, F.J. (1909) Production of silicon carbide. US
Patent 937,119.
Tone, F.J. (1910) Making silicon carbide. US Patent
965,142.
van Dijen, F.K and Metselaar, R (1989) Chemical
reaction engineering aspects of.a rotary reactor
for carbothermal synthesis of SiC J. Eur. Ceram.
Soc., 5, 55-61.
Wei, G.C (1983) Beta SiC powders produced by
carbothermic reduction of silica in a high tem-
perature rotary furnace. J. Amer. Ceram. Soc.,
66(7), C-111-13.
FLUIDIZED BED REACTOR PROCESSES
Alan W. Weimer
BACKGROUND
Fluidized bed reactors are widely used in
the petrochemical (catalytic cracking) and
chemical process industries (phthalic and
maleic anhydride, oxychlorination of ethy-
lene, acrylonitrile, alkykhloride production
etc.). They are often selected as the reactor of
choice for certain processes in which solids
handling or a high heat transfer rate is of
critical importance. Specifically, the success
of fluid catalytic crackers is due to the simpli-
city with which fine particulate catalyst can be
moved between the fluidized bed cracker and
the fluidized bed regenerator (the particles are
required to take part in two different reactions
as part of the same overall process). Likewise,
the successful application of fluidized bed
reactors to highly exothermic oxidation pro-
cesses, such as those cited above for the
chemical process industries, is due to the abil-
ity of the reactor to control the exothermic
reactions which are taking place.
In a gas fluidized bed reactor, gas is passed
upward through a bed of fine particles (typi-
cally 20 to 3000 Jim) which is supported by a
gas distributor (Kunii and Levenspiel, 1991).
At a high enough gas flow rate above the mini-
mum fluidization velocity the solid particles
become suspended and are in continuous
motion as a well mixed 'churning mass'. The
fluidized bed of solids looks very much like a
boiling liquid and in many ways exhibits
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
8
liquid-like behavior. This 'fluidized state' of
the solids allows the reactor to operate in an
isothermal manner. High bed to surface heat
transfer rates allow temperature to be con-
trolled very closely. The fluid-like properties
of the gas-solid mixture within the bed
allow the particles to be transferred easily
from one vessel to another or removed. The
simplified solids handling, high heat transfer
rates and intimate gas-solids contacting are
often the most important properties for select-
ing fluidized beds for industrial processes.
The disadvantages of fluidized beds need to
also be considered. For example, although the
rapid mixing of the particles provides for high
heat transfer rates and a uniform temperature
control, the solids mixing is clearly undesir-
able for continuous processes in which the
particles are being removed as the reacted
product. This continuous stirred tank resi-
dence (CSTR) time distribution of the solids
allows incompletely converted particles to be
removed along with converted ones. Varia-
tions of the process including multiple
fluidized beds in series or an internal baffling
arrangement (to promote plug flow solids
behavior) are desirable if a high solids conver-
sion is of primary importance. In addition,
there can be difficulties associated with the
attrition or break-up of particles caused by
their vigorous agitation in the fluidized state.
This attrition can result in a substantial yield
loss overhead as fines are carried out of the
170 Fluidized bed reactor processes
bed with the fluidizing gas stream. Finally, the
gas generally flows as bubbles through the
bed of solids. The bubbles increase in size
and velocity as they rise through the bed of
solids and provide a means for the gases to
bypass the solids, thus reducing the contact
between solids and gases.
Fluidized beds have been studied exten-
sively and there are several excellent texts
containing information regarding their funda-
mental understanding and basic application
(Davidson, Clift and Harrison, 1985; Geldart,
1986; Kunii and Levenspiel, 1991; Yates,
1983). This chapter will focus entirely on the
specific application of fluidized bed reactors
to the carbothermal reduction synthesis of
non-oxide ceramic powders. Very little has
been reported for this application.
APPLICATION TO CARBOTHERMAL
REDUCTION PROCESSES
GENERAL CONSIDERAnONS
Fluidized bed reactors have been investigated
for the carbothermal reduction synthesis of
non-oxide ceramic powders. They have both
advantages and disadvantages which must
be considered. Since conventional carbo-
thermal reduction processes involve the
highly endothermic reaction of two solid start-
ing reactants (carbon and an oxide), it is criti-
cal that energy be provided efficiently to the
reaction mass and that the reactants be in
intimate contact throughout the process. In
addition, since a third solid species is formed
as the product of the reaction and since it is
difficult to remove unreacted precursors
from the product, it is clear that high conver-
sion of the limiting reactant must be obtained
in the reactor.
Clearly, an advantage of the fluidized bed
reactor for carbothermal reduction synthesis
is the ability to efficiently supply heat to
drive the highly endothermic reactions.
Fluidized bed reactor process throughput
will generally not be heat transfer limited. In
addition, fluidized beds have gas-solid con-
tacting advantages for those nitride synthesis
processes requiring contact of the solid
reactants with gaseous N2 or a nitrogen-
containing gas. This gas-solid contacting
efficiency is also an advantage for sweeping
by-product CO out of the reactor.
On the other hand, for a reaction taking
place between solids such as carbothermal
reduction, the agitation of the solids may pro-
mote the separation of the solid reactants. A
particular concern for carbothermal reduction
is the separation of the carbon from the metal
oxide to be reduced. It is clear that the binder
system, which holds the precursor reactant
particles together, is of critical importance
for achieving high product yields. In addition,
as particles both react and attrite it is likely
that both reacted product and unreacted
attrited precursor fines will be taken overhead
and need to be separated downstream.
Another concern in utilizing a single fluid-
ized bed reactor for carbothermal reduction
is the inherent presence of unreacted precursor
exiting the reactor with converted product due
to the nearly perfect mixing of the solids (CSTR
effect). This difficulty exists because the con-
verted solids rather than the exiting gas are
the product of reaction. A method to alleviate
this problem is to operate multiple fluidized
beds in series (Nishi et al., 1989; Shimizu,
Fukuoka and Fukuhira, 1991) so as to
approach a plug flow reactor (PFR) residence
time distribution. An alternative method of
operation would be to utilize a second reactor
of plug flow design (PFR) downstream of the
fluidized bed (Fukuoka et al., 1993). Then, the
fluidized bed would drive the bulk of the reac-
tion while the secondary PFR reactor insured
completely converted product out.
In summary, for carbothermal reduction
synthesis, the primary advantages of fluidized
bed reactors are the ability to easily move
solids, the high heat transfer rates which will
be used to drive the highly endothermic
reactions, and the subsequent isothermal
conditions which result from rapid mixing.
 Application to carbothermal reduction processes
The primary disadvantages which must be
overcome are associated with the attrition
and the CSTR residence time distribution of
the solids.
ELECTROTHERMAL FLUIDIZED BED
A continuous fluidized bed version of the
Acheson process for manufacturing SiC (elec-
trothermal fluidized bed furnace - EFB) has
been commercialized by Superior Graphite
Company (Goldberger, 1985; Goldberger and
Reed, 1984; Goldberger, Reed and Morse,
1989; Markel and Goldberger, 1979). Silica
sand and petroleum coke are continuously
introduced as free flowing granular solids
into a closed vessel. An inert gas, such as N 2,
or a recycled product gas stream containing
CO, is used to fluidize the solid reactants.
An electrical potential is applied between the
vessel and a centrally positioned electrode
(Figures 8.1 and 8.2) or between electrodes
disposed in direct contact with the particles
to heat the contents of the fluidized bed to
a temperature of approximately 2173 K to
2273 K (1900C to 2000C). The relative feed
rates and type of carbon and silica used, the
reaction temperature, the retention time of
the mixture in the bed and the mode of fluid-
ization are adjusted so that the content of SiC
in the product is controlled up to about 95%,
with the balance mainly free carbon. The
fluidized bed process can be operated in
various modes at high throughput for large
scale commercial production.
In one mode of operation, product SiC is
removed below the fluidized bed, while in
another mode of operation, product SiC is
removed above the bed.
Below bed product discharge
The EFB can be operated to produce a coarse
metallurgical grade SiC in a manner by which
the product is removed below the fluidized
bed as shown in Figure 8.1. An electrically
conductive solid material such as petroleum
171
coke is fluidized within a charge zone by the
furnace walls. The fluidizing gas enters the
furnace through a feed pipe to the plenum
and is distributed through the bed of solids
uniformly through orifices via a horizontal
gas distribution plate. The coke typically is
in the size range of about 1000-3000 11m
while the fluidizing gas velocity within the
bed is approximately 0.46 m/ s (1.5 ft! s).
A centrally located vertical graphite elec-
trode is immersed in the fluidized bed of
particles and serves as one electrode of the
bed. The furnace walls are constructed of
graphite and serve as the other electrode in
direct contact with the bed of fluidized electri-
cally conductive coke particles. A voltage is
applied between the electrodes, thus allowing
the fluidized coke particles to be heated
directly by electrical resistance. The flow of
current causes the bed to be heated to high
temperatures in accordance with the PR con-
version of electrical energy into heat.
Typically, an initial charge of coke is heated
to the desired reaction temperature prior to
feeding the reactants. Once the desired bed
temperature is reached, solid reactants are
fed continuously by gravity through a feed
inlet to the high temperature reaction zone of
the bed. Eventually, the initial charge of coke
used to preheat the bed is replaced by the
reacting feed material. The reactant carbon
and silica may be fed individually as dry pow-
ders through separate feed devices or may be
intimately mixed and fed simultaneously
through a single port as shown. Intimately
mixed solid reactants may be agglomerated
as spherical aggregates or cylindrical pellets
which are held together with a suitable
binder to maintain structural integrity. A
relatively coarse metallurgical grade of SiC
is obtained by reacting a pelletized stoichio-
metric mixture of coke and silica sand.
Because of the inherent rapid mixing of the
fluidized bed solids, the material in the
fluidized bed is a mixture of partially reacted
pellets which range from unreacted feed
pellets to fully converted raw SiC product.
172 Fluidized bed reactor processes
Central Graphite
Electrode
Product
Gas Out

Graphite
Wall

Electically
Conductive
Orifice Solid
(Petroleum Coke)

Distributor

Gas In ...... ===~ ___ ~~~ ___ Plenum

Pellet Product Mixture

Solids Product
Out
Figure 8.1 Electrothermal fluidized bed (below bed product discharge). (Adapted from Goldberger, 1985.)
 Central Graphite
Electrode

Solids Product Gas

In & Fume Out

l
Particulate
Carbon

Graphite
Wall

Graphite
Wall
Electrode

Lower
Zone
Distibutor
SiCIC
Product
Fine
Silica Orifice

Gas In

Solids
Outlet
Valve

Solids Product Out

Figure 8.2 Electrothermal fluidized bed (above bed product discharge). (Adapted from Goldberger, 1985.)
174 Fluidized bed reactor processes
This pellet product mixture IS continuously
withdrawn from the bottom of the fluidized
bed through a discharge port. The overall
electrical resistance of the fluidized bed of
particles and, hence, the temperature can be
adjusted by the addition of graphite or other
particulate solid carbon material if desired.
Product gases comprising inert N2 and by-
product CO are removed through an exhaust
pipe in the top of the furnace. To prevent plug-
ging due to solidification of condensable com-
ponents such as metallic impurities associated
with the reactants, the exhaust pipe is main-
tained at temperatures above the condensa-
tion temperature of the impurities. The high
temperature can be achieved by conduction
from the bed or by resistive heating using a
heating element. An alternative method for
preventing condensation is to add a halogen-
containing gas, such as C12, to the fluidizing
gas stream to react with metallic impurities
and convert them to chlorides which are vola-
tile and will not condense at the exhaust pipe.
In order to maintain a continuous operation, it
is critical that metallic deposition be pre-
vented at the exhaust pipe.
Above bed product discharge
The EFB can be operated to produce a fine
sinterable grade SiC in a manner by which
the product is removed above the fluidized
bed as shown in Figure 8.2. To produce an
SiC fume comprising micron- or submicron-
sized particles, the Si02 source may be an
ultrafine powder having a mean particle
diameter <10 Ji,ID, or a silicon-bearing gas
such as SiCl4 or trichlorisilane and reacted
with a fine carbon source such as carbon
black or with a carbon-bearing gas such as
methane or propane. The particulate carbon
source is fed by gravity through a feed inlet
at the top of the furnace. Finely divided Si02
is fed through a cooled feed nozzle so as to
enter the fluidized bed of relatively coarse
carbon at a point below the upper surface of
the bed.
The fluidizing gas enters the plenum cham-
ber through a gas feed pipe and is distributed
to the bed through the orifices of a gas distri-
bution plate. Process gases exit the furnace
through an exhaust pipe at the top.
The bed is heated as described previously
by passing an electrical potential through the
bed of solids using a centrally located elec-
trode and the furnace wall. The furnace wall
electrode is of a smaller diameter in the
lower zone than in the upper zone. This
allows the electrical resistance of the lower
zone of coarser carbon to be substantially
lower than that for the upper zone of finer
carbon and SiC. In addition, the length of the
electrical path from the central electrode to the
wall electrode is less in the lower zone than in
the upper zone. Hence, there is a much higher
flow of electrical current from the central
electrode to the walls in the lower zone.
These factors allow the lower fluidized bed
zone to be maintained at a much hotter tem-
perature than the upper fluidized bed zone.
A fine SiC product is synthesized by react-
ing volatile Si-containing vapors (such as SiO
or gaseous Si) with volatile carbonaceous
components in the upper fluidized bed zone.
The volatile Si-containing vapors are formed
in the lower fluidized bed zone by maintain-
ing the lower part of the fluidized bed at a
temperature above the decomposition tem-
perature of SiC. The volatile carbonaceous
components may be formed rapidly in the
upper fluidized bed zone by feeding green
petroleum coke as the particulate carbon
source. Then, the rising Si-containing vapors
which are formed in the high temperature
lower zone enter the lower temperature
upper zone and react rapidly with the volatile
carbonaceous components to form an SiC pro-
duct of submicron size. The temperature in the
upper fluidized bed zone is high enough to
form SiC rapidly, but below its decomposition
temperature. This fume product is entrained
in the gases leaving the furnace through the
exhaust pipe and is collected by cooling and
filtering the gases in an unoxidized state.
 Application to carbothermal reduction processes
A fine SiC-C reaction product can be syn-
thesized when feeding fine particulate carbon,
such as finely ground coke, gas blacks, char
or natural graphite fines into the upper zone
and reacting it there with the upward flowing
Si-containing vapors. The fine SiC-C product
is partly removed by entrainment in the
fume as described previously and partly
removed by gravity flow through a discharge
chamber contained within the outside furnace
wall.
Product SiC properties
The product SiC-C, generally free flowing
grains smaller than 3000/Lm in average size,
is removed continuously from the fluidized
bed vessel. The intimate SiC-C product can
be used directly in some applications, for
example as an Si-C additive to molten iron.
175
The mixture also offers other unique proper-
ties as an insulating refractory material and
as a granular conductive material for resistive
heating in oxidizing atmospheres. In addition,
this reaction product can be processed by
various conventional post-treatments for
size reduction, carbon removal and chemical
purification to yield a high purity fine SiC
powder for advanced ceramic applications.
Importance of petroleum coke macroporosity
The mechanism of the reaction is such that the
characteristics of the petroleum coke have a
substantial effect on the rate. Reaction occurs
through the formation and subsequent reduc-
tion of gaseous SiO <equations 3.37 to 3.39).
The photomicrographs shown in Figures 8.3
and 8.4 provide evidence for a gas-solid reac-
tion occurring, most likely between SiO and C.

(A)

(8) (C)

Figure 8.3 The development of SiC coating on particles of petroleum coke (x50): (A) coke particles before
SiC reaction; (B) partially reacted coke - 55% SiC; (C) fully reacted coke - 95% SiC. (Goldberger, W.M.,
Reed, A.K. and Morse, K, 'Synthesis and characterization of HSC silicon carbide,' in Ceramic Transactions,
2,93, 1989. Reproduced with permission of the American Ceramic Society, Westerville, OH.)
176 Fluidized bed reactor processes
(A)
Figure 8.4 The formation of SiC as a coating and within the pore structure of particles of petroleum coke
(x50): (A) partially reacted; (B) fully reacted - 75% SiC. (Goldberger, W.M., Reed, A.K. and Morse, R,
'Synthesis and characterization of HSC silicon carbide: in Ceramic Transactions, 2, 93, 1989. Reproduced
with permission of the American Ceramic Society, Westerville, OH.)
The sequence of photographs in Figure 8.3
illustrates the development of a coating of
SiC on the external surfaces of the coke
particles. The coke particles maintain their
original size as they are converted to SiC.
Polished cross-sections of particles (Figure
8.4) at different degrees of conversion indicate
that reaction occurs within the pores of
the coke as well. The formation of by-
product CO results in a porous product
structure as two-thirds of the reacting carbon
is gasified. Preferably, the coke is highly
macroporous so as to allow for high SiO diffu-
sion rates within the particles. A desirably
high macroporosity is not necessarily indicated
by a high Brunauer-Emmett-Teller (BET) sur-
face area. The high BET surface area may result
from an abundance of micropores which are
less accessible to SiO than a lower surface
area coke having a larger pore structure.
Advantages of the EFB
The EFB design takes advantage of two key
characteristics provided by fluidization: 0)
rapid and uniform heating and (2) simplified
continuous solids flow into and out of the reac-
tor. The inherent rapid heating rates are aug-
mented by direct resistive heating of the
fluidized coke particles. The use of internal
electrodes drives the rapid endothermic reac-
tion very efficiently. The heating rate is fast
,.f..,
~.. ..... ...: "
.... \..~It~~'. . ;.-.', (8)
"~.:<.~ ~"-'~.-: .'
:.
."
:..:
'..
'.~
e~
..~
~
. _,-
_ .., "
.
,:' _/', ','.1,',
"
'/
'.,f' ';..
20KV X50 1000U 004 95000 SHG
enough that heat transfer resistances do not
control the reactor throughput as they do in
conventional Acheson-type batch processing.
The simplified solids flow in and out of the
reactor and the ability to remove products at
various locations (below bed, above bed,
entrainment out top) allow products of differ-
ent grades (coarse, fine, fume) to be manufac-
tured continuously in the same vessel. The fast
intrinsic reaction (Weimer et ai., 1993) of fine
carbon with volatile Si-containing species and
fast heating allow complete or nearly complete
conversion to be obtained, even with the CSTR
type of residence time distribution inherent to
fluidized beds.
OTHER FLUIDIZED BED PROCESSES
Other fluidized bed reactor processes have
been investigated for the synthesis of SiC
and other non-oxide ceramic powders.
A large scale fluidized bed development
effort for SiC and ShN4 synthesis has been
carried out by Nihon Cement Co., Ltd. (Nishi
et al., 1989). This reactor (Figure 8.5) uses
multiple vertically stacked fluidized beds in
series. A solids raw material drying section
is located above the uppermost fluidized bed
reaction zone while a feed gas inlet section is
located below the lowermost fluidized bed
reaction zone. The exiting solids are cooled
in a cooling zone located below the gas inlet
 Application to carbothermal reduction processes 177
Feed
Solids
In

+
Product
Gas
&
Dust

Solids Feed
Drying Zone

Upper Reaction
Zone

Graphite Heating
Discharge Element
Valve
Distributor

Lower Reaction
Zone

Feed Gas
Inlet

Cooling
Zone
~ Gas In

Figure 8.5 Multi-staged fluidized bed reactor for synthesizing SiC and Si3 N 4 . (Adapted from Nishi et al.,
1981.)
178 Fluidized bed reactor processes
Gas Exhaust

Upper Combustion
Zone

Oxygen
......
...... ; W, j
>
>

Feed
Solids

Lower Fluidized
Bed Zone

Gas In ..... _ - .....

; -PI
(CH4. inert) Overflow
.;
Outlet

Figure 8.6 Fluidized bed process heated by combustion for synthesizing SiC. (Adapted from O'Connor
and McRae, 1969.)

section. Gas flows upward counter-current to
downward flowing solids. Each reactor stage
has a gas distributor to support the fluidized
solids and distribute the gas coming up from
below. Solids flow downward through a
valve-operated product discharger, which
controls solids bed height in the particular
reaction stage. The reaction stages, including
the distributor and solids discharger, are
typically fabricated of graphite. Each stage is
heated indirectly by radiation from resistively
heated graphite or SiC heating elements.

The advantages of this design are the effi-
cient heat exchange at the top and bottom of
the reactor, the near plug flow residence (PFR)
time distribution achieved using multiple
fluidized beds in series and the increased
product yields which result from efficient
usage of intermediate reaction gases. The
exiting hot product gases dry and pyrolyze
incoming reactant solids in the upper solids
feed section. Likewise, hot downward flowing
product solids preheat incoming feed gases at
the lower gas inlet section. The vertically
stacked fluidized beds allow completely con-
verted products to exit the reactor. In addition,
volatile SiO is formed quickly in the lowest
reaction zone as an intermediate to the synth-
esis of SiC and Si3N 4. The SiO is converted to
product SiC or Si3N4 in the upper reaction
zones. In more conventional single stage pro-
cesses, the SiO would be lost with the exiting
product gases.
A major engineering challenge is control of
the various solids levels within the individual
reaction zones. This control is complicated by
particle segregation resulting from attrition or
aggregation of particles and the high reaction
temperatures (to 2073 K, 1800C) which pro-
hibit conventional measurement methods for
such parameters as bed height.
For SiC synthesis, O'Connor and McRae
(1969) developed a fluidized bed process
(Figure 8.6) in which the energy required to
drive the endothermic reaction is supplied
by radiation from an exothermic combustion
reaction in the upper part of the bed where
exothermic combustible materials are reacted
with oxygen. Carbon and an Si-containing
compound are reacted in the lower fluidized
bed with product removal from the middle
discharge zone. Clearly, the rapid mixing of
solids in the fluidized bed allows uniform
radiative heating within this zone from
above. Methane, added to the fluidizing gas
stream, cracks to hydrogen and carbon in the
lower fluidized bed. The carbon reacts with
volatile Si-containing compounds to SiC
while the hydrogen is combusted in the
References 179
upper part of the bed with added oxygen.
Feed solids including quartz or carbon-silica
mixtures are fed above the fluidizing bed in
the middle zone. Product SiC is removed
through an overflow outlet while exhaust
gases are removed overhead.
Additional fluidized bed reactor processes
have been evaluated; however, they have
typically been of smaller scale and not
developed to the extent of those described
above. Robb (1963) describes a batch fluidized
bed process developed by General Electric
Company for the manufacture of WC and
Mo2C. A carbothermal nitridation process for
the synthesis of AlN was developed by
Carborundum (Kim, Venkateswaran and
Kujawa, 1992; Kim et ai., 1992) while
Alusuisse-Lonza Service Ltd. (Hofmann et ai.,
1993; Hofmann and Vogt, 1993; Van Dijen,
1994) investigated a fluidized bed process for
the carbothermal nitridation synthesis of
Si3 N 4
REFERENCES
Davidson, J.F., Clift, R. and Harrison, D. (1985)
Fluidization (2nd edn), Academic Press, London.
Fukuoka, H., Shimizu, M., Ochiai, H., Shimizu, H.
and Fukuhira, M. (1993) Preparation of silicon
nitride powder by partially nitriding in a fluidized
bed and then completing nitridation in a moving
bed. US Patent 5,232,677.
Geldart, D. (1986) Gas Fluidization Technology, John
Wiley, Chichester.
Goldberger, W.M. (1985) Method for the continuous
production of carbides. US Patent 4,543,240.
Goldberger, W. and Reed, A.K. (1984) Method of
making ultra-microcrystallite silicon carbide
product. US Patent 4,435,444.
Goldberger, W.M., Reed, A.K. and Morse, R. (1989)
Synthesis and characterization of HSC silicon
carbide, in Ceramic Transactions Vol. 2, The Amer-
ican Ceramic Society, Westerville, OH, p. 93.
Hofmann, H. and Vogt, U. (1993) Manufacture
of silicon nitride powder. OberfI. Werkst., 34(3),
8-11, 13-15.
Hofmann, H., Vogt, u., Kerber, A. and Van Dijen, F.
(1993) Silicon nitride powder from carbothermal
reaction. Mat. Res. Soc. Symp. Proc., 287, 105-20.
180 Fluidized bed reactor processes
Kim, J.J., Venkateswaran, V. and Kujawa, R (1992)
Apparatus for the continuous production of high
purity, ultra-fine, aluminum nitride powder
by the carbo-nitridization of alumina. US Patent
5,108,713.
Kim, J.J., Venkateswaran, V., Katz, J.D., McMurtry,
C.H. and Sane, AY. (1992) Process for the contin-
uous production of high purity, ultra-fine, alumi-
num nitride powder by the carbo-nitridization of
alumina. US Patent 5,154,907.
Kunii, D. and Levenspiel, O. (1991) Fluidization
Engineering (2nd edn), Butterworth-Heinemann,
London.
Markel, RF. and Goldberger, W.M. (1979) Method
for heat treating carbonaceous material in a
fluidized bed. US Patent 4,160,813.
Nishi, Y., Kawasaki, K, Hayashi, M. and Yamagishi,
C. (1989) Process and apparatus for producing
non-oxide compounds. US Patent 4,818,511.
O'Connor, T.L. and McRae, W.A (1969) Fluidized
bed process for the preparation of colloidal
silicon carbide. US Patent 3,368,871.
Robb, W.L. (1963) Process for producing carbides.
US Patent 3,077,385.
Shimizu, M., Fukuoka, H. and Fukuhira, M. (1991)
Preparation of silicon nitride powder. US Patent
5,073,358.
Van Dijen, F.K (1994) The design of a circu-
lating fluid bed reactor for the carbothermal
synthesis of silicon nitride. J. Eur. Ceram. Soc., 14,
397-401.
Weimer, AW., Nilsen, KJ., Cochran, G.A and
Roach, RP. (1993) Kinetics of carbothermal reduc-
tion synthesis of beta silicon carbide. AIChE J.,
39(3),493-503.
Yates, J.G. (1983) Fundamentals of Fluidized-Bed
Chemical Processes, Butterworths, London.
PART THREE
COMBUSTION SYNTHESIS PROCESSES
The combustion synthesis process utilizes
highly exothermic reactions to form a variety
of ceramic, intermetallic and composite
materials. These reactions typically have high
activation energies and generate substantial
amounts of heat. They can take place in both
solid-solid or gas-solid systems. Once the
reactions are initiated, they can become self-
sustaining and will propagate through the
reactant mixture in the form of a combustion
wave. This process is also called self-
propagating high-temperature synthesis (SHS).
The thermochemistry and kinetics of these
processes are discussed at length in Chapter
9. The adiabatic reaction temperatures for
various reactions, stability analysis and the
structure of the combustion front are investi-
gated. The fundamentals of both gasless com-
bustion and gas-solid combustion systems are
included. The application of combustion
synthesis to specific processes, the types of
reactors employed and the quality of the
product powders are discussed in Chapter 10.
OVERALL PROCESS
For solid-solid systems (gasless combustion)
to produce non-oxide products, the reactant
mixture is typically placed in a refractory con-
tainer, degassed and ignited in vacuum or an
inert atmosphere. Ignition can be achieved
using an electrical ignitor, a chemical ignitor
or localized heating. The resulting combustion
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
product might be in the form of a powder or a
dense compact. The purity of the resulting
product powder depends heavily on the
purity of the starting reactants, the complete-
ness of the de gasification process prior to
ignition, the completeness of the reaction
and the compatibility of the container refrac-
tory with the reactants and products. The
product may be crushed, milled, purified
and/ or classified depending on the final
product application.
For gas-solid systems, the gaseous reactant
must be supplied to the reaction front in order
to avoid being depleted. For powder beds of
reactant, a pressure gradient results and reac-
tant gas is supplied to the reaction front from
the surrounding atmosphere by 'filtration'
through the porous mass. The reactant gas
flow can be either co-current or counter-
current to the direction of the propagating
combustion front. Gas-solid combustion reac-
tions are often described as 'filtration combus-
tion' processes. Often, very high pressures of
reactant gas are employed to ensure complete
conversion of the solid reactant. The most
common type of gas-solid system is that
involving the reaction of fine metals (alumi-
num, silicon, boron, transition metals) with
nitrogen (i.e. direct nitridation).
Combustion synthesis characteristics in-
clude rapid propagation of a combustion
wave, the generation of high temperatures
and the rapid heating of the product. Fast
182 Combustion synthesis processes
cooling rates may promote the formation of
a solid product comprising non-equilibrium
phases.
SAFETY ISSUES
A primary safety concern for combustion
synthesis processes is the handling of fine
reactive metal powders. Dust explosions (in
air) of atomized metals could be devastating
due to the large maximum pressure increase
and ultimate pressure of the explosion. Ther-
mal dust explosion testing and detailed
thermodynamic calculations need to be car-
ried out to evaluate the potential for dust deto-
nation within the reaction zone. Since direct
nitridation reactions consume gas, it is impos-
sible for instantaneous reaction to result in an
explosion caused from pressure by an increase
in gaseous product. However, the potential of
thermal shock waves (instantaneous pressure
increase due to instantaneous temperature
rise) to occur needs to be addressed. All
thermodynamic calculations and safety-
related testing need to be carried out prior to
any extensive experimental phase. All testing
should be done at facilities capable of hand-
ling such work.
Special precautions need to be made to
ensure the safety of the front-end powder-
handling equipment and process area. All
recommendations made by the atomized
metal powder supplier should be sought and
implemented. All instrumentation and equip-
ment need to conform to strict electrical classi-
fication requirements. The reaction vessel
should be constructed of material which is
capable of handling the high temperatures
generated by the combustion processes.
These temperatures (as high as 2073-3973 K
0800-3700C can typically reach levels
above the melting temperature of most
common steels (,....,1773 K; 1500C). Metal-fire-
fighting extinguishers need to be used where
appropriate. Operating personnel need to be
trained regarding hazards of the process.
For cases in which the reacting solid is being
processed continuously, it is essential to make
sure the exothermic reaction is quenched so
that propagation can be avoided in down-
stream process lines and equipment. It is
also necessary to plan ahead for any unex-
pected reaction which might occur within
the product collection system. Refractory
liners should be used in certain downstream
equipment areas to ensure that unexpected
reaction heat generation does not result in
melting through steel processing equipment.
Powder collection devices need to be properly
grounded to prevent static ignition. Con-
trolled oxidation processes need to be carried
out prior to exposing any pyrophoric dusts to
air. No blowers should be installed in process
lines upstream of the powder collection equip-
ment because they could provide a static
ignition source.
Finally, industrial hygiene considerations
need to be made with regard to the specific
properties of the dusts being handled. The
Material Safety Data Sheets (MSDS) for the
specific compounds being handled need to be
reviewed and the proper guidelines followed.
Dust collection equipment and personal pro-
tection equipment (respirators) should be
used to reduce dust hazards.
THERMOCHEMISTRY AND KINETICS
Jan A. Puszynski
PRINCIPLES OF COMBUSTION SYNTHESIS
Self-propagating high-temperature synthesis
(SHS), also called combustion synthesis, is a
novel and simple method for making certain
advanced ceramic and intermetallic materials
(Merzhanov, 1993; Pampuch, Stobierski and
Lis, 1994). This method has received consider-
able attention as an alternative to conventional
furnace technology. The principal concept of
this technique is that, once initiated, a highly
exothermic reaction can become self-sustain-
ing and will propagate through the reactant
mixture in the form of a combustion wave.
For this to happen, a chemical reaction must
have a relatively high activation energy and
must also generate a sufficient amount of
heat. Synthesis of refractory high-temperature
materials (e.g. borides, carbides, nitrides and
silicides) from elemental constituents exhibits
both of the characteristics mentioned above.
The historical development of combustion
technology is well documented by Hlavacek
(1991). Combustion synthesis of inorganic
materials is a technology which has been in
existence for more than a century. However,
a systematic study of advanced ceramic
material synthesis was initiated by Merzha-
nov and his associates in 1967. Since then,
many theoretical and experimental papers
have been published on this subject. The
details of this development can be found in
review papers by Merzhanov (1981, 1990,
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
9
1993); Frankhauser et ai. (1985); Munir and
Anselmi-Tamburini (1989); and McCauley
(1990). A wide variety of refractory materials,
ranging from single compounds to multi-
component composites and solid solutions,
have been synthesized by this method. In
general, the combustion synthesis can be
categorized as a gasless combustion or a
gas-solid combustion.
In the case of the gasless combustion, solid
reactants are usually dry or wet mixed in a
blender and the resulting mixture is pelletized
to increase an intimate contact between indivi-
dual particles. The reactant mixture is placed
in a refractory container, degassed and ignited
in a vacuum or inert atmosphere. Purities of
inert gas and solid reactants, completeness of
the degasification process and the compati-
bility of the inert container material affect
the oxygen content in the final product. In
some cases, the purity of a resulting product
might even be higher than that of the starting
reactants due to evaporation of volatile
species and suboxides in the combustion
zone. Recent work (Halverson, Ewald and
Munir, 1995) has shown that dramatic
improvements in microstructural uniformity
with reduced defects can be achieved when
extensive preconditioning measures such as
colloidal pressure filtration and thermal-
vacuum outgassing treatments are combined
to homogenize the reactants and outgas the
system. The gasless combustion process is
184 Thermochemistry and kinetics
Ti + C=TiC
Ti +C
Cold Pressed Powder
Compact
Ti+C
Combustion Reaction Passes
Through Sample
Figure 9.1 Schematic of combustion synthesis.
shown schematically in Figure 9.1. The result-
ing combustion product might be in the form
of a powder or a dense compact. The use of
uniaxial, isostatic or centrifugal force is
required in order to accomplish a simul-
taneous combustion synthesis and densifica-
tion. Various aspects of in-situ densification
are described by McCauley (1990), Merzhanov
and Yukhvid (1990) and Odawara (1990).
A direct reaction between a solid reactant
(aluminum, silicon, boron, transition metals)
and gaseous nitrogen can also be self-
sustaining. However, in many cases, high
nitrogen pressures (PN 2 > 5 MPa (>50 atm
are required to complete the nitridation pro-
cess. Even under very high gas pressures (hun-
dreds of atmospheres), the amount of nitrogen
gas present in the voids of the porous metallic
Ti+C
Ti + Spark Initiation
of Reaction
Final Product
specimen is insufficient for a complete conver-
sion. However, as the gaseous reactant gets
depleted at the reaction front, a pressure
gradient results and nitrogen is supplied to
the reaction front from the surrounding atmo-
sphere by 'filtration' through the porous
sample. As a result, high degrees of conversion
can be achieved, without application of ultra-
high nitrogen pressures. Thus, the prevailing
term for describing gas-solid combustion
reactions is 'filtration combustion'.
The gas-solid reactions can be carried out
using various reactor configurations shown in
Figure 9.2. The metal powder is contained in a
refractory crucible and the nitrogen flow to the
reaction zone is co-current (Figure 9.2(a or
counter-current (Figure 9.2(b to the direction
of the propagating combustion front. In the
 Principles of combustion synthesis 185

(a) Gas

...
Gas

..
(c)

Gas

Product

(d)

Figure 9.2 Reactor configuration for gas-solid reactions. (Agrafiotis, c., Puszynski, J.A. and Hlavacek, V.,
'Experimental study on the synthesis of titanium and tantalum nitride in the self-propagating regime:
Comb. Sci. Technol., 76, 187-218, 1991. Reproduced by permission of Gordon and Breach Publishers,
Lausanne, Switzerland.)
186 Thermochemistry and kinetics
co-current configuration, the gas has to be fil-
tered through the hot product layer to reach
the unreacted metal. For systems that exhibit
melting or sintering of the product, permeabil-
ity is significantly reduced and an incomplete
conversion or extinction of the combustion
wave may occur. The counter-current config-
uration is more suitable in such cases. Combus-
tion of pressed metallic pellets in nitrogen is
governed by a combination of co- and coun-
ter-current filtration (Figure 9.2(c)). However,
at low nitrogen pressures, the nitridation reac-
tion usually takes place only in a very thin layer
on the outer surface of the pellet due to the rela-
tively low initial porosity of the metal specimen.
Complete nitridation inside the pellet can be
accomplished by the application of very high
nitrogen pressures (Hirao, Miyamoto and
Koizumi, 1987a) or by use of a solid nitrogen
source (e.g. NaN3 ) (Holt and Kingman, 1984).
The configuration depicted in Figure 9.2(d) is
essentially equivalent to that shown in Figure
9.2(b). However, in this case, the significantly
shorter filtration path results in the synthesis
of a less sintered and more uniform product
composition. This type of arrangement is
called a cross-flow configuration.
The final product composition and its
morphology for the case of both gasless and
Rate of Energy
Release
Direction of
propagation
Reactant Heating Reaction
Mixture Zone Zone
Figure 9.3 Structure of the combustion wave.
gas-solid reactions depend on:
1. reactant particle size distribution, particle
morphology and purity;
2. initial density of a reacting mixture;
3. initial temperature and pressure of the
reacting system;
4. dilution of the reacting mixture with the
final product;
5. size of the specimen and reactor configura-
tion.
The combustion reaction is initiated locally
by supplying a short intense burst of energy
(e.g. electrical spark, laser beam, resistively
heated wire, chemical igniter etc.). A combus-
tion wave then propagates through the
unreacted material. A typical structure of the
combustion wave is shown in Figure 9.3. How-
ever, this structure might be more complicated
when melting of a product and/ or formation
of new phases take place. Combustion
characteristics include the rapid propagation
of a combustion wave (1 x 1O-4 -O.15m/s;
3.28 x 1O-4-O.49ft/s), generation of high tem-
peratures (2073-3973 K; 1800-3700 C) and the
rapid heating of the product (103-106 K/s).
Due to relatively fast cooling rates, a solid
product consisting of non-equilibrium phases
might also be formed (Borovinskaya, 1974).
Temperature
Conversion
Product(s)

THERMODYNAMICS AND
THERMOCHEMISTRY
ADIABATIC REACTION TEMPERATURE
One of the most important combustion par-
ameters characterizing a combustion process
is an adiabatic temperature rise ~Tad' This
adiabatic temperature rise is defined as a
difference between the temperatures of a
completely reacted product in the absence of
heat losses (adiabatic temperature Tad) and an
initial reactant mixture To. The energy balance
under these conditions has a form
L [H(Tad)]products - L [H(To)]reactants
= -~H(To)
The product formed in the combustion zone
can be solid, liquid or a mixture of the two.
The conditions under which these cases exist
are dictated by the following relationship:
Tad <Tm:
I
Tad
-~(To) = To Cp,solid dT
+ ~Hm + I Tad
m Cp,liquid
When Cp,solid, -~H(To) and the heat of
melting ~Hm are known, the fraction v of a
molten product can be directly estimated. In
the case when more products are formed
and/ or other phase transitions take place, a
procedure similar to that described above
has to be applied. When sublimation of the
product is significant, a term accounting for
the heat of vaporization must also be
included. However, since vaporization takes
Thermodynamics and thermochemistry 187
place over a range of temperatures, the
incorporation of its effect in the energy and
material balance is rather difficult. Fortu-
nately, for most refractory non-oxide cer-
amics synthesized in a combustion regime,
the contribution of evaporation is negligible.
The adiabatic temperature is not normally
reached under combustion conditions due
to the equilibrium in the reacting system
and heat losses to the surroundings. The
reverse reaction can be suppressed by
increasing gaseous reactant pressure. In the
case of gasless combustion, the decomposi-
tion temperature is usually very high and
the maximum combustion temperature
might be close to the adiabatic temperature.
(9.1) In some special situations which are dis-
cussed in the next section, the maximum
combustion temperature might exceed the
adiabatic temperature.
HEAT CAPACITY ESTIMATION
A major problem in estimation of the adiabatic
temperature is an availability of the heat of
(9.2)
fusion and the heat capacity at extremely
high temperatures. When such data are not
available, the heat capacity of a solid product
can be estimated from
(9.3)
Cp(T) = Cp(To)
+ Cp (Tm ) - C (T)
p 0 (T _ To) (9.5)
Tm - To
dT (9.4)
The heat capacity of a solid phase at the
melting point can be estimated from
Cp(Tm) = 29.33n J/mol. K. The heat capacity
of a liquid phase at elevated temperatures
can be assumed constant and equal to
33.52n J / mol K, where n is the number of
atoms in a molecule (Novikov, Borovinskaya
and Merzhanov, 1975). The values of the
heat capacity, heat of reaction, melting
temperature and estimated adiabatic tem-
perature rise of selected carbides, borides,
silicides and nitrides are listed in Tables 9.1-
9.4.
188 Thermochemistry and kinetics

Table 9.1 Heat capacity, Cp ' melting temperature, Till' heat of formation, 1::.f H 298 and adiabatic tempera-
ture rise, 1::.Tad' for selected carbides

Compound C p = a + blO- 3 T + c105 r 2 (I Imol. K) Temperature Tm -1::.f H z98 1::.Tad

interval (K) (klima/) (K)
a b -c (K)

B4C 96.190 22.594 44.852 298-1200 2620 39.0 702

TiC 49.497 3.347 14.979 298-3210 3210 183.1 2912 a
ZrC 47.430 9.234 10.920 298-3690 3690 196.1 3102
HfC 47.447 5.439 13.021 298-3900 3900 230.1 3602a
VC 38.409 13.807 8.159 298-1620 2970 121.3 2102
Nb 2C 66.442 12.552 8.577 298-1890 3360 195.0 2302
NbC 45.145 7.222 8.996 298-1840 3750 140.6 2502
Ta2C 66.442 13.933 8.577 298-3770 3770 197.5 2302
TaC 43.292 11.339 8.786 298-4270 4270 144.7 2402
SiC 41.714 7.615 15.230 298-3100 3100 72.5 1502
Mo 2C 66.609 11.799 15.648 298-2690 2690 48.3 702
Mo3 C2 128.240 21.506 28.075 298-2920 2920 58.6 502
W 2C 89.747 10.878 14.560 298-3070 3070 46.0 502
WC 51.338 8.619 11.213 298-3060 3060 35.1 702

a The liquid phase fractions (v) formed during the combustion synthesis of TiC and HfC are 0.33 and 0.28, respectively.

Table 9.2 Heat capacity, Cp ' melting temperature, T m' heat of formation, 1::.f H 298 and adiabatic tempera-
ture rise, 1::.Tad, for selected borides

Compound Cp = a + blO- 3 T + c105 r 2 (llmolK) Temperature Tm -1::.f H z98 1::.Tad

interval (K) (kllmol) (K)
a b -c (K)

TiB2 62.718 15.606 20.836 298-3190 3190 278.2 2892

104.600 >3190
ZrB2 62.300 23.012 17.489 298-3310 3310 321.8 3012
HfB2 73.764 7.824 23.012 298-3520 3520 334.7 3222
NbB 2 54.392 29.079 13.305 298-1200 3270 175.3 2102
66.860 17.908 1200-3270
TaB 2 59.455 18.828 15.062 298-3370 3370 209.2 2402
CrB2 32.677 6.360 298-1070 2470 125.5 2172
Mo2B 77.111 5.314 298-1000 2540 94.6 1202
MoB 16.066 36.652 298-1000 2820 68.2 1502
MoB 2 38.493 48.869 298-1000 2520 96.2 1202
W 2B 59.706 22.259 298-1000 3040 87.0 1102
WB 43.388 9.372 298-1000 3070 71.1 1002
W2 BS 115.311 50.710 298-1000 2640 146.4 1402
FeB 48.367 7.740 7.573 298-1810 1920 71.1 1402
 Thermodynamics and thermochemistry 189
Table 9.3 Heat capacity, Cp ' melting temperature, Tm' heat of formation, t:. f H 298 and adiabatic tempera-
ture rise, t:.Tad, for selected silicides

Compound Cp = a + blO- 3 T + c105 r 2 (J /mol. K) Temperature Tm -t:.f H 298 t:.Tad

interval (K) (kJlmo/) (K)
a b -c (K)

TisSi3 243.592 24.016 110.709 298-1200 2390 580.3 2202

TiSi 64.559 34.853 298-1350 2190 132.6 1702
TiSi 2 62.509 34.811 19.037 298-1180 1770 135.1 1502
-24.142 75.647 -167.360 1200-1700
NbSi2 2.301 48.451 -135.478 298-2100 2420 125.5 1602
TaSi2 22.845 37.321 -93.052 298-2100 2470 115.9 1502
Cr3Si 94.642 36.819 22.217 298-873 141.0 1202
CrSSi3 247.458 26.861 97.278 298-873 324.7 1402
CrSi2 59.831 44.058 174.724 298-873 119.7 1502
Mo3Si 98.324 20.962 15.983 298-1200 2920 98.3 902
-5.213 74.057 -189.410 1200-2200
MosSi 3 214.221 25.941 14.309 298-1200 2370 283.7 1302
202.966 27.104 73.597 1200-2200
MoSi2 67.488 15.523 7.406 298-1200 2300 131.4 1602
26.347 36.213 -74.643 1200-2200
W S Si3 111.587 75.843 -144.306 1200-2200 2590 194.6 902
WSi2 34.275 36.828 -58.618 1200-2200 2420 93.0 1202

COMBUSTION NITRIDATION Values of P Nz for selected nitrides as a func-

The high values of ~Tad must be considered as
the theoretical upper limits, not only because
of heat losses but also due to the general
tendency of the nitrides to dissociate into
elements at high temperatures. Once formed,
the nitride phase remains stable only if the
prevailing nitrogen pressure exceeds the
dissociation pressure of the nitrides. Thermo-
dynamic analysis provides information on the
minimum nitrogen pressure required to form
the nitride phase, and thus gives a lower limit
for the required nitrogen pressure under
which the nitride is stable. For the reaction
between a metal, M, and nitrogen, i.e.
M(solid) + !N2 (gas) ~ MN(solid)
the minimum nitrogen pressure, P N2 , for the
spontaneous formation of the phase MN is
(Munir and Holt, 1987)
(9.6)
tion of temperature are shown in Figure 9.4.
As can be seen from this figure, even at
relatively high temperatures (e.g. 2000 K;
1727 C), these nitrides can be formed at
a nitrogen pressure of 0.1 MPa (1 atm).
However, higher nitrogen pressures are
required to make the nitridation reaction
self-sustaining. In order to reach the adiabatic
temperature in nitrogen metal combustion
processes, very high nitrogen pressures have
to be applied. Munir and Holt (1987) cal-
culated P N2 of 0.1, 10 and 104 MPa (,...",1,
100 and 105 atm) for AIN, BN and Si3 N 4 ,
respectively.
During the combustion process of titanium
in nitrogen, different phases are formed and
reaction conditions strongly affect the final
product composition. The phase diagram
for titanium-nitrogen shown in Figure 9.5
indicates that both a- and j3-solid solutions
of nitrogen in titanium might be formed
during the initial stage of the nitridation
process. The titanium nitride phase is
190 Thermochemistry and kinetics

Table 9.4 Heat capacity, Cp ' melting temperature, Till' heat of formation, llfH 298 and adiabatic tempera-
ture rise, llTad , for selected nitrides

Compound Cp = a + blO- 3 T +c105 r 2 (J/molK) Temperature Tm -llfH298 llTad

interval (K) (kJ/mol) (K)
a b -c (K)

TiN 49.831 3.933 12.385 298-3220 3220 334.4 4602

66.944 2:3220
ZrN 46.442 7.029 7.196 298-3250 3250 365.8 4602
66.944 2:3250
HfN 45.756 9.318 6.694 298-3580 3580 369.2 4802
66.944 2:3580
VN 45.773 8.786 9.247 298-1600 2320 251.0 3202
Nb 2N 62.383 17.113 298-1000 2670 253.1 2372 a
70.743 8.753 1000-2670
NbN 44.936 8.284 600-1640 2740 236.4 3202
62.760 1640-6000
Ta2N 70.500 17.615 7.071 298-3000 3000 270.3 2702 a
TaN 32.342 32.635 298-1000 3360 250.8 3062a
64.978 1000-3660
Si3N 4 134.198 20.041 9.665 298-4000 2170 745.8 4002 b
BN 15.230 30.292 298-1200 3270 248.3 3402b
43.597 5.188 1200-3270
AIN 22.886 32.635 298-900 2500 318.4 2602c
Be3N 77.454 43.417 18.991 298-2470 2470 581.6 2902
184.347 2450-3500

a Fraction of a liquid phase v in the combustion product: 0.61,0.08, 0.9 for Nb2N, Ta2N and TaN, respectively.
b The heat of sublimation is not accounted for.
C The heat of melting is not accounted for.

formed over a relatively wide range of
nitrogen concentrations and it is the only
stable phase formed during the combustion
of titanium in nitrogen (Deevi and Munir,
1990; Agrafiotis, Puszynski and Hlavacek,
1991). The zirconium-nitrogen system has
a similar phase diagram (Figure 9.6) to
that described above for the Ti-N system.
The tantalum-nitrogen and niobium-nitro-
gen systems are also characterized by the
existence of several phases (Figures 9.7 and
9.8).
IGNITION OF CONDENSED REACTING
SYSTEMS
Initiation of gasless or gas-solid combustion
reactions can be achieved by conductive or
radiant heat flow from an external energy
source (Price et al., 1966; Merzhanov and
Averson, 1971). During a heating-up period,
the reactant concentrations might change
and, therefore, significantly affect the nature
of the ignition process. Based on the thermal
explosion theory, the reactant consumption
can be expressed by the parameter
pCpRT;
'Y = --..!.----
CA (-6.HR )Ea
This value corresponds to the degree of
transformation when reactants are heated by
one characteristic temperature range RT; lEa-
under adiabatic conditions. The case 'Y = 0
corresponds to the model of a zero-order
reaction. When a product formed in the
 Ignition of condensed reacting systems 191
10

~
0 -5
~

<?
a..
~ -10
ZN
a..
C)
0
.....J
-15

-20

4
-25

-30
2 4 6 8 10 12 14
(1/T) .104 [K- 1]

Figure 9.4 Equilibrium dissociation pressures of nitrogen PN2 for selected nitrides; 1 = Si3 N 4 ; 2 = TiN;
3 = AlN; 4 = BN; 5 = ZrN; 6 = HfN. (Munir, Z.A. and Holt, J.B., 'The combustion synthesis of refractory
nitrides - Part I: theoretical analysis,' J. Mat. Sci., 22, 710-14, 1987. Reproduced by permission of
Chapman & Hall, London, UK.)

combustion process is solid (e.g. combustion
synthesis of ceramic materials), the ignition
process depends significantly on the value of
the parameter "I. For small values of "I, the
ignition process can be divided into the
warming-up (0 < t < to) and self-heating
(to < t < t ign ) stages. The warming-up time
to is rather small and the ignition process
has an explosive character. This type of
ignition takes place when the reactants or
products vaporize during the combustion
process. As "I increases, the explosive
character of the ignition process becomes less
distinct and, for values above "lad = 1/00 ,
where 00 is the initial dimensionless tem-
perature, the reaction proceeds only with
continuous heat supply from the external
energy source. For "I < "lad, the combustion
reaction in the heated layer has time to
proceed with a smooth self-acceleration
nearly to completion during the warming-up
period.
Ignition time can be estimated from equa-
tions of thermal ignition theory (Averson,
Barzykin and Merzhanov, 1965):
Tign = (1 - 1.605 + 0.20~)(1 + 8"1 1.505 )(1 + (3)
(9.7)
192 Thermochemistry and kinetics
Atomic Percent Nitrogen
0 10 20 30 40 50
3750

3250

2750
g
...I!!
~
:l
2250
CD
a.
E
{E. 1750

1250

750
0 5 10 15 20
Weight Percent Nitrogen

Figure 9.5 Phase diagram of the titanium-nitrogen system. (Adapted from Wriedt and Murray, 1987.)

where Usually, aluminothermic reduction of iron or

chromium oxides are used for this purpose.
f3 = RTs. However, almost any suitable non-oxide
Ea ' combustion reaction can also be used for the
.
Tign -
_ CA ( -LlHR)kotign
pCp Tsf3 exp
(_
f3
E) ignition process.

COMBUSTION FRONT STRUCTURE AND

In some special cases, the ignition of reacting
systems can be accomplished by use of a
constant temperature source or by a constant
heat flow. An excellent review of different
methods for estimation of ignition charac-
teristics was published by Merzhanov and
Averson (1971).
When very high ignition temperatures
are required, a chemical igniter may be
used instead of a resistively heated wire or
radiant energy flux. The chemical igniter is
a reacting mixture which is easily ignitable.
It generates high combustion temperatures
without excessive gas phase formation.
STABILITY ANALYSIS
Propagation of the combustion wave may be
stable or unstable depending on the kinetic
and thermophysical characteristics of the react-
ing systems. The instability of the reaction front
can be one or multidimensional depending on
the size and geometry of the combustion
system (Matkowsky and Sivaskinsky, 1978;
Merzhanov, 1981; Sivaskinsky, 1981; Dvorya-
kin, Strunina and Merzhanov, 1982; Margolis,
1985). In a cylindrical geometry, different
combustion modes have been observed, such
as planar-stable; planar-pulsating; non-planar,
 Combustion front structure and stability analysis 193
Atomic Percent Nitrogen similarity transformation can be applicable
0 10 20 30 40 50 to the temperature and concentration profiles.
However, close to the system boundaries the
3650
" , combustion wave velocity might increase or
,,/ " ,, decrease depending on boundary conditions
3250 Liq
/' , of the heat transfer (Varma, Cao and
Marbidelli, 1990).
/' " I

,,
/' I
2850 /' STABLE COMBUSTION
/
g 4
!!!
:::::I
li!CD
2450 (Liq + ZrN) -
,, The structure of the combustion wave can be
significantly more complex than that depicted
in Figure 9.3. Experiments have shown that
~ 2050 \
,, temperature profiles observed during the

,,
t! combustion synthesis of inorganic materials
(a+ ZrN) might consist of one or more elementary

1650
1250
850 ......- .......- . . - -....- . , . .....
o 3 6 9 12
Zr
Weight Percent
Figure 9.6 Phase diagram of the zirconium-
nitrogen system. (Samsonov, G.V., Handbook of the
Physicochemical Properties of the Elements, p. 368,
1968. Reproduced by permission of Plenum
Publishing Corporation, New York, NY.)
one- and multi-head spinning; and non-planar-
standing.
The model equations describing gasless and
gas-solid combustion processes are presented
by Puszynski, Degreve and Hlavacek (1987)
and Dandekar, Puszynski and Hlavacek
(1990). These partial differential equations
are stiff and therefore special regridding
techniques have to be applied to obtain a
numerical solution of acceptable accuracy
(Ivleva, Merzhanov and Shkadinsky, 1978;
Smooke and Koszykowski, 1983; Degreve
et al., 1987). In the case of a planar and
stable combustion, the propagation velocity
of a combustion wave is constant and
,,
patterns (Merzhanov, 1990). These character-
istic profiles are depicted in Figure 9.9.
ZrN~
, The temperature profile of Type I represents
a combustion wave which consists of two
zones. The combustion reaction is completed
in the reaction zone which is significantly
narrower than the preheating zone. This type
N
of profile is typical for reactions with a very
high activation energy.
Reactions with a lower activation energy
and structural limitations are characterized
by relatively wide reaction zones (Type 11).
In this case, the reaction zone consists of two
sub-zones, but only the reaction occurring in
the sub-zone, next to the preheating zone, is
responsible for making the combustion pro-
cess self-sustaining. The partially converted
material continues to react beyond the com-
bustion front interface for an extended
period of time. This type of after-burn is
prominent when reactant particles with
larger diameters are used. The experimental
temperature profile characterizing Type II
combustion is shown in Figure 9.10 (Zenin,
Merzhanov and Nersisyan, 1981). A similar
type of wide reaction zone has been observed
in the combustion of metals in nitrogen.
The Type III temperature profile is charac-
terized by the presence of an inflection point.
This type of temperature profile can be
expected when multiple combustion reactions
194 Thermochemistry and kinetics

3275

2275
g
I!?
::I
~
Ql
a.
E
t!
1275

275~----~----~--"~"--~----~----~
o 10 20 30 40 50 60
Atomic Percent of Nitrogen
Ta Ta2N TaN

Figure 9.7 Phase diagram of the tantalum-nitrogen system. (Gatterer, J., Dufek, G., Ettmayer, P. and
Kieffer, R, 'Cubic tantalum and nitride and miscibility with other transition metal nitrides and carbides,'
Monats. Chern., 106, 1137-47, 1975. Reproduced by permission of Springer-Verlag, New York, NY.)

take place simultaneously in the system. The
formation of TiC-WC solid solutions is the
best example.
The temperature profile in the combustion
zone might also be affected by phase trans-
formations and product decomposition (Type
IV). When the phase transformation takes
place in the preheating zone (e.g. the a - t f3
transformation of titanium) it has a very
small effect on the temperature profile and
overall propagation characteristics. In con-
trast, a phase transition or a product decom-
position which takes place in the reaction
zone strongly affects thermal characteristics
(Zenin, Merzhanov and Nersisyan, 1980).
Temperature profiles are commonly measured
using micro-thermocouples or more sophisti-
cated spectral methods; however, knowledge
of intermediate and product concentrations
as well as structural transformations is
essential for a complete characterization of
the combustion wave.
Aleksandrov and Korchagin (1987), with
the aim of an electron microscope equipped
with a hot stage, obtained very valuable
information on the nature of interactions
between a particle of one reactant placed on
a foil of another. They investigated such
interactions during the initial stage of gasless
reactions, namely: Ni-Al, Ti-C, Nb-C, Ta-C,
Ti-B, Ta-B and Hf-B. They concluded that,
in all cases, melting of the less refractory
reactant is the first step in the combustion
process.
No solid-solid reaction was observed in
any of these systems. It indicates that melting
 Combustion front structure and stability analysis 195
of one of the reactants is a necessary step
Atomic Percent Nitrogen to trigger the gas less combustion reaction.
o 10 20 30 40 50 An analysis of intermediate and product
compositions in the reaction zone is the most
2775 J Liq + N2 a + N2
challenging task and will be discussed in the
~=-~--------~--
- - - - ----------
2275
,
......
t-----~---
:11f,',
next section.
The combustion wave velocity u can be
I I Nb2N+N21 I approximated using the basic equation of
g I I f I
!!! 1775 a+Nb 2N I 1 !CUb I classical combustion theory (Merzhanov,
:::l I I NbNI 1981):
~ II ~

(-Ea)()
Q)
I I f I
~ 1275
RT~) ko
r::
Ih
f ex. 1
1 I 2 ( k
~
1 1 I NbN1 u = (-~HR)P F(Xc) exp RTc 9.8
1 I I
775
Nb2N-+ :
where k is thermal conductivity, ko is a
I I reaction rate constant and
275~------~------~------~
o 5 10 15
Weight Percent Nitrogen

Figure 9.8 Phase diagram of the niobium-nitrogen

system. (Samsonov, G.V., Handbook of the Physico- f(X) is a function which represents a
chemical Properties of the Elements, p. 369, 1968. concentration dependence in the reaction
Reproduced by permission of Plenum Publishing rate expression (Table 9.5). The maximum
Corporation, New York, NY.) combustion temperature Tc in the presence

T. T.

Type I Narrow Zones Type II Wide Zones

Type III Chemical Stages Type IV Phase Transition

Figure 9.9 Elementary temperature profiles of combustion waves. (Merzhanov, A.G., 'Self-propagating
high-temperature synthesis: twenty years of search and findings,' in Combustion and Plasma Synthesis of
High Temperature Materials (eds Z.A. Munir and J.B. Holt), pp. 1-53, 1990. Reproduced by permission
of VCH Verlagsgesellschaft mbH, Weinheim, Germany.)
196 Thermochemistry and kinetics
Types II-IV combustion modes differ con-

1
siderably from Type I in which an estimation
1775
11
Formation of
of the maximum temperature is straight-
forward. The conversion Xc in the reaction
1475

\
g Final Product zone is usually assumed to be equal to one.
Ti 5Si 3
The maximum temperature and conversion,
....~ 1175 Melting of
Intermediate when Type II combustion takes place, can be
!!!
Q)
Co 875 Product Ti-Si calculated from the following expressions
E Intermediate (Merzhanov, 1990):
~ Product Formation
575
Ti-Si System
(9.10)
275
0 2 4 6 8 10
X (m) x 10.3 and
Figure 9.10 Temperature profile of combustion Cp(Tc - To)
Xc = -LlHR (9.11)
wave during the synthesis of titanium silicide.
(Zenin, AA, Merzhanov, AG. and Nersisyan,
G.A, 'Structure of a heat wave in some SHS In the case of Type III combustion, the
processes,' Dok/. Akad. Nauk SSSR, 250(4), 880-84, maximum temperature and conversion are
1980. Reproduced with permission of Plenum calculated as in the case of Type I combustion.
Publishing Corporation, New York, NY) However, the values of the heat of reactions
and the heat capacity should correspond to
of heat losses can be estimated from (Pus- the first stage of the chemical reaction only.
zynski, Degreve and Hlavacek, 1987) When Type IV of combustion takes place,
the maximum temperature and conversion
are estimated from
T - T = Tad - To (9.9)
c 0 h 0.5

( 1 + 16k ) (9.12)
(dpCpu?

The simultaneous solution of equations 9.8 When significant heat losses are present, the
and 9.9 yields velocity u and the maximum combustion wave might extinguish. The mini-
combustion temperature TO' for a given value mum combustion front velocity, which can be
of the heat transfer coefficient h. observed under non-adiabatic conditions or in

Table 9.5 Forms of f(X) and F(Xc) for various kinetic expressions

Kinetic expression f(X) F(XJ

Zero-order reaction 1 lX2

2 c
First-order reaction I-X Xc + (1 - Xc) In(1 - Xc)
Second-order reaction (1 - X)2 -Xc -In(1 - Xc)
Parabolic law of oxidation X-I lx 3
6 c
Power law of oxidation X- m Xc + 2/(m + 1)(m + 2)
m
Exponential law of oxidation e-"x cr- 2(e"x, - crXc -1)

Source: Merzhanov, A.G., 'SHS process: combustion theory and practice,' Archivum
Combustionis, 1, 23-48, 1981. Reproduced by permission of Polish Scientific
Publishers Ltd, Warsaw, Poland.
 Combustion front structure and stability analysis 197
the presence of other diffusion barriers was characteristics of different gasless combustion
derived by Zeldovich (1963): systems. They found that changes in the
U min -- u ad e- O.S
mode of combustion can be related to
(9.13)
changes in the quantity of an inert diluent
where Uad is the velocity of the combustion in the initial reactant mixture, particle size
wave under adiabatic conditions and Umin is of the reactants, initial density of the speci-
the velocity at which the combustion process men, and initial temperature.
is going to be extinguished. A development of oscillatory patterns in
gasless reacting systems was first examined
numerically by Shkadinsky, Khaikin and
UNSTABLE COMBUSTION
Merzhanov (1971). These authors described
The stability of planar fronts has been studied the gasless combustion employing a nonlinear
analytically (Maksimov and Shkadinsky, 1971; reaction diffusion model of the first order.
Matkowsky and Sivaskinsky, 1978; Margolis, They found that the neutral stability criterion
1985), as well as numerically (Shkadinsky, is given by
Khaikin and Merzhanov, 1971; Bayliss and
Matkowsky, 1987; Dimitriou, Puszynski and a = RTad ( 9. 1Tad _
Ea Tad - To
2.5) (9.14)
Hlavacek, 1989). The phenomenon of an oscil-
latory combustion is caused by unbalanced For a > 1, the front propagates at constant
heat generation and heat conduction fluxes velocity (stable combustion), whereas for a <
in the reaction and preheating zones, respec- 1 the combustion proceeds in the oscillatory
tively. In the stable combustion mode, the regime.
rates of heat generation and heat removal Matkowsky and Sivashinsky (1978) per-
from the reaction zone are equal to each formed stability analysis based on an asympto-
other. However, in the oscillatory combustion tic activation energy principle. Their criterion
mode, the rate of the heat generation might for the stability parameter is
become higher than the rate of the heat
removal and the combustion wave velocity a = ~(T
2RT2 a
d - To) (9.15)
might increase for a certain period of time. ad
During that time, the width of the preheating The propagation combustion wave is stable
zone decreases, the temperature profile when a > 2+ VS.
becomes steeper and the maximum com- Margolis (1985) extended this analysis,
bustion temperature rises and in some taking to account melting effects. His criterion
cases might exceed an adiabatic temperature reads
(Shkadinsky, Khaikin and Merzhanov, 1971;
Puszynski, Degreve and Hlavacek, 1987). (9.16)
Next, the velocity decreases because the tem-
peratures in the preheating zone are very where
low. During this period, the rate of heat trans-
ferred from the reaction zone becomes faster
(steep temperature gradients) than the heat
M= (1-1+ ~Hm:(-~HR))
released by the chemical reaction. The
preheating zone becomes wider. When ther-
mal conditions for a combustion reaction
x exp [~(1-
RTc
TO)(~m
Tc
-1)] (9.17)

are reached again, the cycle is repeated. where X is a dimensionless parameter describ-
Borovinskaya et al. (1974) and Dvoryakin, ing an increase of reaction rate due to melting,
Strunina and Merzhanov (1985) reported the and the dimensionless temperature ~m is
198 Thermochemistry and kinetics
1400 1400

1200 1200

g 1000 g1000
~ ~
:::l :::l

~ 800 Puszynski
~ 800
Q) et a7. (1987) a.
Q)
a.
E E
Matkowsky & ~ 600
~ 600 :l
Sivashinsky
(1978)
400 400

200 200
0 20 40 60 80 100 0 20 40 60 80 100
Dilution ("!o) Dilution ("!o)
(a) (c)

1400 Margolis (1985) has shown that for hetero-

geneous reactions X [1 + (~Hm)/( -LVi)],
1200 so that equations 9.16 and 9.17 yield

a
Ea(Tad - To)
= """';';"''---'-'",,--=-:''':''
g 1000 2RT;d
~
:::l
Ea(Tm-Tad))]-l (9.19)
~ 800 x [1 - exp ( 2
Q)
a. RTad
E
~ 600 Munir and Sata (1992) compared different sta-
bility criteria with experimental data for ZrB2'
400 HfB2 and TiB2 syntheses from elemental pow-
ders. These results are shown in Figure 9.1l.
Oscillation patterns become increasingly
200
0 20 40 60 80 100 complex far from the oscillatory limit, and
Dilution ("!o) relaxation oscillations are replaced by har-
(b) monic oscillations. The numerically predicted
oscillations were verified experimentally by
Figure 9.11 SHS diagrams: (a) ZrB 2 ; (b) HfB 2 ; (c) Shkiro, Nerysiyan and Borovinskaya (1978),
TiB 2 . (Munir, Z.A. and Sata, N., 'SHS diagrams: who studied the structure of oscillations in
theoretical analysis and experimental observa- the tantalum-carbon system. Aldushin et al.
tions,' Int. J. of Self-Propagating High-Temperature (1973) have shown that the oscillation patterns
Synthesis, 1(3), 355-65, 1992. Reproduced with
might change from single to double period
permission of Allerton Press, Inc., New York, NY.)
oscillations away from the stability limit.
A bifurcation analysis of this phenomenon
given by and detailed numerical studies have been
presented (Bayliss and Matkowsky, 1987;
(9.18) Dimitriou, Puszynski and Hlavacek, 1989). It
was found that the general trend in the

evolution of the multiple period oscillations
leads eventually to chaos through the period
doubling. The stability loss is usually accom-
panied by a non-planar character of the
combustion front propagation.
Maksimov et al. (1979, 1981) observed a spin
regime during combustion of a titanium and
aluminum mixture at low pressures. In these
experiments, the reaction front propagated in
a spiral way. These authors presented a sys-
tematic experimental study of the transition
from stable to planar pulsation and finally to
spin combustion for the titanium-boron
system. The number of the spinning hot
spots depends on the size of the specimen
(Ivleva, Merzhanov and Shkadinsky, 1980;
Puszynski et al., 1988).
Margolis (1985), by applying nonlinear
perturbation analysis, has shown that various
types of combustion modes bifurcate super-
critically from the uniformly propagating
front. One type corresponds to a propagating
pulsating reaction with waves traveling in
both clockwise and counter-clockwise direc-
tions along its front. The former type of
solution corresponds to the spinning propaga-
tion. The traveling wave solutions describing
spinning propagation are shown to be stable,
whereas the standing wave solutions are
unstable. Similar nonlinear analysis of spin
combustion regimes was performed by
Vol' pert, Vol' pert and Merzhanov (1982). The
unstable combustion process is undesirable
because it influences the product composition
and its microstructure. However, in order to
eliminate these effects, an understanding of
the combustion phenomena and propagation
characteristics is essential for design of the
combustion reactor.
GASLESS COMBUSTION
MACROKINETICS AND STRUCTURAL
CHANGES
The diagnostics of a combustion process are
of great importance for understanding the
Gasiess combustion 199
interactions of reactants and intermediate
products in the reaction zone. The product
formation of a specific morphology and com-
position can be accomplished when such
information is available. Usually the kinetics
of chemical reactions are studied under iso-
thermal conditions. However, in the case of
strongly exothermic reactions, a significant
self-heating of reactants takes place, so the
evaluation of kinetic constants using iso-
thermal techniques is inadequate. A hetero-
geneous character of gasless combustion
processes, structural changes, melting, forma-
tion of metastable phases and intermediate
products, nucleation and recrystallization of
the combustion product at very high tem-
peratures make this evaluation even more
difficult.
By quenching the combustion system in
liquid argon, analysis of intermediate and
product cqmpositions in the reaction zone
can be accomplished. This technique does
not provide any information on intermediate
steps of the combustion synthesis.
Aleksandrov and Korchagin (1987); Kor-
chagin and Aleksandrov (1981) and Holt et al.
(1990) applied an intense source of synchrotron
radiation (1010 photons/s) and a position-
sensitive photodiode array detector to obtain
time-resolved x-ray diffraction (TRXRD) pat-
terns. The typical scanning time was 20 ms.
This novel experimental approach has allowed
the in-situ analysis of chemical reactions and
phase transformations which occur in the
reaction zone.
Holt et al. (1990) have shown that titanium
carbide formation is preceded by the melting
of titanium. This melting process takes place
within 200 ms (Ti (101) peak disappears) and
during that time titanium carbide is formed
(TiC (200) diffraction peak appears). Within
the next 0.4 s the TiC peaks grow until the
TiC phase is completely formed. Next, the
TiC (200) peak position shifts toward larger
2() angles. Based on these experimental results,
the authors concluded that the first step in the
combustion process is the melting of titanium
200 Thermochemistry and kinetics
particles. Subsequently, the molten titanium
reacts with the solid carbon particles.
Aleksandrov and Korchagin (1987) sug-
gested that the formation of TiC is limited by
the dissolution and precipitation processes
rather than diffusion through a growing tiC
layer. Their model assumes that the carbon
dissolves in the molten titanium and then
precipitates-out and grows. The total reaction
time for the complete formation of TiC is less
than 0.5 s. The TRXRD patterns have shown
no evidence of intermediate phase formation
in this system.
The synthesis of nickel aluminide (NiAl) is
far more complex. The reaction between Ni
and Al begins at about 1573 K (1300C).
Within 0.3 s, the nickel melts. However,
several small and sharp peaks which belong
to the Ni-phase can still be observed. After
the nickel melts, there is a period of nearly
8 s before an unidentified intermediate phase
is formed. This phase then disappears and
three other intermediate phases are formed
before the peak corresponding to Ni-AI
phase appears (",30 s after the combustion
wave passed). It should be noted that none
of the intermediate phases were identified as
an equilibrium phase present in the Ni-AI
phase diagram.
This very promising TRXRD technique is
still under development. However, once
correlated with combustion wave velocity
and temperature profile measurements, it
should be the most powerful tool for evalua-
tion of intrinsic kinetic data in gasless and
gas-solid combustion systems.
The mechanism of gasless combustion reac-
tions which involve two or more reactants is
very complex. For many years the reaction
rate expression has been presented in the
form of linear, parabolic or exponential laws
(Merzhanov, 1981). These kinetic expressions
have a formal character and do not take into
account the effect of the reactant particle size
and its morphology.
A number of various reaction kinetic
models for solid-solid reactions have been
proposed in the chemical engineering litera-
ture (Szekely, Evans and Sohn, 1976; Dorais-
wamy and Sharma, 1984). A shrinking core
model is applicable to the reacting systems
with non-porous solid reactant particles. As
the reaction progresses a product shell is
formed and the second reactant has to diffuse
through this shell to the reaction interface.
Depending upon the type of layer formed,
either the diffusion through the product
layer or the surface reaction can be a control-
ling mechanism.
Hardt and Phung (1973), based on the
assumption that the reactants' geometry can
be approximated by a structure of alternating
layers of solid components, derived the
expression for the combustion front velocity
u -2KDe
-- ( )
9.20
- d2 Cp Ps
where K is a constant.
In the case where diffusion through the
product layer (formed on the spherical
particle) is the rate-controlling step, the rate
expression has the form
dX 3De CAo (1 - X)1/3
(9.21)
dt apBR~[(l - X)1/3]
where Rp is the particle radius and a is a
stoichiometric coefficient.
In many cases, the morphological structure
of the non-melting reactant and product
formed is porous. In such cases, the low-
melting reactant does not need to diffuse
through the thick layer of the product to
reach the interface. The overall rate of the
process is controlled by the diffusion through
the submicron product layer formed on the
micro grains of a porous, non-melting particle.
The model for this type of process limitation
was described by Kumar, Puszynski and
Hlavacek (1990). The rate expression for a
reaction of the type
aA(solid, liquid and/or gas) + B(solid)
----> P(solid)
 Gasless combustion 201
2.0 -r---------------------,

-
1.5
1::(.)
:J

'-'"
C)

....0
1.0

0.5 -I--------;----,----r------r-------1
2.5 3.0 3.5 4.0 4.5 5.0

Figure 9.12 Dependence of the combustion front velocity on the co~bustion tempe:ature: = Hf;- 2B;
0= Ti + 2B; .. = Zr + 2B. (Borovinskaya, I.P., Merzhanov, A.G., Novikov, ~.P. and FIlonenko, .A.K., Gas-
less combustion of mixtures of powdered transition metals with boron,' FIZ. C?or. Vzryva (PhYSICS of.C~m
bustion and Explosion), 10(1), 4-15, 1974. Reproduced by permissIon of Plenum Pubhshmg
Corporation, New York, NY.)

has the form The overall reaction rate expression is usually

dX = MAkoC AO (1 _ X)O.667 e- Ea / RT
dt aMBfJBRp
Aleksandrov and Korchagin (1987) proposed
the model which assumes that a gasless reac-
tion takes place between solid and liquid
reactants. A layer of the product is formed at
the interface with solid reactant B. The thick-
ness of this layer is assumed to be constant
because a fraction of the product formed is dis-
solved in the liquid reactant. The concentration
of the liquid reactant is continuously decreased
during the process and crystallization of fine
product grains takes place. This reaction-
crystallization process continues until all
liquid reactant is consumed. In this case, the
reaction rate expression reads
dX = ko(1- X)5/3 e- Ea / RT
dt
complicated by non-uniform shapes and sizes
(9.22)
of reactant particles. The method of taking into
account the effect of particle size distribution
is described by Sasaki (1964).
The kinetic parameters can be evaluated
from simultaneous measurements of com-
bustion wave velocity and the maximum
combustion temperature. The maximum com-
bustion temperature and combustion front
velocity can be varied by changing the initial
temperature of the reactants or by diluting the
reactant mixture with the final product. A
straight line relation is obtained for Type I
combustion by plotting In(uITJ vs liTe. The
activation energy can be calculated from
the slope of this line which is equal to Ea/2R.
Typical plots for TiB 2, ZrB2 and HfB2 are
(9.23) shown in Figure 9.12 (Borovinskaya et al.,
1974). Another method for activation energy
 202 Thermochemistry and kinetics
320 Based on experimentally measured tem-
~ 2000 T 'l' perature profiles, T(l), where I is length, the
~ 240 ~
~ 1500 x spatial distributions of the degree of reactant
e~ 1000 160 .;:;; conversion, X(l), and the rate of heat
10J E
",'

'E
evolution, <1>(1), can be calculated (Zenin,
X 0.: t!I2 500
80 ::i Merzhanov and Nersisyan, 1981). Energy
and material balances for a one-dimensional
-0.5 0.0 0.5 combustion process read
Distance (m x 10.3)
d 2T dT
(al
k dl 2 - uCPPdf + f(X) = 0 (9.25)
480
2500 f(X) dX
~
T 400 b..- (-6.HR ) = uPdf (9.26)
~ 2000
320 x
e 1500
::J
240 '7<1! The boundary conditions are:
160 '"'E
Q)

'1
c.
X 0.5
E 1000
t!I2
500
0 0
0.0 0.5 1.0
(bl Distance (m x 1O~
Figure 9.13 Temperature, conversion and reaction
rate profiles: (a) single stage combustion (Nb + 2B);
(b) two-stage combustion (Nb + B). (Zenin, AA,
Merzhanov, AG. and Nersisyan, G.A., 'Thermal
wave structure in SHS processes,' Fiz. Gor. Vzryva
(Physics of Combustion and Explosion), 7, 79-90,
1981. Reproduced by permission of Plenum
Publishing Corporation, New York, NY.)
evaluation was proposed by Zenin, Merzha-
nov and Nersisyan (1981). This technique is
very useful, especially for the two-stage com-
bustion processes (Type III).
Examples of single-stage and two-stage
profiles are shown in Figure 9.13. A direct reac-
tion between niobium and boron powders is a
single-stage process when the mixture consist-
ing of Nb + 2B is ignited. The two-stage process
takes place in the case of Nb + B combustion.
Similar types of combustion profiles have
been observed in titanium-boron and tanta-
lum-boron systems. The existence of a two-
stage combustion synthesis of borides is the
result of a consecutive reaction scheme
Me + B ....... 0.5MeB + 0.5Me ....... MeB
where Me is a transition metal.
::i T = To and X = 0 at I ....... -00 and T = Tc
80 .a-
and X = 1 at I ....... 00
After integration and substitution of k =
X(k2 - k1 ) - kJ, the following relation for
conversion X(l) is obtained:
dT
uC (T - To) - kl -
X(l) = PdT dX (9.27)
(k2 - k1 ) dX + (-6.H) ( -6.H)up
where f(X) is a function which represents the
concentration dependence in a reaction rate
expression, and kl and k2 are thermal con-
ductivities of solid reactants and product(s),
respectively.
The activation energies for the combustion
synthesis of selected transition metal borides
are listed in Table 9.6.
PHASE TRANSFORMATION AND MELTING
EFFECTS
Aleksandrov and Korchagin (1987) have
shown that the melting of one of the reactants
is a necessary step in gasless systems to trigger
the combustion reaction. The mechanism of
transition metal carbide synthesis has been
extensively studied by Vadchenko, Grigorev
(9.24) and Merzhanov (1976). The complexity of
phase diagrams, in addition to structural
changes occurring during the combustion
 Gasiess combustion 203
Table 9.6 The activation energies of selected transi-
tion metal borides Vapour + (C)
4050
Reaction Ea
(kJ/mol)
3650
Nb+2B 146.7
Ta + 2B 209.5 L
Ta + B 125.7
Zr + 2B 210.0
Hf + 2B
Ti + 2B
389.7
318.4
,
Ti + B 251.4 , I

, I TiC + (C)

,,
Source: Munir, Z.A. and Anselmi-Tamburini, U., 'Self-
propagating exothermic reactions: the synthesis of high I
temperature materials by combustion,' Mater. Sci. Rep., 3,
277-365, 1989. Reprinted with kind permission from
Elsevier Science SA, Lausanne, Switzerland. ,
I

,,
'TiC

processes, make the quantitative analysis of

such processes very difficult.
The typical phase diagram for the Ti-C
system is shown in Figure 9.14. Titanium
carbide, similar to other transition metal
carbides, exists as a homogeneous phase
over a relatively wide range of compositions.
An attempt to include complex phase trans-
formations and melting effects in modeling
studies of combustion reactions was made
by Smolyakov, Nekrasov and Maksimov
(1984). The model proposed by these authors
was primarily derived for the titanium-boron
system; however, it can be used for the
analysis of combustion wave structures in
other gasless reacting systems.
Another factor which significantly affects
the wave structure is the dynamic structural
transformation of condensed phases which
are caused by melting, sintering and a molar
volume change when reactants are conv~rted
to products. Smolyakov (1988, 1990) has
derived different mathematical models for
the overall reaction rate expression which
include individual contributions of the above
mentioned effects. Based on a numerical
solution of the governing material and
energy balances, it has been concluded that
melting and volumetric changes strongly
40 60 80
Atomic Percent Carbon
Figure 9.14 Phase diagram of the titanium-carbon
system. (Adapted from Toth, 1971.)
affect both velocity and structure of the com-
bustion wave.
Nekrasov et al. (1978) have reported that
two different modes of combustion might be
present depending on the initial particle size
of reactants: (i) diffusion and (ii) capillary
processes. In the latter mode, the combustion
process is controlled by the rate of the capil-
lary spreading of the molten metal through
particles of carbon or boron when carbides
or borides are synthesized. In the former
mode, the reaction is controlled by diffusional
processes between the reactants and/or
products. The diffusion-controlled mode is
dominant in systems with metallic particles
smaller as compared to the refractory reactant
particles. Capillary spreading is rate control-
ling in systems with coarser metallic particles.
The former takes place when particle size
204 Thermochemistry and kinetics
of the metal reactant obeys the following
relationship:
8r3
r6 _r_ (9.28)
J-LDe
where 8 is surface tension and J-L is viscosity.
According to Nekrasov et al. (1978), the
capillary spreading is dominant under the
following condition:
r6 krrJ-Lu 2 ln ( ~: -=- ~) (9.29)
It has been shown that a transition between dif-
fusion and capillary regions for the titanium-
carbon system corresponds to the approximate
size range of titanium 100 < ro < 103 J-Lm. The
existence of these combustion modes has
been verified experimentally for the syntheses
of TiC and TiB2 phases (Kirdyashkin,
Maksimov and Merzhanov, 1981). The effect
of metal particle size on the combustion front
velocity for both reacting systems is shown in
Figure 9.15.
The initial specimen porosity and pre-
treatment of solid reactants (degasification,
intimate mixing etc.) also have a significant
effect on the capillary spreading. Nekrasov
et al. (1978) have shown that the maximum
benefit from spreading is attained when the
molten phase fills the voids of the porous
specimen completely. Thus, the optimum den-
sity of the sample is one in which the volume
fraction of the pores is approximately equal to
the volume fraction of the molten metal.
Lower metal volume fractions lead to the par-
tial filling of the pores and, hence, they reduce
contact between reactants. Conversely, higher
metal volume fractions lead to the formation
of excess liquid, beyond what is necessary to
fill the pores. The excess liquid will act as a
heatsink, much like an added diluent, and,
thus, lower the combustion temperature. In
both cases, the intensity of the reaction is
diminished leading to a decrease in the com-
bustion temperature and combustion wave
velocity (Munir and Anselmi-Tamburini,
1989). The dependence of the combustion
24,--------------,
18
18
12
'l' '"o
o
><
6
6
o
o-J---=-~::;~~~
0.0 0.5 1.0 1.5 2.0
Figure 9.15 Dependence of the combustion front
velocity u on the particle size r: --- = Ti + 2B sys-
tem; - = Ti + C system. Initial temperatures: (e,
'V) Tin = 293 K (20 C); (0, 0) Tin = 473 K (200 C);
(0) Tin = 673 K (400 C). (Kirdyashkin, A.L, Maksi-
mov, Yu.M. and Merzhanov, A.G., 'Effect of capil-
lary spreading on gasless combustions,' Fiz. Gor.
Vzryva (Physics of Combustion and Explosion),
17(6), 10-15, 1981. Reproduced by permission
of Plenum Publishing Corporation, New York, NY.)
wave velocity on the initial specimen density
for the titanium-boron system is shown in
Figure 9.16.
Merzhanov et al. (1990) have published an
excellent paper on macrokinetics of structural
transformations during the gas less combus-
tion of a titanium and carbon mixture.
These authors have analyzed the temperature
profiles and phase transformation in the
combustion and cooling zones. The initial
thickness of the molten layer is substantially
smaller than the diameter of the titanium par-
ticles and the ignition temperature is very
close to the eutectic temperature of 1920 K

6 15
~o
5 11
4 7
'"b
)(
;::0- 3 3
'11)
E E
:r 2 -1
-5
+---.--.--,...--.----;r--t--9
0.3 0.4 0.5 0.6 0.7 0.8
Prel
Figure 9.16 Dependence of the combustion front
velocity on the relative density of Ti + 2B mixture.
Effect of titanium particle size, ro: (1 p,m boron
particle) A = 20 p,m, <> = 20 p,m (average boron
particle size, dp = 1 p,m), = 300 p,m, 0 = 820 p,m,
t-,. = 1150 p,m, 0 = 1650 p,m. (Kirdyashkin, A.I.,
Maksimov, Yu.M. and Merzhanov, A.G., 'Effect of
capillary spreading on gasless combustions,'
Fiz. Gor. Vzryva (Physics of Combustion and
Explosion), 17(6), 10-15, 1981. Reproduced by
permission of Plenum Publishing Corporation,
New York, NY.)
(1647C). The width of the reaction zone
ranges from 100 to 300/-Lm, and the combus-
tion wave velocity is approximately 0.03 m/ s
(rvO.1ft/s). The estimated spreading time of
titanium on the surface of a carbon particle
ranges from 10-3 to 10-2 s and cannot be
neglected in the overall combustion process
description. As a result of the interaction
between the carbon and the molten titanium,
a solid TiC x phase and a carbon-saturated
melt are formed. With an increasing combus-
tion temperature, the amount of carbon dis-
solved increases substantially and titanium
carbide crystals precipitate. The average size
of crystals formed in the combustion zone
ranges from 0.1 to 1 /-Lm. This grain size is
observed even though larger carbon particles
(10/-Lm) are used. These experimental results
indicate that, after the titanium melt is
saturated with carbon, further reaction is
Gasless combustion 205
limited by the diffusion of reactants through
the carbide layer, which has a dendrite type
of microstructure. Titanium carbide, formed
in the combustion zone, might have a non-
b stoichiometric composition within an indivi-
)( dual grain. The final product recrystallization
is completed in the so-called 'burn-out' zone.
'71/)
The increase of the particle size diameter is
:r governed by the solution of small TiC x
grains followed by a subsequent growth of
larger crystals. This process takes place in
the kinetic regime because the diffusion
path in the melt (1-5 s after the combustion
zone passed) significantly exceeds the charac-
teristic particle size and the width of the
interlayer between the particles in the melt.
The analysis of the morphology of the prod-
uct in the 'burn-out' zone shows that the
product consists of rounded titanium carbide
particles with an average particle size of
several microns.
A similar behavior may be expected in
various metal-carbon and metal-boron sys-
tems because of similarities in product
morphology formed during the combustion
process (Maksimov, Lepakova and Rasko-
lenko, 1988).
GASLESS COMBUSTION WITH
REDUCING STEP
The synthesis of non-oxide ceramics directly
from oxides can also be accomplished in a
self-sustaining regime when a strong reducing
metal is used. This type of combustion reac-
tion is called a thermite process (Walton and
Poulos, 1959). The thermite reactions might
be used when the cost of the elemental
powders is very high (Ta, Hf, B etc.) or when
the direct elemental reaction does not generate
a sufficient amount of heat to be self-sustain-
ing (B4 C, SiC, WC). Borides, carbides, silicides
and nitrides can be synthesized by taking
advantage of this technique. A metal oxide is
formed as a by-product of this reaction. This
oxide has to be later chemically leached in
order to obtain high purity powders. There
206 Thermochemistry and kinetics
exist a limited number of inexpensive redu-
cing agents. Magnesium and aluminum are
prime candidates; however, the former is
more desirable because the resulting magne-
sium oxide by-product is easily leachable
with hydrochloric acid. When aluminum
metal is used as a reducing agent, a very
stable a-aluminum oxide is formed which
cannot be easily separated from the reduction
product. In such cases, alumina-based com-
posites (Al20 r TiC, A120 3- TiB2, Al20 r MoSi2
etc.) can be directly used as a valuable ceramic
material.
The chemical scheme of the Mg-thermite
reaction can be written
AmOn + BpOr + (n + r)Mg
-+ AmBp + (n + r)MgO (9.30)
Magnesium oxide formed during the combus-
tion process is uniformly distributed among
very fine grains of the combustion product
(Merzhanov,1990).
Rigtrup and Cutler (1989) have studied
the synthesis of SiC by the reduction of silica
with magnesium in the presence of carbon.
They have postulated the following reaction
mechanism:
Si02 + Mg -+ SiO + MgO (9.31)
SiO + 2C -+ SiC + CO (9.32)
Mg + CO -+ MgO + C (9.33)
The ignition temperature of this reduction
process is affected by the size of the Mg reac-
tant particles. The reactant mixture, with
magnesium powder of average size less than
45/-Lm, ignites at 823-863 K (550-590C), but,
when coarser magnesium powder (110-
180/-Lm) is used, the ignition process takes
place at 933-953 K (660-680C). Since the
vapor pressure of magnesium is high (100 Pa
(0.75 torr) at 853 K (580C, it is not surprising
that the reduction process can be initiated
below the melting point of magnesium.
Carbon stoichiometry and morphology
also affect the ignition process. Combustion
temperatures in excess of 2873 K (2600 C)
are generated when stoichiometric mixtures
are ignited; however, they can be reduced by
diluting the starting reactant mixture with the
end product (Rigtrup and Cutler, 1989).
The addition of the inert material is
required to moderate the relatively violent
character of this process. The calculated
adiabatic temperature decreases from 3078 K
to 2178 K (2805-1905 C) as the amount of
MgO filler increased from 0-70wt%. The
reaction ignition temperature increased from
860-899 K (587-626C) as the filler content
increased from 0-60 wt% (Cutler, 1990).
It has been shown that the particle size and
morphology of SiC powder formed during the
magnesium thermal reduction of Si02 in the
presence of carbon are controlled by the size
of the carbon reactant. In Figure 9.17, the
specific surface area of submicron SiC
powder, after leaching with hydrochloric
acid, is shown to be a function of the specific
surface area of the carbon reactant.
Thermodynamic analysis is very important,
especially in the case of multicomponent
systems, where the combustion product
150,---------------------------,
)(
f 100
Ci
()
i:i5
'0
~ 50
CD
~:;,
en
o;-------.-------.-------.-~
o 200 400 600
Surface Area of Carbon Reactant (riflkg) x 103
Figure 9.17 Surface area SiC synthesized by mag-
nesium thermal reduction of Si02 in the presence
of carbon. (Adapted from Cutler, 1990.)

B:P3
Optimal Composition Region
Mg
Mg
Figure 9.18 Equilibrium ternary diagram for the
Ti02-B 2 0 3-Mg system. (Merzhanov, A.G., 'Self-
propagating high-temperature synthesis: twenty
years of search and findings: in Combustion and
Plasma Synthesis of High Temperature Materials (eds
Z.A. Munir and J.B. Holt, pp. 1-53, 1990. Repro-
duced by permission of VCH Verlagsgesellschaft
mbH, Weinheim, Germany.)
composition is not apparent because of com-
peting side reactions and phase transforma-
tions. For the Ti02-B20 r Mg system, besides
TiB2 and MgO, other phases like magnesium
boride, unreacted titanium, boron, boric oxide
and magnesium may be present. The opti-
mum conditions, where only a single boride
phase (TiB 2) is formed, have been presented
by Merzhanov (1990) and are shown in
Figure 9.18.
THERMAL EXPLOSION AND CHEMICAL
OVENS
In general, any strongly exothermic reaction
with high activation energy might proceed in
two different regimes: low temperature or
high temperature. In Figure 9.19, different
thermal operational modes are shown. Curve
1 describes the temperatures generated by the
chemical reaction under adiabatic conditions
and curves 2, 3 and 4 represent the heat trans-
fer characteristics (conduction flux) inside the
specimen.
When the initial temperature of reactants is
low, the chemical reaction takes place in the
low temperature regime (point I) under
almost isothermal conditions. In this case,
Gasless combustion 207
Figure 9.19 Combustion modes: I-V steady-state
solutions; 1 = heat release by a chemical reaction,
2-4 = heat removal by convection, radiation and
conduction.
the rate of reaction is very slow, and long
reaction times are required in order to reach
a high degree of conversion. The chemical
process cannot be self-sustaining even if very
high ignition temperatures are applied.
However, when the initial temperature of
a reactant mixture Tin is high enough, the
reactants are ignited spontaneously without
any additional external energy pulse. This
thermal explosion region is characterized by
very high temperatures generated in the
specimen at the same time (point V).
In the intermediate region of initial tem-
peratures for which both low and high
temperature regimes can coexist (points II
and IV), the reactant mixture is normally
characterized by point II. However, when an
external energy flux is delivered locally to
this system, the ignition process takes place
(point IV) and a high temperature combustion
wave is formed which propagates through the
reactant mixture. The principles of this pro-
cess have been described previously.
In many cases, it is difficult to ignite solid
reactants. The use of high power heat fluxes,
which can be supplied by a laser beam, makes
208 Thermochemistry and kinetics
it possible to achieve very high temperatures.
However, the use of a high energy flux is
undesirable because it is accompanied by
sublimation and/ or particle ejection from the
heated surface. It was observed that a
chemical reaction extinguished after the high
intensity radiation source was removed
(Baklan et al., 1986).
Ignition of reacting systems, characterized
by a high activation energy and a relatively
low heat of reaction (e.g. WC, SiC, B4 C, WB2 )
is very difficult, and in many cases cannot be
achieved without significant preheating of the
reactant mixture. In order to eliminate the use
of resistively heated or induction furnaces,
the reacting system with low exothermicity
can be preheated by another reacting system.
The heat generated by the strongly exothermic
reaction (e.g. Ti and C, or B2 0 3 , C and Mg etc.)
is transferred to the reacting system with the
low heat of reaction. Then, after the required
preheating temperature is achieved, the
reaction is completed in a self-propagating
or thermal explosion regime. The products of
both reactions must eventually be separated.
However, when a proper reactor configura-
tion is used, the contamination and separation
effort can be minimized significantly.
The analysis of thermal conditions in
chemical ovens has been described by
Dimitriou, Puszynski and Hlavacek (1988).
GAS-SOLID COMBUSTION
KINETICS AND MECHANISM OF TRANSITION
METAL INTERACTIONS WITH NITROGEN
AND HYDROGEN
The direct synthesis of refractory nitrides from
elements can be carried out in two different
regimes.
Conventional methods of synthesis involve
heating of a solid reactant in a nitrogen
atmosphere below its ignition point. The rate
of chemical reaction and the diffusion of
nitrogen through the product layer are low
at these conditions. This method of nitride
synthesis is time consuming and energy
intensive (e.g. direct nitridation of silicon at
temperatures up to 1723 K (1450 C.
The direct reactions between aluminum,
silicon, transition metals and nitrogen are
strongly exothermic. When the ignition con-
ditions (temperature and nitrogen pressure)
are met, the nitridation process can be
completed in a self-sustaining regime and
the combustion temperature might exceed
2773 K (2500C). Merzhanov and Borovins-
kaya (1972) were the first to report experimen-
tal values of combustion wave velocities in
transition metal-nitrogen systems.
When a pure transition metal burns in
nitrogen or hydrogen, the heat generated
during the reaction is so high that melting of
the reacting metal or metal nitrides, and/or
product dissociation may occur (synthesis
of TiN, ZrN, transition metal hydrides).
However, several other transitions metals
(tantalum, niobium) do not melt during the
nitridation in the combustion regime. Exces-
sive melting of the solid reactant can cause a
significant decrease in the permeability of a
solid specimen. Consequently, incomplete
nitridation will result. Dilution of the metal
reactant with an inert additive (product of
the nitridation reaction) is commonly used as
an effective means to reduce the combustion
temperature and, therefore, the extent of
melting. Nitridation processes in a combus-
tion regime of titanium, tantalum, niobium
and hafnium powders were studied by Merz-
hanov and Borovinskaya (1972); Filonenko
and Vershenikov (1975); Borovinskaya and
Loryan (1978); Holt and Kingman (1984);
Hirao, Miyamoto and Koizumi (1987a);
Eslamoo-Grami and Munir (1990); and
Agrafiotis, Puszynski and Hlavacek (1991).
The combustion temperatures in these sys-
tems were significantly lower than the
corresponding adiabatic temperatures. This
indicates that only a partial conversion is
achieved in the combustion zone, and the
reaction is completed in the after-burn zone.
When pure titanium metal is ignited in

nitrogen PN2 < lOMPa (lOOatm), significant
melting takes place and low conversion of
the metal to the corresponding metal nitride
(",,27%) is reached.
There exists an intermediate optimum value
for the dilution at which the heat generated is
still sufficient to keep the process self-sustain-
ing, but melting is significantly suppressed.
When titanium powder (average particle size
<45/Lm) is diluted with titanium nitride (50-
60wt%), very high degrees of nitridation
(>95%) can be achieved. Further dilution
leads to a decrease in conversion and sub-
sequently to extinction. The effect of titanium
powder dilution with titanium nitride on total
conversion is shown in Figure 9.20. In the case
where tantalum reacts with nitrogen, no
melting takes place over the whole range of
initial concentrations.
Gas-solid combustion 209
There exists a wide range of nitrogen pres-
sures and solid phase dilutions for which
both the titanium-nitrogen and tantalum-
nitrogen systems exhibit a steady-state
propagation. At low pressure, the velocity of
propagation increases almost linearly with
increasing pressure, but at high pressures,
PN2 > 3-4 MPa (30-40 atm) it becomes almost
independent of pressure. This type of behavior
is shown in Figures 9.21 and 9.22 for titanium-
nitrogen and tantalum-nitrogen systems,
respectively. As seen from these figures, the
propagation velocity depends strongly on the
solid phase dilution. At a specific value of gas
pressure, progressive dilution decreases the
speed of propagation and the combustion tem-
perature, and eventually leads to extinction.
The analysis of the effect of metal par-
ticle size on combustion wave propagation

100

90

--
80
;It.
c 70
0
'!
~ 60
c
0
(.)

!
50

40

30 ~ P= 1 MPa
/:::" P=4MPa
20
0 20 40 60 80
Solid Phase Dilution (wt %)

Figure 9.20 Effect of solid phase dilution and nitrogen pressure on conversion of titanium nitride in a
combustion regime; average particle size of titanium, dp = 29 {tm. (Agrafiotis, c., Puszynski, J.A. and
Hlavacek, V., 'Experimental study on the synthesis of titanium and tantalum nitride in the self-propagating
regime,' Comb. Sci. Technol., 76, 187-218, 1991. Reproduced by permission of Gordon and Breach
Publishers, Lausanne, Switzerland.)
210 Thermochemistry and kinetics

1.50 ....- - - - - - - - - - - - - - - . . ,

1.25

'1'
o
>< 1.00

I
~ 0.75
8 50%
J 0
'E 0.50
~
60%
0.25
'Y 65% 'Y
"i1 "i1
0.00-+----;,---,---,.---....,--...-----1
0.0 1.5 3.0 4.5 6.0 7.5 9.0
Pressure (MPa)

Figure 9.21 Effect of nitrogen pressure and dilution of the initial reactant mixture on the combustion front
velocity; average particle size of titanium, dp = 29 p,m (titanium-nitrogen system). (Agrafiotis, c.,
Puszynski, J.A. and Hlavacek, V., 'Experimental study on the synthesis of titanium and tantalum nitride
in the self-propagating regime,' Comb. Sci. Technol., 76, 187-219, 1991. Reproduced by permission of
Gordon and Breach Publishers, Lausanne, Switzerland.)

characteristics has shown that the combustion
wave velocity decreases with increasing tita-
nium particle size. However, for a tantalum-
nitrogen system, it is independent over a
wide range of tantalum particle sizes (8.5-
200 j.Lm) (Agrafiotis, Puszynski and Hlavacek,
1991).
This unexpected behavior can be
explained by a porous microstructure of tan-
talum particles which retain their shape after
the nitridation process is completed. SEM
photographs of tantalum and tantalum
nitride powders are shown in Figure 9.23.
When tantalum powder is nitrided at low
nitrogen pressures, the f3-Ta2N phase is
mainly formed. At moderate nitrogen pres-
sures (0.5--4.0 MPa (5-40 atm, hexagonal
phase c-TaN is present. However, when
high nitrogen pressures are
(PN2 > 40MPa (400 atm)) , cubic tantalum
used
nitride is formed. In Figure 9.24, different
pathways are illustrated (Borovinskaya,
1974).
The kinetic expression for nitridation of
tantalum and titanium powders in the
combustion mode have been proposed by
Agrafiotis, Puszynski and Hlavacek (1991).
The reaction model for the synthesis of tanta-
lum nitride has been derived based on the
assumption that the tantalum particle is
porous and the reaction rate is determined
by the diffusion process at the micrograin
level. The activation energy for the nitridation
process of tantalum can be obtained from the
'Arrhenius-type' plot which is shown in
Figure 9.25.
The function F(Xc) is defined as
F(Xc) = JXcX-X
0 f(X) c dX (9.34)
 Gas-solid combustion 211
1.75

No Dilution

1.50

'l' 1.25
0
)(

I~
1.00

20% Dilution
'0
0 0.75
~ o
E
e
u. 0.50 30% Dilution

0.25

0.0
0 2 3 4 5 6 7 8
Pressure (MPa)

Figure 9.22 Effect of nitrogen pressure and dilution of the initial reactant mixture on the combustion front
velocity (tantalum-nitrogen system), average particle size of tantalum, dp = 85/-Lm. (Agrafiotis, c.,
Puszynski, J.A. and Hlavacek, V., 'Experimental study on the synthesis of titanium and tantalum nitride
in the self-propagating regime,' Comb. Sci. Technol., 76, 187-218, 1991. Reproduced by permission of
Gordon and Breach Publishers, Lausanne, Switzerland.)

where Xc is the degree of nitridation in the
combustion zone, and
f(X) = (1 - X)2/3
for the kinetically controlled nitridation
process
(1 - X)1/3
f(X) = 1 _ (1 _ X)1/3
for the diffusion controlled nitridation
process
The combustion technique has been suc-
cessfully applied for the synthesis of transition
metal hydrides despite their low decomposi-
tion temperatures (Agababyan et ai., 1979;
Zenin, Nersisyan and Nersisyan, 1982). It has
been shown that the combustion synthesis of
transition metal hydrides proceeds in two
stages: the first stage involves the formation
of a f3 solid solution of hydrogen in the
metal, while the second involves the forma-
tion of lhe hydride phase. Transition metal
hydrides are unstable at temperatures above
773-1273 K (500-1000 Dc). The hydride phase
is initially formed in the reaction zone; how-
ever, due to the high temperatures generated
in this process, a decomposition reaction
becomes significant. The temperature in the
after-burn zone decreases progressively and
the hydride phase is formed as the final
combustion product. Zenin, Nersisyan and
Nersisyan (1982) have proposed a reaction
mechanism for titanium and zirconium
hydride combustion reactions. The reaction
paths and the characteristic temperature pro-
files in the combustion wave for titanium and
zirconium hydride formations are shown in
Figures 9.26 and 9.27, respectively. It has
been shown that the combustion temperature
increases with increasing hydrogen pressure.
However, the final conversion to the metal
212 Thermochemistry and kinetics

(a)

(b)
Figure 9.23 SEM photographs: (a) tantalum powder, average particle size 20 {Lm; (b) combustion
synthesized TaN (bar sizes: left = 100 {Lm; right = 10 {Lm). (Agrafiotis, c., Puszynski, J.A. and Hlavacek,
V., 'Experimental study on the synthesis of titanium and tantalum nitride in the self-propagating regime:
Comb. Sci. Technol., 76, 187-218, 1991. Reproduced by permission of Gordon and Breach Publishers,
Lausanne, Switzerland.)
 Gas-solid combustion 213

Combustion of
lTantalum in Nitrogen I
r r
Low Nitrogen
Pressures
P<0.3MPa
-Very High Nitrogen
Pressures
P>200 MPa
I-

I
Moderate Nitrogen
Pressures
(0.5-5 MPa)

r
Hexagonal
Ta2N
~ I Cubic
TaN
-1 Hexagonal
TaN
I
~

I
- I
High Nitrogen
Pressures
P>10 MPa

Figure 9.24 Combustion synthesis of tantalum nitride. (Borovinskaya, L.P., 'Combustion processes and
chemical synthesis,' Archivum Combustionis, 5(2), 145-61, 1974. Reproduced by permission of Polish
Scientific Publishers Ltd, Warsaw, Poland.)

hydride remained unchanged for PH2 > nitridation of high purity silicon powder
0.1 MPa (>1 atm). with a 95mol% N 2-5mol% H2 gas mixture.
Rossetti and Denkewicz (1989) envisioned
silicon nitridation to proceed by two parallel
MECHANISM OF SILICON NITRIDATION
reaction pathways, one producing Q-Si3N4
Silicon nitride is a very promising non-oxide and the other leading to ,B-Si3N4' and repre-
ceramic material. The simplest route to the sented the kinetics by
silicon nitride powder synthesis is a direct
nitridation of silicon powder. The heat of d~" = k,,{l - X,,) (9.35)
this reaction is very high (AHR = -737.4 kJ /
mol), and the nitridation process can be dXf3 = kl>{l _ X(3)2/3 (9.36)
carried out in two regimes. One, which is dt fJ

characterized by very low reaction rates and Varma, Pigeon and Miller (1991), on the basis
almost isothermal conditions. The overall of Rahaman and Moulson's experimental data
kinetics of the nitridation in this regime are (1984) have proposed the following rate
governed by the diffusion of nitrogen through expressions:
a product layer, its chemisorption, nucleation
and finally the growth of the nitride nuclei dX" = k (I - X - XI (9.37)
dt " " fJ
(Atkinson, Moulson and Roberts, 1976;
dXf3 0.5
Ziegler, Heinrich and Wotting, 1987). Silicon dt = kf3{l - X" - X(3) (9.38)
nitride can exist in two allotropic forms: Q-
and ,B-phases. Rahaman and Moulson (1984) where the values of k" and kf3 at 1623 K
have reported kinetic data for the synthesis (1350C) were estimated to be 2.87h- 1 and
of Q- and ,B-silicon nitride phases by a slow 0.331 h- 1, respectively.
214 Thermochemistry and kinetics

-8~----~1-------r------~1------r-1-----'

-9
'.
'.'. .
' -
<>

.
~~. Reaction

.
~-. Control
~ <> -
.........
-10
'

'.~'" ..............
.
-11 -
g
u.. '."
~

-12 '.'.'..... -
~
:s -13
'.'.
'. '.
Diffusion
Control
-14 ~ -
Mean Particle Size, dp
-15 - 8,51lm
851lm
<> 200ilm
-16~------~----~------~------~~----~
3.5 4.0 4.5 5.0 5.5 6.0

Figure 9.25 'Arrhenius-type' plot for the evaluation of activation energy (tantalum-nitrogen system).
(Agrafiotis, c., Puszynski, J.A. and Hlavacek, V., 'Experimental study on the synthesis of titanium and
tantalum nitride in the self-propagating regime: Comb. Sci. Technol., 76, 187-218, 1991. Reproduced
by permission of Gordon and Breach Publishers, Lausanne, Switzerland.)

A first-order reaction for a-Si3N4 suggests
that the step involving nucleation of the
nitride is rate controlling. Similarly, in the
absence of a liquid phase, ,B-Si3N4 is formed
by the reaction of nitrogen and silicon, with
nitrogen diffusing through the solid silicon
nitride product layer (Ziegler, Heinrich and
Wotting, 1987).
Myhre and Motzfeldt (1990) have presented
a detailed kinetic study of silicon nitridation in
the temperature range 1573-1613K (1300-
1340C) at nitrogen pressures ranging from
3.3 to 26.7kPa (24.8-200 torr). The nitridation
kinetics of silicon powder (32-45/lm) have
been measured using a thermogravimetric
analyzer. The typical kinetic curves are
shown in Figures 9.28 and 9.29. The rate of
the nitridation process is markedly dependent
on the N2 pressure; higher pressure gives
higher initial rate but a lower final extent of
reaction. Also, the reaction rate is extremely
slow at relatively low conversions (9-30%).
An x-ray diffraction analysis of the product
shows that the ratio of a to ,B Si3N4 (a/,B)
increased with increasing nitrogen pressure.
The initial nitridation yields the a-phase
only, while the ,B-phase starts to appear
when the degree of conversion has reached
2-3%. The Si3N4 is initially formed on the
silicon powder surface and further nitridation
results in the formation of new crystals grow-
ing on top of those already formed.
Myhre and Motzfeldt (1990) have proposed
a kinetic model for the nitridation of silicon
below its melting point. They distinguish
several regions with different rate deter-
mining processes. As a result of their
analysis, the following kinetic equation has
 Gas-solid combustion 215
1275 ....- - -. .- - - - -. . .

,
1200 _----3
_----2
g
\
\
\
,
\ ,, !!!
~ 800
\
, ~
E
a+j3 , ~
,
\ 400
\
\
275,..,.-~r_-...- _ .....- .. -2 o 2 4
0.0 0.5 1.0 1.5 2.0 Distance (M) x 10.3
HfTi (a)
(a)

1250~-------"------"

1275 ....- - -. .- - - - -. . ~1000

~
!!!
:::J
1025 ~ 750
Q)
Q.

~
F 500

525~----------T---~
\ , -0.3 -0.2 -0.1 0.0 0.1
Distance (m) x 10.3
0.2 0.3

a+y
:1
, I

I
yHi (b)

Figure 9.27 Temperature profiles of the combus-

275 .....- - , . . . -......-~1IIIIIIII. .
0.0 0.5 1.0 1.5 2.0
HlZr
(b)
Figure 9.26 Reaction pathways for the combustion
synthesis of: (a) titanium hydride; (b) zirconium
hydride. (Zenin, A.A., Nersisyan, G.A. and Nersis-
yan, M.D., 'Mechanism and macrokinetic of tita-
nium and zirconium hydride formation by SHS:
Fiz. Gor. Vzryva (Physics of Combustion and Explo-
sion), 4, 66-73, 1982. Reproduced by permission
of Plenum Publishing Corporation, New York, NY.)
been proposed:
tion zone in: (a) Zr-H2 and (b) Ti-H2 systems.
PH,: l=lMPa (lOatm), 2=0.5MPa (5atm), 3=
0.1 MPa (1 atm). (Zenin, A.A., Nersisyan, G.A. and
Nersisyan, M.D., 'Mechanism and macrokinetic of
titanium and zirconium hydride formation by
SHS: Fiz. Gor. Vzryva (Physics of Combustion and
Explosion), 4, 66-73, 1982. Reproduced by
permission of Plenum Publishing Corporation,
New York, NY.)
where kol is a kinetic constant for linear
growth of nuclei, ko2 is a rate constant for
'branching' and koa is a constant describing
the relative rate at which product pores are

t= -
ko2
1 In [(k02)3]
X -
ko1
- - In 1 - -
koa Xf
1 ( X) (9.39)
closing. Based on the experimental results
and theoretical analysis presented by these
authors, it can be concluded that both 0:- and
216 Thermochemistry and kinetics
3.0-r------------~
q>
~ 2.5
)(
1C 2.0
~ 1.5
r::
'iii 13.33 kPa
~ 1.0 1574K
s::.
C>
~ 0.5
O.a.=----~--__r---r__---'
o 15 30 45
Time (s) x 10 3
Figure 9.28 Effect of pressure on nitridation of
silicon powder in the low temperature regime.
(Myhre, B. and Motzfeldt, K., 'Kinetics of the
nitridation of silicon,' in The Physics and Chemistry
of Carbides, Nitrides, and Borides (ed. R. Freer),
pp. 29-44, 1990. Reproduced by permission of
Kluwer Academic Publishers, Dordrecht, The
Netherlands.)
,B-Si3N4 phases are formed by the nitridation
of gaseous silicon.
Due to a very high heat of reaction,
silicon can be nitrided in a self-sustaining
regime (Holt, Kingman and Bianchini, 1985;
Mukas'yan et ai., 1986, 1990; Hirao, Miyamoto
and Koizumi, 1987b, Lis et ai., 1991a). The
silicon powder can be ignited and the nitri-
dation process can be self-sustaining only at
elevated nitrogen pressures. Hirao, Miyamoto
and Koizumi (1987b) and Lis et ai. (1991b)
have reported a minimum N2 pressure of
3 MPa (30 atm), while previously Holt, King-
man and Bianchini (1985) and Mukas'yan et ai.
(1986) needed significantly higher values, 50
and 8 MPa (",500 and 80 atm), respectively.
The second requirement for ignition and
propagation to occur is a dilution of silicon
reactant with silicon nitride powder.
The combustion temperature generated
by the direct reaction between silicon and
nitrogen at moderate pressures (3.0-10MPa;
30-100atm) is significantly lower than the
adiabatic temperature. The reason is that the
2 . 5 - r - - - - - - - - - - - - : -17617":2:-:K7 1
q> 1602 K
~ 2.0
=-_----1586 K
)(
l>5
~
1583 K
1573K
.~ 1.0
~
E
.~0.5
;:
o.o------...----~-----i
o 12 24 36
Time (s) x 103
Figure 9.29 Effect of temperature on nitridation
of silicon powder (PN2 = 0.0134 MPa; 101 torr).
(Myhre, B. and Motzfeldt, K., 'Kinetics of the
nitridation of silicon,' in The Physics and Chemistry
of Carbides, Nitrides, and Borides (ed. R. Freer),
pp. 29-44, 1990. Reproduced by permission of
Kluwer Academic Publishers, Dordrecht, The
Netherlands.}
Si3N4 tends to dissociate at high temperatures.
The combustion temperature is given by
the local equilibrium at the reaction front.
Mukas'yan et ai. (1986) have reported com-
bustion temperatures of 2200 K (1927C)
and 2400 K (2127C) at nitrogen pressures
6MPa (",60atm) and 50MPa (",500atm),
respectively.
In order to obtain high degrees of con-
version, a significant portion of silicon has to
be converted to Si3N4 in the after-burning
zone. Hirao, Miyamoto and Koizumi (1986,
1987b) reported that the combustion of small
diameter samples resulted in high o:-Si3N4
content. However, when specimens with a
larger diameter were ignited, a high content
of the ,B-Si3N4 phase was observed. The for-
mation of o:-Si3N 4 phase in the outer layer
of the specimen can be explained by heat
transfer conditions at the interface between
the solid reactant and gaseous N2 (Puszynski,
Majorowski and Hlavacek, 1990).
The mechanism of a silicon powder nitrida-
tion in a combustion regime has been studied
 Gas-solid combustion 217

3500

3000

~
In
2500
r:::
~ 2000
~ 1500
(5
In
.c
<C 1000

500
0
25 30 35 40 45 50 55 60 65
Two-Theta (Oe9.)

Figure 9.30 X-ray diffraction patterns of combustion-synthesized silicon nitride.

by Mukasyan et al. (1990). These authors, based
on the x-ray diffraction and SEM analyses of
quenched samples, have concluded that the
,8-Si3N4 phase is formed in the combustion
zone mainly by the nitridation of silicon
vapor. They have suggested that silicon is
transported to the gas phase by evaporation
and formation of silicon monoxide (SiO) gas
as a result of the reaction between initially
present silicon dioxide (Si02 ) and silicon (Si),
rather than the nitridation of liquid silicon.
These authors distinguished the following
three zones.
I. The silicon particles are solid and the
initial macrostructure of the solid phase
is unchanged.
II. This zone is characterized by higher tem-
peratures and formation of Si3N4 nuclei.
Both the reaction rate and nitrogen con-
sumption are very low.
III. In this zone, the silicon particles evaporate
and growth of ,8-Si3N4 crystals proceeds
by a vapor-liquid-crystal (VLC) mechan-
ism; silicon vapor condenses and reacts
with nitrogen at the tips of Si3N4 crystals.
The overall rate of this process is governed
by mass transfer of silicon vapor from molten
silicon to ,8-Si3N4 crystals. The purity and
microstructure of combustion synthesized
silicon nitride depend on the purity of silicon
reactant, its particle size, the initial amount
and specific surface area of the silicon nitride
used as a diluent, nitrogen gas pressure,
the reactor charge and reactor configuration.
The typical x-ray diffraction pattern, micro-
structure and physico-chemical properties of
the combustion-synthesized Si3N4 are shown
in Figures 9.30 and 9.31 and Table 9.7, respec-
tively (Lis et al., 1991a).
ANALYSIS AND MODELING OF GAS-SOLID
REACTIONS
The mathematical analysis of combustion
processes in gas-solid (liquid) systems
where a solid product is formed (synthesis of
nitrides and hydrides) is very complicated.
The combustion wave velocity, temperature
and gas pressure profiles in the preheating
and reaction zones, intraparticle gas diffusion,
structural changes due to a chemical reaction
and melting, and final conversion of reactants
to product are affected by the initial charac-
teristics of the reacting systems (initial
porosity, temperature, dilution, reactant
218 Thermochemistry and kinetics

Figure 9.31 Microstructure of combustion-synthesized silicon nitride.


Table 9.7 Physico-chemical properties of combus-
tion synthesized nitride
Property Value
Chemical
;3-Si3N 4 >95%
Oxygen <0.5wt%
Carbon <0.1 wt%
Nitrogen <38.5wt%
Aluminum <1000 ppm
Iron <600 ppm
Physical
Average particle size
Surface area
particle size distribution, gas pressure, reactor
configuration). The experimental measure-
ments might result in a correlation among
these parameters, however the complete
understanding of the interactions during the
combustion process can be accomplished by a
detailed mathematical analysis of the reacting
system.
Early pioneering studies of gas-solid com-
bustion systems were presented by Aldushin,
Merzhanov and Seplyarskii (1976,1980). Most
of these studies were analytical in nature and
helpful in defining the basic regimes of opera-
tion.
Sukhov and Yarin (1980) have performed a
two-dimensional stability analysis under
conditions of complete and incomplete
conversion, without limitations on the length
of perturbations for filtration combustion
waves. From the study, they concluded that
under conditions of complete conversion
(high pressure), the stability of the filtration
combustion wave is governed by chemical,
thermophysical and filtration properties of
the system. However, under incomplete con-
version conditions (low pressure), they found
the system to be always stable.
Dandekar et al. (1990) and Dandekar, Pus-
zynski and Hlavacek (1990) have presented
the detailed numerical analysis of the filtration
combustion using one- and two-dimensional
models. They analyzed both counter-current
Gas-solid combustion 219
and cross-flow configurations. The model
equations represent a system of coupled,
highly nonlinear, parabolic-hyperbolic, par-
tial differential equations exhibiting solutions
with steep gradients which move rapidly over
the space. These equations were solved
numerically by using an adaptive mesh
generator (Degreve et al., 1987). In the case of
counter-current filtration combustion (Figure
9.2(b at very high pressures (thousands of
atmospheres), all the solid reactants are con-
verted to product in the reaction zone (Figure
9.32). When lower pressures are applied (tens
or hundreds of atmospheres), only partial
conversion is achieved by the counter-current
propagating front. Subsequently, a new
co-current front is generated which moves
very slowly and eventually complete conver-
sion can be accomplished (Figure 9.33). In
some cases, when permeability of the solid
material is significantly changed by melting
or sintering, this secondary wave might be
extinguished.
Stability of the combustion is governed
mainly by two parameters: the activation
energy and heat of reaction. At high pressure
the relation obtained by Shkadinsky, Khaikin
and Merzhanov (1971) for solid-solid systems
serves to predict the parametric conditions
which cause unstable and stable propagating
waves. However, as the pressure decreases,
the combustion wave becomes more and
more stable. At very low pressure even the
systems which exhibit severe instability at
high pressures show stable behavior.
In the case of cross-flow configuration
depicted in Figure 9.2(d), the combustion
wave is also strongly affected by the gaseous
reactant pressure. At low pressures, the front
is often skewed traveling ahead in the upper
layers as compared to the inner layers, thus
causing incomplete conversion when severe
sintering takes place. At high pressures,
sufficient gas is available inside a solid reac-
tant structure, so that the conversion of the
solid reactant is always complete. At low
and moderate pressures, the height of a
220 Thermochemistry and kinetics

o.00
rr"""~
-1. 00

-2. 00
~
~ -3.00

g- -4.00-
CD

{E
-5.00

-6. 00 ~)/JJ) J j ) ) J ) j; .J
-7.""
vv
0.00 0.20 0.40 0.60 0.80 1.00
Axial Coordinate Axial Coordinate

1.00

~ ~~
1.00 6 ~
0.80
0.80
I:
0.60
~
0
:::::
'i!!
Q) I:
> 0 0.60 T7"
I:
0 0.40
'i!!
0 ~
I:
0
0 0.40 ;- 1-
3 2 1
0.20
0.20 -
0.00+-L....I.-4-.J........4...J.....L.....L,-I-"'--'r-'--i
0.00 0.20 0.40 0.60 0.80 1.00
Axial Coordinate 0.00
0.00 0.20 0.40 0.60 0.80 1.00
Figure 9.32 Counter-current filtration combustion. Axial Coordinate
Dimensionless temperature and conversion profiles Figure 9.33 Counter-current filtration combustion.
at high nitrogen pressures. (Dandekar, H.W., Dimensionless temperature and conversion profiles
Puszynski, J.A., Degreve, J. and Hlavacek, V., at low nitrogen pressures. (Dandekar, H.W.,
'Reaction front propagation characteristics in non- Puszynski, J.A., Degreve, J. and Hlavacek, V.,
catalytic exothermic gas-solid systems,' Chern. Eng. 'Reaction front propagation characteristics in non-
Cornrnun., 92, 199-224, 1990. Reproduced by catalytic exothermic gas-solid systems,' Chern. Eng.
permission of Gordon and Breach Publishers, Cornrnun., 92, 199-224, 1990. Reproduced by
Lausanne, Switzerland.) permission of Gordon and Breach Publishers,
Lausanne, Switzerland.)
solid layer is the critical parameter. It has
been found that there exists a certain depth of the solid reactant(s) leads to a decrease
of the bed for a particular pressure of opera- in porosity. Since the permeability of the
tion which, if exceeded, causes a combustion system is a strong function of the porosity,
front, initially formed, to extinguish. the gas flow to the inner layers is severely
Another critical factor is the porosity of the restricted. This might cause only the upper
solid. When the reaction is accompanied by layers of the solid reactant to react leaving
an increase in volume of the solid, conversion unconverted material at the bottom. To
 Synthesis of complex composites and solid solutions
avoid this situation, the initial bed porosity
should be high to make sure that there is a
sufficient gas flow to the inner layer of solid
reactant. The effect of structural changes
caused by sintering, melting and the product
volume change has been analyzed by
Smolyakov (1988, 1990) and Shkadinsky et al.
(1991).
SYNTHESIS OF COMPLEX COMPOSITES
AND SOLID SOLUTIONS
The potential of combustion reactions for the
in-situ synthesis of composite materials,
especially alumina-based composites (AI 20 r
TiC, AI2 0 r TiB 2 ), has been recognized since
the early stages of the discovery of SHS
(Walton and Poulos, 1959). The SHS method
also allows the synthesis of non-oxide
ceramic-ceramic composites and solid solu-
tions. Different reactants and their combina-
tions can be used in this synthesis. For
example, TiB 2- TiC composites can be synthe-
sized via either of the two following reaction
schemes (McCauley et al., 1982):
2Ti + 2B + C ~ TiB 2-TiC (9.40)
3Ti + B4C ~ 2TiB2 - TiC (9.41)
Thus, the selection of an optimum reaction
scheme, in terms of the economic considera-
tions for synthesis (cost of the precursor
powders etc.), becomes important. When
the miscibility of two phases is high, solid
solutions can be formed. Examples of solid
solutions which can be easily formed in the
combustion regime are carbonitrides and
boronitrides of transition metals (Me-Cx-N y
and Me-Bx-Ny respectively) (Avakyan et al.,
1975) and sialons (solid solutions based on
the Si-Al-O-N system) (Lis et al., 1991b). A
solid solution in the system TiC-TiN can be
formed by combustion of titanium powder
in nitrogen in the presence of titanium carbide
or by the direct reaction between titanium
powder and carbon in the presence of
titanium nitride. The direct reaction
among three elements - titanium, carbon and
221
nitrogen - leads to significant melting of the
product and is not recommended for the
synthesis of powdered titanium carbonitride.
COMPOSITES
Silicon nitride-silicon carbide composite
powders can be directly synthesized by com-
bustion of silicon in nitrogen in the presence
of carbon. As presented in the previous sec-
tion, the ,B-Si3N4 powder can be synthesized
in the self-propagating regime by the reaction
of silicon powder with nitrogen gas under a
pressure above 3 MPa (,...,30 atm) (Lis et al.,
1991a). Silicon nitride must be added in the
reactant mixture as a diluent because it acts
as a seeding phase for the synthesis. The
direct reaction between silicon and carbon
is significantly less exothermic (6.HR =
-69.55kJ/moD than that between silicon
and nitrogen and no propagation can be
achieved without significant preheating
(Pampuch, Stobierski and Lis, 1989). How-
ever, the heat generated by the highly
exothermic reaction between the silicon and
nitrogen generates enough energy to preheat
a weakly exothermic reaction between silicon
and carbon. This is achieved by igniting a
mixture of Si, Si3N4 and C powders at
elevated nitrogen pressures (PN 2 > 3 MPa
(30 atm)). The following two reactions then
take place simultaneously:
3(1 - x)Si + xSi3 N 4 + 2(1 - x)N2 ~ Si3N4
(9.42)
ySi + yC ~ ySiC (9.43)
and the overall reaction scheme would then be
[3(1 - x) + y)]Si + xSi3 N 4 + yC + 2(1 - x)N2
~ Si3N4 + ySiC (9.44)
The details of the combustion process in
the Si-Si3NcC system have been reported
by Agrafiotis et al. (1990). The precursor
powders (silicon, carbon and silicon nitride,
with average particle sizes of 3.5, 0.25 and
0.5 J.lm, respectively) are dry mixed in a jar
222 Thermochemistry and kinetics
mill for 8 h. The powdered reactant mixture
is then placed in a graphite container. A
stainless steel vessel, in which the container
is placed, is initially pumped down to
6.7kPa (5.0 x 10-2 torr) and consequently
filled with nitrogen gas to a desired pressure.
The reactants are then ignited by a resistively
heated molybdenum wire. The velocity of
the propagating front is measured by using
a video camera/recording system. The com-
bustion temperatures can be measured by
using tungsten-rhenium thermocouples.
It has been shown that reacting systems
containing more than 20 wt% carbon could
not be ignited below a nitrogen pressure of
7 MPa (69 atm). The region of initial concentra-
tions, for which the combustion process
remains self-sustaining under 3 MPa (30 atm)
nitrogen pressure, is shown in Figure 9.34.
The combustion of these mixtures exhibits
many features in common with combustion
of the silicon powder in nitrogen, namely
the unstable character of the combustion
process and independence of the combustion
temperature on reactant composition. This
SiL-~~~~~~~~~~~SLM
90 80 70 60 50 40 10 ~~
Figure 9.34 Ignition region for the Si-Si3 N 4 -C
system under nitrogen pressure of 3 MPa. (Agrafio-
tis, c., Lis, J., Puszynski, J.A. and Hlavacek, V.,
'Combustion synthesis of silicon nitride-silicon
carbide composites,' J. Am. Ceram. Soc., 73(11),
3514-17, 1990. Reproduced by permission of
the American Ceramic Society, Westerville, OH.)
behavior is rather expected since silicon nitride
synthesis is the primary reaction taking
place, 'driving' along the reaction between
carbon and silicon. The combustion product,
consisting of a mixture of silicon nitride and
silicon carbide, forms a thick core which is
enclosed by a thin outer layer of unreacted
powder.
The results of propagation velocity are
shown in Figure 9.35. An interesting observa-
tion was noticed. As the carbon content
increased, the propagation velocity also
increased. However, as the carbon content
reached a critical value, extinction abruptly
took place. The same trend was observed
under 7MPa (69 atm) of nitrogen. Combustion
temperature, on the other hand, seems to be
independent of carbon content.
However, the region of carbon concentra-
tion within which ignition has been observed,
becomes narrower for higher nitrogen pres-
sures. This unexpected phenomenon has also
been observed in some combustion experi-
ments in Si-AI-Si3NcAI203-N2' At higher
pressures, the cooling effect of the surround-
ing gas becomes more important, thus com-
positions very close to the extinction limit
might be adversely affected by an increase in
N2 pressure. X-ray diffraction patterns of the
reaction products reveal that the product
consists of ,B-Si3N4 and ,B-SiC and contains a
small amount of unreacted Si. The unreacted
Si can be eliminated when larger batches of
reactants are combusted.
SOLID SOLUTIONS
When the miscibility of solid combustion
products is high, the solid solution is formed
instead of a composite powder material. TiN-
TiC solid solution can be synthesized in a
manner similar to TiN. The details of such a
synthesis have been described in the former
section. The experimental results have
shown that a TiC-TiN solid solution can be
synthesized directly from the elements. How-
ever, due to high exothermicity of both the
 Synthesis of complex composites and solid solutions 223

2600
"t
0 6
x
~
g
.s 2400 ~
::l
.2:- ~
'0 Q)
0
4 a.
~ E
c:
0 2200 ~
c:
~ 0
Ol
<ll
~
::l
a. .c
e
a. 2
E
0
2000 ()

1800
0~----~-----.----~------~----4
o 5 10 15 20 25
Amount of Carbon (wt%)

Figure 9.35 The dependence of combustion front velocity and combustion temperature on the carbon
content in a reaction mixture. (Agrafiotis, c., Lis, J., Puszynski, J.A. and Hlavacek, V., 'Combustion syn-
thesis of silicon nitride-silicon carbide composites,' J. Am. Ceram. Soc., 73(11), 3514-17, 1990.
Reproduced by permission of the American Ceramic Society, Westerville, OH.)

involved reactions: product (Agrafiotis, Puszynski and Hlavacek,

Ti +! N2 ---> TiN
Ti + C ---> TiC
significant melting takes place.
In order to reduce the melting of the
product, a dilution of the reactant mixture
with the final product is required.
In the case of the TiC-TiN synthesis, it
is possible to use TiC or TiN as one of the
reactants. In both cases, the combustion
process is self-sustaining due to the heat gen-
erated by nitridation of titanium powder or
direct reaction between Ti and C. In order to
obtain TiC-TiN without any melting, it is
necessary to add additionall0-15wt% of the
TiC-TiN phase. This fraction of inert material
in the reacting mixture did not cause any var-
iation in a homogeneity of the combustion
1991).
(9.45) The typical x-ray diffraction patterns of
(9.46) combustion synthesized titanium carbonitride
are shown in Figure 9.36. Nitrogen and
oxygen contents were 12.1 wt% and 0.29 wt%,
respectively. The content of free carbon did
not exceed 0.03 wt%. The average particle
size of TiC-TiN was 8 Mm after 2 h of
dry milling. The mean lattice parameter a =
4.2814 x 10- 10 m (4.2814A estimated from
XRD patterns) has been in good agreement
with the value estimated from Vengard's
rule for the lattice parameter of mixed crystals
(a = 4.2819 x 10- 10 m (4.2819 A.
Recently, Lis et al. (1992, 1995a,b) have
reported the formation of a Ti3 SiC2 phase by
conducting a reaction in a self-propagating
high-temperature regime. This compound,
rather than the mixture of Ti2C and SiC, was
224 Thermochemistry and kinetics

3.0-
M 2.5-
0
~ 2.0-
~ 1.5-
m
c:
(I) 1.0
'E
0.5
0.0
l.l
20 40 60 80
TiC

TE I
20
I
40
I 60
I
80
TiN

'3~
0 I I I
I I
20 40 60 80
Two-Theta (Oeg.)

Figure 9.36 X-ray diffraction patterns of combustion-synthesized titanium carbonitride.

formed when stoichiometric amounts of Ti,
Si and low ash carbon black were mixed
with WC-Co media in a ball mill for 24h,
then subsequently ignited in vacuum by a
resistively heated molybdenum coil. After
ignition, a combustion front with a maximum
temperature between 2100 and 2300 K (1827
and 2027C) propagated through the system.
It was found that high conversions to Ti 3SiC2
were obtained when highly reactive and well
mixed powders were used. This new product
is characterized by very low hardness. Despite
its ceramic-like covalent structure, it performs
like a metal. The fracture toughness of
multi phase material Ti3 SiCr TiC synthesized
by the combustion technique is higher than
7MPam 1/ 2 .
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Sivaskinsky, G. (1981) On spinning propagation
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432-38.
Smolyakov, V.K (1988) Effect of structural changes
on the combustion of metal powder compacts in
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Smolyakov, V.K (1990) Macrostructural transfor-
mation in gasless combustion processes. Fiz.
Gar. Vzryva, 26(3), 55-61.
228 Thermochemistry and kinetics
Smolyakov, V.K., Nekrasov, E.A and Maksimov,
Y.M. (1984) Modeling of gas-free combustion
with phase transition. Fiz. Gor. Vzryva, 20(2), 63-73.
Smooke, MD. and Koszykowski, M.L. (1983) Two-
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Sukhov, G.S. and Yarin, L.P. (1980) Two-dimen-
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Szekely, J., Evans, J.W. and Sohn, H.Y. (1976) Gas-
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PROCESSES
Stephen D. Dunmead
INTRODUCTION
As discussed in Chapter 9, the combustion
synthesis process takes advantage of highly
exothermic reactions to form a variety of
ceramic (e.g. TiC, Si3 N 4 ), intermetallic (e.g.
NiAI, TiNi) and composite (e.g. AlzO r B4 C,
TiC-NiAl) materials (Munir, 1988; Munir
and Anselmi-Tamburini, 1989; Holt and Dun-
mead, 1991). These reactions can take place in
both solid-solid and gas-solid systems. Once
the reaction is initiated, it can sometimes take
the form of a self-propagating combustion
wave. In this chapter, discussions will focus
on the use of these highly exothermic reac-
tions for manufacturing advanced non-oxide
ceramic powders. Examples will be given
that illustrate how the nature of these reac-
tions impacts the product characteristics,
reactor design and process development.
SOLID-SOLID REACTIONS
TITANIUM CARBIDE (TiC)
The reaction between titanium (Ti) and carbon
(C) has been the most widely studied of the
combustion synthesis reactions (Prokudina
et ai., 1975; Shkiro and Borovinskaya, 1975;
Merzhanov et ai., 1979; Holt and Munir,
1986; Dunmead, 1987; Dunmead et ai., 1989;
Kecskes and Niiler, 1989; Mullins and Riley,
1989; Holt and Dunmead, 1991). This is due
to the fact that TiC is a valuable refractory
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
10
and abrasive material and that the Ti-C
system is considered to be a model for com-
bustion synthesis. Referring to Table 9.1, one
sees that the reaction between Ti and C,
Ti +C ----> TiC (10.1)
is highly exothermic, liberating 183.1 kJ/mol
and yielding a theoretical adiabatic combus-
tion temperature, Tad, of 3210 K (2937C) (the
melting point of TiC). Work carried out on this
reaction in Russia (Prokudina et ai., 1975;
Merzhanov et ai., 1979, 1981) was successful
in developing a semi-industrial scale process
for producing TiC powder used in the manu-
facture of abrasive wheels and pastes.
A schematic illustration of the reactor used
in the Russian process is shown in Figure 10.1
(Prokudina et ai., 1975). The basic reactor
consists of a water-jacketed stainless steel
chamber that is connected to atmospheric con-
trols (vacuum and gas supply). The reactants
are loaded into porous refractory containers
which enable gases generated during the com-
bustion reaction to be released. As a safety
consideration, the reactor is equipped with a
pressure relief device. Increased pressure,
caused by either gas generation or increases
in temperature, can be vented through it. As
is common in SHS experimental equipment,
the ignition system consists of a tungsten coil
connected to a power supply. Batch reactors of
this basic design having a volume of 20 I (20 kg
(44.1Ib) capacity) were used. For the 20kg
(44.1Ib) reactions, the synthesis was reported
230 Processes

rin r--_ _ .....,.M!"'-iX_in_g_~--~

o 0

Vacuum

Figure 10.1 Schematic illustration of reactor system for combustion synthesis of TiC abrasives. (Proku-
dina, V.K., Ratnikov, V.I., Maslov, V.M., Borovinskaya, I.P., Merzhanov, A.G. and Dubovitskii, L.I.,
Technology of titanium carbide,' in Combustion Processes in Chemical Engineering and Metallurgy (ed. A.G.
Merzhanov), pp. 1-13, 1975. Reproduced with permission of the Institute of Structural Macrokinetics,
Russian Academy of Sciences, Chernogolovka, Moscow, Russia.)

to last approximately 60-90 s, while cooling of
the reactor took an additional 1.5-2 h, result-
ing in an overall production rate of approxi-
mately 10kg/h/reactor (22lb/h/reactor;
0.5 kg/h .1).
In most cases, if the desired product is stoi-
chiometric TiC with minimal free carbon, the
reactant mixture used is very close to theoreti-
cal (i.e. 20.05wt% C and 79.95wt% TO. For
cases when the Ti is grossly contaminated
with oxygen (Prokudina et al., 1975), addi-
tional C must be added to account for that
which is lost by carbothermal reduction of the
oxide contaminant. It is the combination of
the production of carbon monoxide (CO) and
the release of adsorbed gaseous contaminants
on the surface of the carbon black that necessi-
tates the use of both the porous refractory con-
tainer and the pressure relief device discussed
above. If such a container is not used, the rapid
generation of these gases can lead to the hot
reactants and/ or products being violently
blown about the reactor. Several investigators
(Hansen et al., 1986; Holt and Munir, 1986;
Kecskes and Niiler, 1989) have studied the
gases generated from such reactions. The
main gases coming off during combustion
are hydrogen (H 2) and CO which are gener-
ated due to impurities in the raw materials.
The H2 is either from water vapor adsorbed
onto the surface of the carbon black (Holt
and Munir, 1986) or from TiH2 present on the
surface of the Ti (Keckes and Niiler, 1989). As
was alluded to above, the CO is likely gener-
ated by carbothermal reduction of the Ti0 2
layer present on the surface of the Ti.
The method of loading the reactor (Proku-
dina et al., 1975) has been found to be one of
the production variables that strongly influ-
ences the properties of the final product. It
was found that when the reactant mixture
was fed into the reactor in a pelletized form
(as opposed to loosely poured) the amount
of fixed carbon was significantly higher and
the amount of free carbon lower. This effect
has been explained by more intimate contact

of the metallic particles and carbon black in
the pelletized form. Similarly, increases in
the free carbon content have been seen when
large quantities of gas are generated. Here,
however, the intimate contact between the Ti
and carbon black is disrupted by the violent
nature of the gas release.
One method of controlling the characteris-
tics of SHS products is to decrease the
combustion temperature by dilution of the
reaction with the end product. The effect of
dilution on Tad for the Ti-C system (equation
10.1) is shown in Figure 10.2. Here, Tad
remains unchanged until the diluent content
reaches 20 mol%. Over this range, the theore-
tical fraction of molten TiC in the product, S,
decreases from 33% to 0%. For this system, it
Solid-solid reactions 231
has been shown experimentally (Shkiro and
Borovinskaya, 1975) that dilution decreases
both the synthesis temperature and the rate
of combustion. As an example of the utility
of this temperature control, in the Russian
process (Merzhanov et al., 1979) the product
for the undiluted reaction is a heavily sintered
dark gray mass. In order to make a useful
powder, the mass must be pulverized using
a rather severe mechanical treatment. It was
found that, by adding between 10 and
20 wt% TiC to the reactant charge, the degree
of sintering could be decreased to the extent
that the reaction product was in the form of
powder and did not need to be pulverized.
Not only can dilution control the degree of
sintering of the product mass, but also its

3300 r - - - - - - r - - - " T - " - - - r - - - - , - - - , 60

3200 50

3100 40

-
~
30
-
~
~
as 3000
"0
r- a:>

2900 20

2800 10

2700 L-_ _-L._ _ _ ~ _ _ _ _ _.........._ _--I 0

o 10 20 30 40 50

TiC (mol %)

Figure 10.2 Calculated adiabatic combustion temperature (Tad) and fraction of molten product (8) for
Ti + C =} TiC when diluted with TiC (Dunmead, 1987).
232 Processes

(a)

(b)

Figure 10.3 SEM of (a) high temperature and (b) low temperature combustion synthesi:z;ed TiC.
(Dunmead, S.D., Readey, D.W., Semler, C.E. and Holt, J.B., 'Kinetics of combustion synthesis in the
Ti-C and Ti-C-Ni systems,' J. Am. Ceram. Soc., 72(12), 2318-24, 1989. Reproduced with permission of
the American Ceramic Society, Westerville, OH.)

morphology. Scanning electron photomicro-
graphs (SEMs) of the product of the Ti-C
reaction when diluted with 5 and 13 wt% TiC
are shown in Figure 10.3 (Dunmead et al.,
1989). The higher temperature specimen
(Figure 10.3(a contains many acicular crys-
tals which are of the order of 111m in width.
These crystals indicate that at least part of the
TiC was precipitated from a melt. In the lower
temperature specimen (Figure 10.3(b, on the
other hand, none of the acicular crystals were
found. These results indicate that, as the

combustion temperature decreases, the
mechanism of the reaction changes. In this
particular system, a decrease in temperature
only effects product powder morphology. In
more complex systems (e.g. Si-N), changes
in the combustion also alter the phases present
in the final product.
SILICON CARBIDE
Self-propagating high temperature synthesis
(SHS) reactions will not be self-sustaining
unless Tad is greater than approximately
1800 K (1527C) (Novikov, Borovinskaya and
Merzhanov, 1975; Munir and Anselmi-Tam-
burini, 1989). This 'rule of thumb' is generally
adhered to. Again, referring to Table 9.1, the
reaction between Si and C is exothermic
(flH298 = -72.5kJ/mol,Tad = 1800K(1527C
but not nearly as exothermic as the Ti and C
reaction. Consequently, the SiC reaction
Si + C -> SiC (10.2)
is not self-sustaining when ignition is
attempted at room temperature (Yamada,
Miyamoto and Koizumi, 1986).
The most commonly used method of deal-
ing with reactions that are not self-sustaining
due to their low to moderate exothermic
nature is to preheat the reactants prior to igni-
tion (i.e. raise To). An increase in To results in
an increase in Tad unless we are at an invariant
point such as melting. In some cases, however,
preheating of the reactants can lead to the
formation of the end product by a solid-state
reaction. This basically is an in-situ dilution of
the desired reaction and consequently this
approach may not always be viable.
For the Si-C system this in-situ dilution
problem was solved (Yamada, Miyamoto
and Koizumi, 1986) by limiting the time that
the reactant powders are exposed to high tem-
peratures. A cold-pressed pellet of the Si and
C reactants is placed between two carbon elec-
trodes, as shown in Figure 10.4. A constant
voltage is then applied across the electrodes
and the pellet is heated as electric current
Solid-solid reactions 233
Carbon Rod for Electrode
ArGas
Figure 10.4 Schematic illustration of resistance
heating thermal explosion apparatus. (Yamada, 0.,
Miyamoto, Y. and Koizumi, M., 'Self-propagating
high-temperature synthesis of SiC,' J. Mater. Res.,
2(3/4),275-79, 1986. Reproduced by permission
of the Materials Research Society, Pittsburgh, PA.)
begins to flow through the sample. The time
dependencies of the applied voltage, resultant
current, sample temperature and applied elec-
tric power are shown in Figure 10.5. The over-
all reaction can be divided into four stages. In
the first stage, the sample is preheated by
resistive heating to a temperature of 1000 K
(727C). Because of the short duration of this
preheating (7-8 s), minimal SiC is formed. In
the second stage, the SHS reaction initiates in
the middle of the sample. As SiC is formed
in this region, the resistivity increases rapidly,
resulting in a sudden drop in current without
a change in voltage. In the third stage, the
reaction propagates towards both ends of the
sample raising the temperature to greater than
2300 K (2027C). The duration of the reaction
stage was reported to be 0.1 s for a 30 mm long
sample. The final stage is characterized by
exponential cooling after all of the heat from
the reaction has been liberated. Even though
the SiC produced by this method (Yamada,
Miyamoto and Koizumi, 1986) was fairly
high quality (stoichiometric and submicron)
and in very high yield (>98%), it is difficult
to envision how such a process could be
scaled to an industrial level.
234 Processes
200 60
~
~ 150
-- 45
~
-
0
a..
:5 ~ <Il
100
30~
(.)
<Il E (5
iIi <{
"0
.91 50 15
a.
a.
<{
5 10
Time (8)
Figure 10.5 Applied voltage, resultant current
and power for resistance thermal explosion of
Si + C ..... SiC. (Yamada, 0., Miyamoto, Y. and
Koizumi, M., 'Self-propagating high-temperature
synthesis of SiC,' J. Mater. Res., 2(3/4), 275-79,
1986. Reproduced by permission of the Materials
Research Society, Pittsburgh, PA.)
A second approach which appears to be
more amenable to scale-up has been devel-
oped (Pampuch et al., 1987; Pampuch, Sto-
bierski and Lis, 1989). This method is based
upon the 'thermal explosion' technique that
was theoretically discussed in the previous
chapter. The thermal explosion technique
differs from typical SHS reactions, because
even though the reaction is self-sustaining,
it is not necessarily self-propagating (i.e. a
combustion wave does not form). On a
laboratory scale, pellets approximately
20 mm in length and 22 mm in diameter con-
taining Si and C were placed in a graphite
crucible in an induction furnace. The samples
were then rapidly heated (120 K/min) to a
temperature in the range of 1523-1573 K
(1250-1300C) where ignition (thermal explo-
sion) occurs. The thermal history of such a
reaction can best be understood by looking
at the three representative curves in Figure
10.6. When the samples were heated to
1473 K (1200C) no ignition occurred (curve
a). When the samples were heated to 1573 K
(1300C) (curve c), however, ignition
occurred. The most typical example is where
20
15
> g
1900
1700
ci. b
.s
Cl
10 E 1500
Q) a
> I-
5 1300
o 2 4 6 8 10 12 14 16 18
Time (min)
Figure 10.6 Temperature histories for bulk heating
thermal explosion of Si + C -+ SiC with external
heat source temperatures of (a) 1473K (1200 C), D
(b) 1523 K (1250 DC) and (c) 1573 K (1300C).
(Pampuch, R., Stobierski, L. and Lis, J., 'Synthesis
of sinterable ,B-SiC powders by a solid combustion
method,' J. Am. Ceram. Soc., 72(8), 1434-35, 1989.
Reproduced by permission of the American
Ceramic Society, Westerville, OH.)
the temperature of the external heat source
(graphite crucible) reaches 1523 K (1250C)
(curve b). Here, the start of the reaction
causes a gradual increase in temperature
during an induction period. This is followed
by a rapid increase in temperature to greater
than 2473 K (2200C) (the true maximum is
off scale in Figure 10.6). The morphology
of the submicron SiC produced by this
method is shown in Figure 10.7. Similar
work (Rigtrup and Cutler, 1992) has shown
that ,B-SiC can be produced by exposing
mixtures of Si and C to temperatures from
1873 to 1973K (1600-1700C) for approxi-
mately 2 min. Reportedly (Pampuch, Sto-
bierski and Lis, 1989), the principles of this
method form the basis of a large-scale
tunnel kiln process for producing sinterable
,a-SiC powder.
The final method that will be discussed in
dealing with reactions that are not self-
sustaining is referred to as the 'chemical
oven' (Holt and Munir, 1983; Halverson,
Lum and Munir, 1989; Yamada et al., 1989;
Anselmi-Tamburini and Munir, 1990). As was

Figure 10.7 SEM of submicron SiC made by bulk heating thermal explosion from the elements. (Pampuch,
R, Stobierski, L. and Lis, J., 'Synthesis of sinterable .a-SiC powders by a solid combustion method:
J. Am. Ceram. Soc., 72(8), 1434-35, 1989. Reproduced by permission of the American Ceramic Society,
Westerville,OH.)
discussed in the previous chapter, this
approach uses the heat generated by a highly
exothermic reaction to drive a weakly exo-
thermic one. The synthesis of TiB2 from its
elements,
Ti + 2B ---> TiB2 (10.3)
would be an example of a highly exothermic
reaction. In the formation of SiC, a pellet of Si
and C (equation 10.2) can be surrounded by a
larger pellet of Ti and B, as described by Holt
and Munir (1983): the Ti and B mixture was
ignited and the resultant reaction produced a
reaction in the Si + C pellet yielding SiC. Even
though the SiC was in the form of powder and
could be readily separated from the TiB 2, the
waste associated with the TiB2 places the
industrial utility of such a process in question.
This waste is not a problem, however, if all of
the reactants are mixed together, e.g.
25%(Ti + 2B) + 75%(Si + C)
---> 25% Ti~ + 75%SiC (10.4)
and the composite product has some utility.
Such an approach has been used to form
B4C-TiB2 composites for use as preforms for
Solid-solid reactions 235
~
1.0 !-,m
molten metal infiltration (Halverson, Lum
and Munir, 1989). An analogous chemical
oven technique that utilizes thermite-type
reactions to form a composite powder con-
taining an oxide will be discussed in a later
section.
One of the most interesting chemical oven
techniques involves the use of a gas-solid
chemical oven to drive a solid-solid reaction
(Yamada et al., 1989). Here, the reaction
between Si and C (equation 10.2) was ignited
from ambient temperature (300 K (27C in a
moderately high pressure (3 MPa (",,30 atm
nitrogen (N 2) atmosphere. From the mecha-
nistic discussion of the Si-N2(g) system in
the previous chapter we know that, under
sufficiently high N2 pressures, Si3N4 can be
formed by gas-solid SHS processes. The
details of such processes will be discussed in
a subsequent section. A typical thermal
history for this reaction is shown in Figure
10.8 (Yamada et al., 1989). Here, the reaction
ignites due to the highly exothermic (6.H298 =
-736kJ/mol) reaction given in equation
10.5:
(10.5)
236 Processes
g 2500
!I?
~
~ Tr
~ 2000
l-
e
o both Fe and A12 0 3. As a result, the higher
~
:>
.0
E or boat and can be physically separated from
8 1500
10 100
Time (s)
Figure 10.8 Temperature history for Si + C +
N 2 (g) ----> SiC + N 2 (g) chemical oven reaction.
(Yamada, 0., Hirao, K., Koizumi, M. and Miya-
moto, Y, 'Combustion synthesis of silicon carbide
in nitrogen atmosphere,' J. Am. Ceram. Soc., 72(9),
1735-38, 1989. Reproduced by permission of
the American Ceramic Society, Westerville, OH.)
The temperature then rapidly increases to
approximately 2500 K (2227 DC) as the com-
bustion front passes. After reaching this
maximum, the temperature decreases to
2100 K 0827 DC) and remains there for about
10 s where the SiC product forms. It was pro-
posed (Yamada et al., 1989) that this reaction
produces SiC by first making an Si3N4 inter-
mediate which then dissociates. After disso-
ciation, the Si vapor reacts with C to form
SiC. The interesting aspect of this process is
that the chemical oven (i.e. formation of
Si3N 4) is generated by the formation of an
intermediate which is not present in the
final product. As a result, a unit operation
involving physical or chemical separation is
not necessary.
THERMITE REACTIONS
All of the 'thermite reactions' that will be
discussed below are extensions of the
Goldschmidt process for the reduction of an
ore to its constituent metals (Goldschmidt
and Vautin, 1898). An example of this
reaction is the alumino thermal reduction of
iron ore,
(10.6)
The temperature reached during the reaction
(equation 10.6) is above the melting point of
density Fe sinks to the bottom of the crucible
the oxide. Not only did Goldschmidt's work
lay the foundation for the synthesis of ceramic
materials via thermite reactions, but also dis-
covered the self-propagating nature of such
reactions. This self-propagating aspect also
led to the development of a thermite process
for welding rail joints (Goldschmidt, 1909).
Thermite reactions are often used in the
synthesis of ceramic materials for three basic
reasons: 0) as a chemical oven, (2) for
economic raw materials or (3) because the
composite product is useful.
Boron carbide
The earliest references to the synthesis of a
non-oxide ceramic via a thermite reaction are
for the synthesis of boron carbide (Gray, 1953;
Deutsche Edelstahlwerke Aktiengesellschaft,
1955; Gray, 1958):
(10.7)
Referring to Table 9.1, the heat of formation of
B4C is only -39kJ/mol, yielding an adiabatic
temperature of 1000 K (727C). As was the
case with the direct synthesis of SiC from its
elements (equation 10.2), the synthesis of
B4C cannot be carried out in a self-sustaining
fashion from ambient conditions. Thus, the
use of the magnesiothermic reaction
2B2 0 3 + C + 6Mg -+ B4C + 6MgO (10.8)
can be classified as a chemical oven. This
reaction is much more economical than the
direct reaction of expensive elemental boron
via a thermal explosion reaction analogous to
that previously described for the synthesis of
SiC (Pampuch, Stobierski and Lis, 1989;

Rigtrup and Cutler, 1992). This particular reac-
tion (equation 10.8) has a .6.H298 = -1135 kJI
mol of B4C formed, resulting in a Tad of
2740K (2467C) (the melting point of B4C).
Boron carbide was synthesized via the stoi-
chiometric reaction given above in equation
10.8 by continuously passing boats through a
tube furnace at 1203-2273 K (930-2000C)
(Gray, 1953, 1958). When the boats were
heated to 1203 K (930C), the reaction ignited
in a thermal explosion mode and quickly
increased the temperature of the boats to
1573-1673K (1300-1400C). In order to main-
tain or increase this reaction temperature,
further heating was necessary. By varying
this temperature, the particle size of the B4C
in the product could be controlled as shown
in Table 10.1 (Gray, 1953). As one would
expect, the B4 C particle size increases with
increasing reaction temperature. It has also
been found that the reaction temperature can
be increased by decreasing the particle size of
the reductant Mg (Gray, 1953). Here, a
decrease in the particle size of the Mg resulted
in a faster reaction. Because of the increased
reaction rate, the effects of heat losses were
decreased, the reaction became more adiabatic
and the combustion temperature increased
(i.e. tends towards Tad). After cooling, the
product was leached with hot dilute acid
(hydrochloric, sulfuric or nitric). This leaching
Table 10.1 Effect of furnace temperature and mag-
nesium particle size on resultant B4 C particle size
in magnesiothermal production of B4 C (adapted
from Gray, 1958)
Furnace Mg particle B4 C particle
temperature size size
(K (OC)) (p,m)
<1723 coarse <2
(1450) (+100 mesh)
1823-1923 coarse 0-5
(1550-1650) (+100 mesh)
2123 fine 7-20
(1850) (-100 mesh)
Solid-solid reactions 237
treatment removed not only the MgO but also
contaminant metals and salts. Boron carbide
products produced by this method were
somewhat less than the 4B:IC stoichiometry
(Table 10.2).
Deutsche Edelstahlwerke Aktiengesell-
schaft (DEA) (1955) extended the work of
Gray (1953) to include the formation of the
carbides of W, Mo, V, Ti, Ta, Nb and Cr.
These reactions would not all be classified as
chemical ovens. For example, TiC is formed
from the elements by SHS (equation 10.1). In
the DEA process, no energy was added except
that necessary to ignite a primer of sodium
peroxide and aluminum. After ignition of the
primer, the reaction became self-propagating
resulting in a more economical process than
that originally developed by Gray (1953).
The DEA process targeted the production of
carbides for usage in sintered hard metals.
As such, a variation of the process was devel-
oped in which the binder phase of the hard
metal (e.g. Ni, Co or Fe) is simultaneously
synthesized by a thermite reaction. In addi-
tion, it was found that the particle size of the
carbide could be controlled by adding grain
growth inhibitors such as V.
One of the main difficulties with the ther-
mite B4 C reaction is its potentially violent
nature resulting from the generation of gases
during the reaction. The B2 0 3 is the main
source of these gases. Because of its hygro-
scopic nature, B2 0 3 tends to form boric acid
(H 3 B03 ) when exposed to the atmosphere.
Upon heating during the thermite reaction,
the chemically bound water is released at
573 K (300C) generating large volumes of
gas. In addition, Tad for this reaction is well
above the boiling point of B2 0 3 (2133 K
(1860C. The generation of gases poses a
safety concern and can result in a decrease in
the yield of B4 C. These problems were both
solved by adding MgO (also CaO, A12 0 3 or
Si02 ) as an inert diluent (Kabushiki Kaisha
Hitachi Seisakusho, 1966a,b). The addition of
the solid diluent decreased both the ultimate
combustion temperature and the rate of
238 Processes
Table 10.2 Effect of inert diluent and sulfate catalyst contents on yield for thermite process
to form B4 C via reaction 2B2 0 3 + 6Mg + C (adapted from Kabushiki Kaisha Hitachi
Seisakusho 1966a,b)

Temperature MgO Potassium Yield B/C

(K (OC)) (wt%) sulfate (wt%) (% theoretical) mole ratio

Theoretical 3.60
1473 (1200) 70.5 3.31
1473 (1200) 9.1 92.6 3.28
1373 (1100) 0.0
973 (700) 9.1 67.9 2.96
973 (700) 8.3 8.3 94.9 3.19

reaction. The final result (Table 10.2) is an the lower temperature (0.1 MPa; ",I atm Ar)
increase in the overall yield of more than case, the maximum temperature reached was
20% as compared to the undiluted case. It is below the melting point of B and the reaction
also shown in Table 10.2 that the ignition tem- to form B4C occurred in the solid state. For the
perature decreases when a sulfate catalyst is higher temperature (3 MPa; ",30 atm Ar) case,
added. the maximum temperature was greater than
Recent work (Wang, 1991; Wang, Munir the melting point of Band B4 C was most
and Holt, 1994a,b, 1995) has improved the likely formed by the reaction of molten B
understanding of the mechanism of the mag- and C.
nesiothermic (equation 10.8) and alumino-
thermic reactions to form B4 C. By increasing
Titanium diboride (TiB 2 )
the inert gas (Ar) pressure under which the
reaction was ignited, it was found that the The direct reaction of Ti and B to form TiB2
rate, combustion temperature and morphol- (equation 10.3) can be carried out in a self-
ogy of the product could be altered. When propagating combustion mode (Chapter 9).
the inert gas pressure was increased to greater The cost associated with the use of elemental
than 3MPa (",30 atm), the combustion tem- B, however, is prohibitive with respect to
perature increased above the melting point industrial applications. The speed and cost
of boron (2050 K; 1777C) (Table 10.3). The
reaction rate increased as well (Table 10.3).
These results were attributed to a suppression Table 10.3 Effect of argon pressure on the combus-
of Mg vaporization. As the Mg vaporization tion temperature (Tc) and wave velocity (u)
was suppressed, the heat available to (adapted from Wang, 1991)
raise the temperature of the specimen
Argon Combustion Wave
increased and thus Tc increased. Scanning pressure temperature velocity
electron photomicrographs (SEMs) of the (MPa (atm)) (K (OC)) (m/s (in/min))
acid-leached B4C product from ignition
under 0.1 and 3MPa (",I and 30atm) Ar are 0.1 (""I) 2097 (1824) 0.0058 (13.7)
shown in Figure 10.9. The B4C produced 1.3 (12.8) 2294 (2021) 0.0097 (22.9)
3.0 (29.6) 2396 (2123) 0.0090 (21.3)
under the higher pressure is approximately
10.0 (98.7) 2541 (2268) 0.0090 (21.3)
one order of magnitude larger. This rather 15.0 (148.1) 2354 (2081) 0.0090 (21.3)
large difference was due to a change in the 20.0 (197.4) 2352 (2079) 0.0081 (19.1)
mechanism of the reaction (Wang, 1991). In
 Solid-solid reactions 239

(a)

(b)

Figure 10.9 SEM of B4 C made by the magnesiothermal thermite reaction under argon at (a) 0.1 MPa
(~1 atm) (bar = 1.9911,m) and (b) 3.0 MPa (29.6 atm) (bar = 1.89I1m). (Wang, L.L., Munir, Z.A. and Holt,
J.B., 'Formation of MgO-B 4 C composite via a thermite-based combustion reaction: J. Am. Ceram. Soc., 78(3),
756-64, 1995. Reproduced by permission of the American Ceramic Society, Westerville, OH.)
240 Processes
effectiveness of an SHS reaction can still be
achieved by using relatively inexpensive raw
materials according to the following thermite
reaction:
Ti0 2 + B20 3 + 5Mg --t TiB2 + 5MgO (10.9)
This reaction has been studied in some
detail (Logan and Walton, 1984; Logan,
1987, 1989) for producing submicron TiB2
powder. By varying the stoichiometry of the
reaction given in equation 10.9, it was found
(Logan, 1989) that the amount of contami-
nants in the form of borates and titanates
can be minimized by using an excess of
approximately 10% of both the B20 3 and
the Mg. Acid leaching of the MgO was
done with a dilute HN03 solution at a pH
of about 0.5-8. When the leaching solution
was extremely acidic (less than about
0.5 pH), titanates were found to readily
form. When the solution was alkaline (pH
of more than about 8.0), borates formed.
The TiB2 product was found to be submicron
and mostly amorphous (as shown by selected
area diffraction).
A comparison of selected characteristics of
thermite and conventional carbo thermal TiB2
(Logan, personal communication, 1992) is
presented in Table 10.4. The thermite-
produced TiB2 is inherently finer and, thus,
more reactive than the carbothermally pro-
duced TiB 2. This increased reactivity results
in a material that can be hot pressed to full
density in 2h at 20.4MPa (,-,.,3000psi) and
1773 K (1500C). The carbothermally pro-
duced powder, on the other hand, required
8 h at temperatures in excess of 2273 K
(2000C) and a higher pressure of 27.2 MPa
(,-,.,4000 psi). It still only reached 98% density.
The typical morphology of the TiB2 product
is shown in Figure 10.10. This powder was
hot pressed to 100% density. The resulting
part had a fracture toughness of
5.5 MPa . m 1/2. From an economic point of
view, the thermite powder requires a very
simple reactor, minimal energy and no
milling. It does, however, require a leaching
step to remove the MgO. The thermite
process appears to be economically com-
petitive with the conventional carbothermal
process.
As one would expect, the particle size of an
SHS product is not only dependent upon the
temperatures reached during the reaction but
also the residence time at temperature. The
TiB2 product crystallized and grain growth
occurred as the size of the reactant batch was
increased (Logan, 1989). This can be attributed
to increased residence time at temperatures
caused by increasingly adiabatic conditions.
The apparatus shown schematically in
Figure 10.11 was designed in an effort to
achieve rapid quenching and retain the fine
particle size. In this unit, the reactant feed
mixture was gravity fed through a funnel
into a hot zone where ignition occurred.
After ignition, some of the product escaped
out the top as a fine smoke while the majority
was quenched and recovered at the base of
the column. This type of reaction concept
demonstrates that SHS reactions can poten-
tially be developed into continuous synthesis
processes.
Composites
In the Goldschmidt process (Goldschmidt and
Vautin, 1898), a variety of reductant metals
can be used (e.g. AI, Zr or Ti). In the area of
ceramic synthesis, however, a majority of the
literature deals with the use of Mg because it
can be easily removed from the product
powder by hydrochloric acid leaching (Chap-
ter 19). The other commonly used reductant
metal in SHS thermite reactions is AI. The
product of these reactions (e.g. TiBz-A1203)
is typically used as a composite material. A
variety of materials have been made using
this technique including: TiBz-A120 3 (Logan,
1990; Logan and Walton, 1991), TiC-A120 3
(Hida, 1991c), SiC-A120 3 (Hid a, 1991a,b),
MoSi2-A120 3 (Abramovici and Hida, 1991)
and A120 r B4 C (Holt et al., 1991; Wang, 1991;
Wang, Munir and Holt, 1994a,b; 1995).
Table 10.4 Comparison of properties of TiB2 powder made by magnesiothermal thermite reaction and conventional carbothermal route

Powder Raw Temperature Atmosphere Post-treatment Particle size Particle size Crystallinity Surface area Trace
materials (K (a C)) reduction (j.Lm) (m 2 /g) components

Thermite TiB2 Ti02, B20 3 , 298 (25)a Air HN03 leach None <1.0 Amorphous or 25-49 Borates, titanates,
Mg crystalline other borides
Carbothermal TiB2 Ti02, B4 C, 2273-2473 Inert None WC milling 2-10 Crystalline 1-7 Ti02, B20 3,
Cb (2000-2200) some carbides

aHot filament to ignite.

bPotentially can use Ti02, B20 3 , C.
Source: Data courtesy of K.V. Logan, 1992, Georgia Institute of Technology. Published by permission of Georgia Tech Research Corporation, Atlanta, GA.
242 Processes
Figure 10.10 SEM of submicron TiB2 made by the magnesiothermal thermite reaction. (Photo courtesy of
K.V. Logan, 1993, Georgia Institute of Technology. Published by permission of Georgia Tech Research
Corporation, Atlanta, GA.)
Because the oxide-based composites are
beyond the scope of this text, the reader is
referred to the list of references cited above.
METAL MATRIX PRECURSORS
Martin Marietta Corporation (Brupbacher,
Christodoulou and Nagle, 1987, 1990a,b;
Nagle, Brupbacher and Christodoulou, 1988,
1990) has developed an SHS-based process
for forming a ceramic-metal composite that
is used as a raw material for the formation
of a metal matrix composite. This process
is best described by the use of an example.
The reaction for the SHS portion of the process
is
34wt%Ti + 16wt%B +50wt%AI
----t 50 wt% TiB2 + 50 wt% Al (10.10)
The mixture shown in the reaction given in
the left side of equation 10.10 was pressed
into a compact and heated in a furnace to
1073 K (800C). Upon reaching a temperature
1.0jJm
of approximately 943 K (670C), the tem-
perature rapidly increased to 1523 K
(1250C). A typical time-temperature curve
for such a reaction is shown in Figure 10.12.
It should be noted that this type of reaction
was also shown to be capable of being carried
out in a self-propagating mode (Brupbacher,
Christodoulou and Nagle, 1990a,b). Upon
cooling, the product was found to contain a
fine dispersion of TiB2 (0.1-3 J.Lm) in an Al
matrix. Because the Ti and B both dissolve
in the Al and lower the ignition temperature
by approximately 1000 K (as compared to
TiB2 reaction in equation 10.3), this process
is referred to as being 'solvent-assisted'
combustion.
The ceramic-metal composite produced by
the solvent-assisted combustion reaction has
been used as a raw material for the formation
of ceramic-metal, ceramic-intermetallic or
ceramic-ceramic composites. For the case of
the precursor powder formed according to
reaction 10.10, a ceramic-metal composite
was prepared by adding the precursor
 Solid-solid reactions 243

Ti0 2 . 8 2 3' Mg
Feed

Rotary Valve - - - - .

Resistance
Heater

MgO Product
Collection Crucible Ti8 2 . MgO Product

Figure 10.11 Schematic illustration of apparatus for the thermite production of TiB2 . (Adapted from
Logan, 1989.)
244 Processes
1900

1500 1700

1500

G
~ 1000
1300 g
ci ci
E 1100 E
Q)
~ I-
900
500 700

500

300
4 8 12 16 20 24

Time (min)

Figure 10.12 Typical temperature history for a solvent-assisted combustion reaction to form TiB2-AI
composite. (Adapted from Brupbacher, Christodoulou and Nagle, 1990.)

powder to a bath of molten Al and then cast-
ing. Here, the final product was an ingot of Al
with finely dispersed TiB 2. Such an ingot can
be processed into shapes using conventional
metallurgical methods (i.e. casting, extrusion,
rolling etc.). For the formation of the ceramic-
intermetallic composite, the product was
formed by adding the precursor powder to a
molten bath of some metal other than AI,
say Ti. Here, the final product was an ingot
of Ti-Al intermetallics (e.g. TiAl or Ti3 Al)
with finely dispersed TiB 2. In the final case
(ceramic-ceramic), the ceramic-metal compo-
site described above was reacted with a gas.
For example, the TiB 2-Al composite produced
via reaction 10.10 was extruded and then
reacted for 12 h at 823 K (550C) in 200 MPa
(",2000 atm) of N2 (Brupbacher, Christo-
doulou and Nagle, 1990b). This treatment
produced a shape having an outer surface of
TiBz-AlN and a central core of TiB2-Al
cermet.
One of the more intriguing variations of the
Martin Marietta process involves the forma-
tion of ceramic whiskers (Chapter 16) during
the combustion reaction (Brupbacher, Christo-
doulou and Nagle, 1990a). It was found that
when certain complex borides (e.g. Ti-Nb
boride or Ti-Ta boride) or complex carbides
(e.g. Ti-V carbide or Ti-Ta carbide) were
formed during the solvent-assisted combus-
tion reaction, they precipitated in the form of
whiskers. One of the largest benefits of this
technology is that the whiskers in-situ forma-
tion avoids all of the potential health concerns
associated with inhalation of these materials.
In addition, because the ceramic phases
(either whiskers or particulates) are directly
precipitated from the molten metal they are
not exposed to the atmosphere and, thus, the
interfaces between the metal and ceramic are
much cleaner than those in conventionally
produced materials.
GAS-SOLID REACTIONS
As discussed in Chapter 9, not only can SHS
reactions take place in solid-solid systems but
also in gas-solid systems (Dunmead, Munir
and Holt, 1989; Holt and Dunmead, 1991).
 Gas-solid reactions 245
In the gas-solid systems, additional con- 1123 K (850C). Here, at some temperature
siderations of reactant gas availability and between 1123 and 1173 K (850 and 900C),
dissociation of the product become important. the nitridation rate increases rapidly. One con-
In this section, we will examine processes for cern is that the Al melts (933 K (660C prior
the synthesis of AlN and Si3N4 that utilize the to reaching this zone of rapid nitridation. As a
exothermic nature of the direct nitridation result, the Al will melt and coalesce into a pool
reactions. This discussion will not only cover before the reaction begins. This coalescence
reactions that are carried out in a combustion acts to restrict flow of N2 to the reaction site.
mode, but also in a more controlled fashion. A second concern with the direct nitridation
of Al is that the heat generated Ctl.H298 =
-268kJ/mol, Tad = 4900K (4627C), not
ALUMINUM NITRIDE
accounting for the heat of dissociation) is
high enough to cause dissociation of the AlN
Controlled direct nitridation
(,...,.,2473 K (2200C that is formed. Hence,
In theory, the simplest method of producing control over the exothermic nature of the
AlN is to heat Al in the presence of N2 as reaction is extremely important in this direct
shown by nitridation process for achieving high degrees
2AI + N 2(g) ----+ 2AIN (10.11) of conversion and producing quality product
powder.
As illustrated in Figure 10.13 (Choi and Lee, Union Carbide Corporation (Mandorf,
1985), however, this simple process is com- 1967) developed a method of dealing with
plicated by the fact that the nitridation of Al both the coalescence and dissociation con-
does not occur at a significant rate until the cerns by blending a carrier material with the
temperature is greater than approximately AI. The carrier material (either AlN or AIF3)
prevented coalescence by allowing molten Al
to spread over the surface of the carrier. In
100 addition to preventing coalescence, the carrier
~ material acted as a diluent which controlled
~
Z 80
the exothermic nature of the reaction. As was
C( the case with the synthesis of TiC, it has been
.8 found that the higher the diluent (AlN or
C(
'0
60 AIF3) content, the less sintered the product
0 (Mandorf, 1967; Uchimura et al., 1987). In
~
a: 40
most cases, the use of an AIN carrier is pre-
c: ferred so as to eliminate the need to separate
0
.~
Ql
the carrier from the product. On the other
>
c: 20 hand, if AIF3 is used it must be removed by
0
() a post-treatment at 1673 K (1400C) where it
dissociates. The AIF3 does, however, have
the added benefit that it has a very high
Nitridation Time (min) vapor pressure at the reaction temperatures
of interest. Therefore, the surface area and
Figure 10.13 Low temperature kinetics of the nitri- degree of porosity of the support material
dation of aluminum. (Choi, S.W. and Lee, S.J.,
'Synthesis of aluminum nitride from metal alumi- increase as the AIF3 sublimes. The reaction
num powders,' J. Korean Ceram. Soc., 22(6), 80, becomes more and more efficient.
1985. Reproduced by permission of the Korean From a process point of view, the Union
Ceramic Society, Seoul, South Korea.) Carbide method (Mandorf, 1967) involves an
246 Processes
extended heat treatment at temperatures in
the range of 1073-1373K (800-1100C). In
the particular example cited (Mandorf, 1967),
a 4.2 kg (9.31b) mixture of AI, AlN and AIF3
(43wt%, 43wt% and 14wt%, respectively)
was heated to 1123 K (850C) while the N2
flow rate was maintained at 4.7 slm (standard
liters per minute) (0.17 sefm (standard cubic
feet per minute. Once the temperature of
the reactant mixture reached 1123 K (850C),
the reaction became self-sustaining and the
temperature began to increase. The rate of
reaction was regulated in such a way as to
maintain a temperature below 1373 K
0100C) by adjusting the N2 flow rate into
the reactor. After the reaction was complete,
the temperature of the charge dropped
below 1098 K (825C). From the data given
in this example, one can estimate that the
reaction time was approximately 3 h. Because
of the exothermic nature of the AlN reaction,
power consumption was negligible (Mandorf,
1967) after the initial heating of the reactant
mixture to 1123 K (850C). The synthesized
AlN product was then crushed and milled to
an acceptable size (Chapter 18).
Several other methods for dealing with the
coalescence of Al have been developed by
Toyo Aluminum Co. (Ito and Yoneda, 1987,
1988; Uchimura et al., 1987). In the first
improvement of the Union Carbide process,
Toyo (Ito and Yoneda, 1987) carried out an
in-situ formation of the carrier (diluent) by
pretreating the Al metal in N2 below the
melting point of AI. Here, a skin of AlN
formed on the Al particles which served to
prevent the coalescence during a second heat
treatment above the melting point of the Al
0073-1273K (800-1000C. The nitrided
product was found to be free of residual AI.
A second method of dealing with coalescence
(Ito and Yoneda, 1988) involved the formation
of an A120 3 skin on the Al particles by a
variety of chemical oxidation methods. One
of the chemical oxidation methods used was
to place the starting atomized Al for a short
time 0-30 min) in a hot water (323-363 K;
50-90C) bath. The oxide skin was of suffi-
cient thickness to increase the oxygen content
of the Al powder from 0.3 to 1.5 wt%. The pre-
treated Al powder was then nitrided by heat-
ing to a furnace temperature of 1173 K (900C)
(actual reaction temperature was significantly
higher) for 1 h. Post-reaction chemical analysis
could not detect residual Al in the AlN
product. With either of these two solutions,
however, the amount of diluent formed
during the pre-treatment is relatively small.
As a result, careful control over the reactor
temperature still must be maintained. With
respect to production rate, both of the Toyo
methods are improvements on the original
Union Carbide process (Mandorf, 1967)
because the volume of the reactor is not
partially filled with a diluent. The chemical
oxidation method (Ito and Yoneda, 1987) has
the drawback that it increases the oxygen
content in the AIN product. For applications
where thermal conductivity is important
(Chapter 1), this increase in oxygen content
is undesirable.
A process flow diagram for the controlled
direct nitridation of Al is shown in Figure
10.14. This flow diagram is based upon the
available open literature concerning direct
nitridation as a method of making AlN. A
high purity Al metal source is blended with
approximately 30-50% recycled AlN diluent
to decrease the net exothermic effect of the
reaction and to serve as a carrier (Mandorf,
1967). The Al is potentially pretreated to
form an oxide or nitride skin (Ito and
Yoneda, 1987, 1988). On an industrial scale,
the synthesis step would most likely be
carried out in a pusher or trough-type reactor
(Chapter 6). From the examples cited in the
literature (Mandorf, 1967; Ito and Yoneda,
1987, 1988), the reaction time would be
approximated at 2-3 h at a temperature of
1173-1373K (900-1100C) in the presence of
N2 and/or NH3. The lightly sintered AlN
product would then be crushed and milled
(jet milled or attritor milled) (Chapter 18)
into a free flowing powder. Optionally, an
 Gas-solid reactions 247

:--------------- -------------,
: :
: Pretreatment
:L______________
I
:
:
I A~IN----~I~~------~
L-___

Optional
_____________ :
+
Blending

Reaction 2AI+N2(g) -+ 2AIN

>1073 K

Intermediate Milling

Secondary Reaction

Optional
Ultrafine Milling

Oversize

Optional Diluent Recycle

Packaging

Figure 10.14 Block flow diagram for controlled direct nitridation of AIN.
248 Processes

H
(a) 1.0pm

(b) 10pm

Figure 10.15 SEM of (a) ART (photo courtesy of Advanced Refractory Technologies, Inc., Buffalo, NY) and
(b) Toyo direct-nitrided AlN products.

intermediate milling step to expose fresh
surfaces and a second heat treatment can be
carried out to complete the conversion.
Finally, according to the end-use application,
surface treatment (surface oxidation) and
classification steps would be used. Scanning
electron photomicrographs (SEMs) of two
different grades of direct nitrided AlN are
shown in Figure 10.15.
Self-propagating direct nitridation
In light of our previous discussions regarding
SHS reactions, the highly exothermic nature of
the direct nitridation of Al would, at first
glance, indicate that an SHS reaction between
Al and N2 gas would be a simple extension of
the more controlled Union Carbide (Mandorf,
1967) and Toyo (Ito and Yoneda, 1987, 1988)
processes. Because of the rapid nature of
SHS reactions, however, problems associated
with N2 availability and product dissociation
become increasingly important. For the con-
trolled nitridation of AI, N2 availability for
reaction with Al was inhibited by the melting
Gas-solid reactions 249
and subsequent coalescence of the AI. In gas-
solid SHS reactions, however, N2 permeation
also becomes important. The degree of con-
version to a nitride of a metal particle depends
on the local availability of N 2. The more
porous the compact, or the higher the N2 pres-
sure, the more N2 is present and, hence, more
favorable conditions for nitride formation
result. If a sufficient concentration of N2 for
complete conversion does not exist on a local
level, then a pressure differential exists
between the combustion front and the N2
gas outside the compact. As a result, N2 gas
must be transported to the combustion front
and permeation of the N2 through the com-
pact and/ or product becomes important. The
calculated critical N2 pressure (at 298 K; 25C)
is plotted as a function of compact density
for both the AIN and Si3N4 formation reac-
tions in Figure 10.16 (Dunmead, Munir and
Holt, 1989). It should be noted that the critical
N2 pressure was calculated assuming N2 to
be an ideal gas and, thus, is an upper limit.
The calculations presented in Figure 10.16
illustrate that, unless the SHS reaction is

3500 350

-
E
~
Q)
3000 11
..... 2500' D
D Si
(?
a..
5
Q)
.....
::s .Ti - 250 ::s

C/)
C/) Nb C/)
C/)
Q)
..... 2000 D .....
Q)
a..
c:
D
a..
c:

-
1500

Q)
150

-
Q)
0) 0)
0
..... D 0
.....

D
Z 1000 r- D Z
(tj
i (tj
u
+='
.;::
()
500 ~ g i 50
u
+='
.;::
()
0 I I I I
0
30 40 50 60 70 80

Porosity( %)
Figure 10.16 Calculated critical nitrogen pressure of complete nitridation of AI, Si and Nb compacts with-
out nitrogen permeation. (Dunmead, S.D., Munir, Z.A. and HoIt, J.B., 'Gas-solid reactions under a self-
propagating combustion mode,' Solid State Ionics, 32-33, 474-81, 1989. Reprinted with kind permission
of Elsevier Science-NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)
250 Processes
carried out under very high pressures, N2
permeation will be a factor and, thus, must
be considered.
Prokudina et al. (1981) first examined the
synthesis of AIN in a truly self-propagating
mode. An 81 (2.1 gal) reactor similar to that
used for the synthesis of TiC (Figure 10.1)
was used at elevated pressure. The effect of
added diluent AIN on the product nitrogen
content for two different sources of Al com-
busted under 10MPa (98.7 atm) ofN2 pressure
is shown in Figure 10.17. It is clear from these
results that the level of nitriding greatly
depends on the purity of the starting AI. The
low purity Al (90% - curve 2) does not nitride
above 31 % at any level of dilution while the
higher purity Al (99% - curve 1) nitrides to
>33% (theoretical AlN = 34.1 % N). The opti-
mum level of AIN dilution for the higher
~ Combustion (ed. AG. Merzhanov), 1981. Repro-
!
-
32
c Macrokinetics, Russian Academy of Sciences,
1!l
c
0 30
()
c
-
Q)
e
Ol
28
Z Nitrogen (N2) pressure is the other major
26 ~ ____L-____L-____ ~ ____ ~ __
o 20 40 60 80
AIN Diluent Content (wt %)
Figure 10.17 Effect of AIN diluent content on
degree of nitridation for combustion of (1) high
and (2) low purity Al sources under nitrogen at
10 MPa. (Prokudina, V.K., Shestakova, T.V., Boro-
vinskaya, I.P., Kuznetsova, I.G., Gracheve, N.A
and Nedel'ko, E.I., 'Production of aluminum nitride
of the SHS type and highly dense ceramics made
from it,' in Problems of Combustion Technology-
Materials of the Third All-Union Conference on the
Technology of Combustion (ed. AG. Merzhanov),
1981. Reproduced with permission of the Institute
of Structural Macrokinetics, Russian Academy of
Sciences, Chernogolovka, Moscow, Russia.)
3
i~ 32
r<.X-X-X
X4
E
1!l
c
8 30
c
Q)
g
Ol
Z 28
26 ~--~~--~----~----~---
6 8 10 12 14
Nitrogen Pressure (MPa)
Figure 10.18 Effect of nitrogen pressure on degree
of nitridation for combustion of Al when diluted
with (3) 65 and (4) 50 wt% of AIN. (Prokudina,
V.K., Shestakova, T.V., Borovinskaya, I.P., Kuznet-
soya, I.G., Gracheve, N.A and Nedel'ko, E.I.,
'Production of aluminum nitride of the SHS type
and highly dense ceramics made from it,' in
Problems of Combustion Technology-Materials of the
Third All-Union Conference on the Technology of
duced with permission of the Institute of Structural
Chernogolovka, Moscow, Russia.)
purity Al was found to be approximately
60wt%AlN.
factor (in addition to dilution) which influences
the SHS of AlN (Marin-Ayral et al., 1995). The
degree of nitridation as a function of N2 pres-
sure is shown in Figure 10.18 (Prokudina et al.,
1981) for two different amounts of diluent AlN.
The results indicate that N2 pressures of
approximately 10 MPa (98.7 atm) are sufficient
for maximum nitridation. Residual Al results
when the N2 pressure is too low. It was also
reported (Prokudina et al., 1981) that an optimal
loading level of approximately 2 kg (4.4lb)
existed for the 81 (2.1 gal) reactor (Prokudina
et al., 1981). At lower loadings, the thermal
losses to the reactor walls become significant,
while at higher loadings (increased density)
N2 permeation is decreased.

100
~
80
;g
~
c: 60
0
" the apparent need for elevated N2 pressures
CD
> Density of AI
40 Compact
()
054%
20 .65%
.70%
0
100 200 300
0
Nitrogen Pressure ( MPa)
Figure 10.19 Effect of nitrogen pressure on conver-
sion of undiluted Al compacts in an SHS mode.
(Dunmead, S.D., Holt, J.B. and Kingman, D.D.,
'Simultaneous combustion synthesis and densifica-
tion of AIN,' in Combustion and Plasma Synthesis of
High-Temperature Materials (eds Z.A. Munir and
J.B. Holt), pp. 186-94, 1990. Reprinted with
permission of VCH Verlagsgesellschaft mbH,
Weinheim, Germany.)
The combined effects of N 2 pressure and
green compact density on conversion are
shown in Figure 10.19 (Dunmead, Holt and
Kingman, 1990) for undiluted Al samples. As
the N2 pressure is increased from 20.7MPa
(204 atm) to 103 MPa (1020 atm) the degree
of conversion increases. This result can be
explained by the fact that the local availability
of N2 increases with increases in N2 pressure.
As shown in Figure 10.19 (Dunmead, Holt and
Kingman, 1990), it appears that for all three
'green' compact densities that the product
is approaching full conversion in the 120-
140MPa (",1200-1400atm) N2 pressure range.
Indeed, when Al samples were combusted at
310 MPa (3060 atm) all of the products were
fully converted. These data (Figure 10.19)
also show the effect of compact density on
the extent of conversion. At a given N2 pres-
sure, the degree of conversion decreases with
an increase in 'green' compact density. This is
Gas-solid reactions 251
due to a decrease in the local availability of N2
as the pore volume decreases. As the N2 pres-
sure increases, the degree of conversion for all
three densities approaches the same level.
From a process point of view, the synthesis
of AIN in an SHS mode is complicated by
during the reaction. The benefits that are
gained from short reaction times may be
offset by the increased capital necessary to
handle high N2 pressures. In addition, for
the synthesis of AlN, the adaptation of the
high pressure batch-type SHS reactions into
an industrial scale continuous synthesis pro-
cess would be very difficult. Again, the advan-
tages that SHS-type reactions offer begin to be
lost as the process becomes more and more
complicated.
Reactor concepts
The reaction kinetics of the direct nitridation
of atomized Al particles at higher tempera-
tures relative to those shown in Figure 10.13
are given by Hotta et al. (1988) (Figure 10.20).
The reactivity increases gradually up to 1623 K
(1350C) where a dramatic increase occurs. It
has been claimed (Hotta et al., 1987) that the
rate-controlling step at temperatures below
1623 K (1350C) is N2 diffusion through a
protective AlN layer that surrounds the Al
particles. At temperatures greater than
1673 K (1400C), however, it is believed that
thermal stresses cause a degradation of the
AlN layer, allowing the molten Al to escape
and subsequently be nitrided. This results in
an extremely high reaction rate. These data
(Figure 10.20) indicate that, under proper
conditions, atomized Al can be completely
nitrided in 3-5 s.
The rapid rate of reaction for direct nitrida-
tion (Shintaku, 1986) has been utilized by
atomizing molten Al into an N2 atmosphere
at elevated temperatures. As shown in
Figure 10.21, the atomized Al is introduced
at the top of a vertical reactor and flows co-
current with a recirculating N2 gas stream.
252 Processes

100r---------~._----~------~------------------~

80

~ 60
c:
0
.~

~
c:
0
() 40
1823 K
A. 1773 K
1723 K
20
~ 1673 K

1423 K

0~----~----~------~----~----~------6~~

Nitriding Time (5)

Figure 10.20 High temperature kinetics of the nitridation of AI. (Hotta, N., Ichiya, 1., Saito, N., Yasukawa,
S., Tada, K. and Kitamura, T., 'Continuous synthesis and properties of fine AIN powder by floating
nitridation technique: Nippon Ceramics Kyokai Gakujutsu Ronbun-shu, 97(7), 731-35, 1988. Reproduced
with permission of the Ceramic Society of Japan, Tokyo, Japan.)

Over the temperature range studied (1193-
1248 K; 930-975C), the highest degree of
conversion was only 60%. It is likely that the
high residual Al contents were the result of a
combination of low temperature and short
residence time. The AIN-AI product from
the reactor shown in Figure 10.21 was subse-
quently post-treated at 1473-1773 K (1200-
1500C) in N2 to obtain pure AlN.
Showa Aluminum Company (Tsukamoto,
Isoyama and Horita, 1987) developed a con-
tinuous 'floating nitridation process' that
also utilizes the rapid reaction rate at even
higher temperatures. A schematic of the reac-
tor used is shown in Figure 10.22 (Tsukamoto,
Isoyama and Horita, 1987). This reactor com-
prises a reactant supply section, a reaction
section and a product collection section. The
reactant supply section comprises a vessel
housing the reactant Al powder and an agita-
tor for stirring it. Means of supplying N2 and
feeding atomized Al are also provided. Alu-
minum powder is entrained by the N2 gas
and floats upwards through the reaction
section in dilute flow. The agitator in the
reactant supply section serves to prevent
coagulation of the Al powder and aids in
entrainment of the AI. The reaction section
comprises a heated vertical tube that is
maintained between 1623 and 1823 K (1350
and 1550 C). Finally, after exiting the reaction
section, the product is separated from the N2
gas and collected. Using an apparatus such as
that shown in Figure 10.22 makes it possible to
control the residence time at temperature by
altering the gas velocity and the length of the
reaction zone. Typical reaction times reported
(Hotta et al., 1987) were approximately 5 s. The
product made by this method is reported to
have a crystal size of from 0.1 to 0.3 fJ,m, a
surface area of 8 m 2/ g and an oxygen content
of 1.2 wt%. Several improvements, including
 Gas-solid reactions 253

Atomized AI

Heaters

'-+

AIN Product
Figure 10.21 Schematic illustration of apparatus for atomization and nitridation of molten AI. (Adapted
from Shintaku, 1986.)
254 Processes

AIN Product

Nitrogen --+ ==::;g::=:::;,

. ....
o

....- .......
0" 0

...:::
. . ... . -:
~
~
I- . .. -.

Agitator
Figure 10.22 Schematic illustration of apparatus for floating nitridation of atomized Al powder. (Adapted
from Tsukamoto, Isoyama and Horita, 1987.)

multiple pass reactors and the use of NH3
instead of N2 have been reported (Horita
et al., 1988; Tada et al., 1988; Yoshimoto,
Horita and Kitamura, 1988a,b; Yoshimoto
et al., 1988; Hotta et al., 1994; Chang, Rhee
and Baik, 1995).
One of the major concerns with the floating
nitridation processes (Shintaku, 1986; Hotta
et al., 1987) is the production of AlN whiskers
on the feeding tube (Watanabe et al., 1994) or
on the wall of the reaction vessel. It is believed
that the highly exothermic nature of this
reaction drives temperatures, on a local level,
to the boiling point of Al (2793 K (2520C.
This results in vapor phase growth of AlN
whiskers on the cooler walls of the reactor
(thermophoresis effect). This phenomenon
has been utilized to develop a process for
manufacturing AlN whiskers (Tsukamoto,
Isoyama and Hotta, 1987). Periodically, when
the deposit of whiskers became substantial,
the N2 flow rate was pulsed to blow the AlN
whiskers into a collection chamber. In order to
run the floating nitridation process (Hotta
et al., 1988) in a continuous mode, the whiskers
had to be periodically scraped from the walls
of the reactor with a tungsten wire. The forma-
tion of these whiskers on the walls of the
reactor is a hindrance to the continuous
production of AlN powder by this method.
Problems associated with whisker forma-
tion in a floating nitridation process were
recently dealt with by adding an AlN diluent
to the reactant feed (Weimer et al., 1992, 1993,
 Gas-solid reactions 255
1994). In this case, the inert AIN particles, AIN property comparison
because of their lower temperature and
The only two commercial processes for the
closer proximity, acted as preferential reaction
manufacture of AlN powder are by carbo-
sit~s relative to the hotter reactor walls. By
thermal nitridation of Al2 0 3 and direct
USing a 50/50 mixture of Al and AIN, the
nitridation of AI. Comparative physical prop-
wall deposition was decreased from greater
erties of AIN powder made by the carbo-
than 50 wt% to less than 3 wt%. A schematic
thermal, direct nitridation and SHS synthesis
of the entrained flow reactor used in this
routes are given in Table 10.6. One of the
work is shown in Figure 10.23. Here, the
apparent major differences between the direct-
high puri~ atomized Al is dispersed at high
nitrided/SHS and carbothermal powders is
velocIty Into a vertical reaction chamber
the presence of Ca as an impurity in the
where it enters as a dust cloud. The walls of
carbothermally produced powders. Calcium
the reactor are maintained at a temperature
(Ca) is typically present in A12 0 3 , while it is
in the range of 1873-2373 K (1600-2100C).
r~rely present in metallic AI. For most applica-
As was the case with the floating nitridation
tions, however, since Ca tends to act as a sinter-
method (Hotta et al., 1988), the residence
ing aid in AlN ceramics, the presence of these
~ime at temperature can be controlled by alter-
levels of Ca is not of significant concern. The
Ing the geometry of the reactor tube (diameter
data in Table 10.6 also show that the metallic
and length) and the gas velocity. After exiting
impurity contents in AIN, produced by direct
the react~r tube, the product is rapidly
nitridation or SHS, vary greatly depending
quenched In an expanded cooling zone prior
upon the quality of the Al raw material used.
to product collection. The quenched product
It should also be noted, however, that the
typically contains small amounts of residual
higher purity Al raw materials will also carry
Al that must be converted into AlN using a
a cost premium. As a result, both the powder
lower temperature (1373 K (1100 DC~ finishing
manufacturer and the part producer must
treatment.
evaluate the cost-performance ratio on an
The effect of temperature on the character-
application by application basis. With respect
istics. of the AIN product produced by this
to oxygen and carbon contents and surface
entrained flow process are shown in Table
areas, all of the powders listed in Table 10.6
10.5 (Weimer et al., 1992). These data show a
tend to fall in the same range. The other
minimum in the surface area of the product
factor that, in general, differentiates a direct-
at approximately 2073 K (1800 DC). Below this
nitrided/SHS powder from a carbothermal
temperature, the surface area increases with
one is the width of the particle size distribu-
decreasing temperature due to less particle
tion. ~ecause a grinding step is generally
growth. As the temperature increases above
us.ed In the direct nitridation/SHS processes
2073 K (1800C), on the other hand, the
(FIgure 10.14), the particle size distribution in
surface area increases as more and more fine
these powders is typically wider. Depending
AlN particles are formed from the reaction
on the application, this wider particle size dis-
betwe~n gaseous Al and N 2 In addition, by
tribution mayor may not be of benefit. The
operating the reactor near the dissociation
presence of any large particles inhibits densifi-
temperature of AlN (approximately 2473 K
cation by pressureless sintering (Chapter 2).
(220~ C extremely high surface area (e.g.
20 m / g) product could be made. At these
SILICON NITRIDE
high temperatures, it is likely that substan-
tially all of the AlN is formed from the gas Silicon nitride (Si3 N 4 ) is commercially pro-
phase during cooling in the cooling portion duced using processes based upon (1) direct
of the reactor. nitridation of silicon metal (Pompe et al.,
256 Processes
Fresh AI

Blender
Recycle
AIN

Reactor

...
Heat Feed
Treatment

......
.~
I I

.."...
r:o;:::.I

Reactor

Particle
Classifier

Milling

Coarse Fine
Product Product
Packaging Packaging

Figure 10.23 Schematic illustration of transport flow process for rapid direct nitridation of mixtures of Al
and AIN. (Weimer, AW., Cochran, G.A, Eisman, G.A, Henley, J.P., Hook, B.D., Mills, L.K., Guiton, I.A,
Knudsen, AK., Nicholas, N.R., Volmering, J.E. and Moore, W.G., 'Rapid process for manufacturing
aluminum nitride powder: J. Am. Ceram. Soc., 77(1), 3-18, 1994. Reproduced by permission of the
American Ceramic Society, Westerville, OH.)
 Gas-solid reactions 257
Table 10.5 Effect of reactor temperature on AIN powder properties made by rapid direct nitridation
process (adapted from Weimer et al., 1992)

Temperature Residence Oxygen Nitrogen A1N yield Surface area

(K (OC)) time content content (%) (m 2 /g)
(5) (wt%) (wt%)

1873 (1600) 5.4 0.60 31.6 93 4.2

1973 (1700) 5.0 0.49 29.3 86 3.7
2073 (1800) 5.3 0.45 29.5 86 2.0
2173 (1900) 4.6 0.28 29.9 91 2.2
2273 (2000) 5.2 0.23 30.8 90 2.5
2373 (2100) 4.3 0.14 25.5 75 5.5
2473 (2200) 4.3 0.16 27.1 79 19.7

1985; Ito, 1990), (2) carbothermal nitridation of
Si02 (Komeya and Inoue, 1975; Cochran et al.,
1994) and (3) thermal decomposition of silicon
diimide (Iwai, Kawahito and Yamada, 1980,
1983; Yamada, 1994). As would be expected,
the product quality and cost are greatly
dependent upon the route which is used. In
this section, the direct nitridation reaction
will be discussed with respect to how its
nature impacts the process considerations
and product characteristics.
As was the case with the direct nitridation
of AI, the direct nitridation of Si (equation
10.12) appears very simple at first glance.
3Si + 2N2 (g) ---> Si3N4 (10.12)
Referring to the data given in Table 9.4, it can
be seen that this reaction is highly exothermic,
liberating 745.8kJ/mol and yielding an adia-
batic temperature of 4002 K (3729C) (not
accounting for the heat of dissociation).
Because of the exothermic nature of this reac-
tion, many of the same concerns that compli-
cate the AlN process are also present in the
Si3N4 process.
As was discussed in Chapters 1 and 2, Si3N4
exists in two main polymorphic forms, low
temperature a-Si3N 4 and high temperature
;3-Si3N4. Use can be made of the a to ;3
phase transformation (approximately 1873 K
(1600C)) in the densification of Si3N 4. This
phase transformation tends to create elon-
gated grains (Chapter 2) in the microstructure
which increase the fracture toughness of Si3N4
parts which are made (Pyzik and Carroll,
1994). Consequently, high quality Si3N4

Table 10.6 Comparison of selected powder properties of AIN made by various routes

Method Manufacturer Surface area Oxygen Carbon Ca Si Fe d so

(m 2 /g) (wt%) (wt%) (ppm) (ppm) (ppm) (/-lm)

Carbothermal Dow 2.7 0.9 <0.06 100 60 20 1.5

Carbothermal Tokuyama Sodab 3.2 1.0 0.05 300 80 10 2.2
Direct nitridation Toyoc 4.3 1.0 0.03 60 50 2.0
Direct nitridation ARTd 2.5 1.1 0.10 1000 1000 1.6
SHSe ISMAN f 1.0 0.8-1.2 0.2 7 570 1200 2.4

a XUS35548 grade.
b H grade.
cUF grade.
d A200 grade.
e Measurements done at The Dow Chemical Company.
f Powder courtesy of A.G. Merzhanov.
258 Processes
powders typically contain high concentrations
(i.e. >90%) of the low temperature 0: phase. In
order to make a high quality Si3N4 product by
the direct nitridation route, the exothermic
nature of the reaction must be controlled so
as to keep the reaction temperature below
that of the 0: to (J transition. This control, how-
ever, must be balanced with the need to obtain
complete conversion of the Si metal in a
reasonable amount of time.
Controlled direct nitridation
Results of a nitridation study in which Si metal
was heat treated at 1573 K (1300C) for 5 h in
an atmosphere containing various ratios of H2
and N2 are shown in Figure 10.24 (Ito, 1990). It
is clear from these results that, even after 5 h,
the reaction is not complete. In addition, the
amount of the low temperature 0: phase
tends to increase with increasing H2 contents.
Similar results are shown in Figure 10.25 (Ito,
1990) where the Si conversion and 0: phase
content are plotted as a function of the ratio
of Si to Si3N4 diluent in the feed material for
pure N 2. Here, it can be seen that as the dilu-
ent content increases, both the conversion and
the 0: phase content tend to increase. It is
believed that both the Si3N4 in the feed and
the H2 in the reactant gas act as diluents

100 ~---r----~--~----~---,--~'-----~---r----r----' 100

#
~
;g-
oo
~

~
+
"<t 50 50 co:
Z +
~
(')

~
-... ~
"<t
Z
(')

00

a ~--~--~~--~--~----~--~----~--~----~--~ a
o w 100

Figure 10.24 Effect of H2 content on degree of conversion (2) and a-phase content (1) for controlled direct
nitridation of Si. (Ito, T., 'Preparation of pure alpha-silicon nitride from silicon powder,' J. Mater. Sci. Lett.,
9,19-20, 1990. Reproduced by permission of Chapman & Hall, London, UK.)
 Gas-solid reactions 259

100 r_--,_---r---.r---~---r_I--,----r---,----~--~ 100

2
------. -------- .. ------- ........... . ........
~

--"---0--- ....
~
~
1 -----0-----_ -- ...... -Q
..............
Z
"<t
-- "- -.. ....
(')

i:i5 .... ~

.9
"0
Q) 50 r- - 50
t::
Q)
>
c:
0
()
c:
0
g
i:i5

o ~__~__~__~___~1_ _~1__~1_ _~1~_ _ L __ _~~

o
o W 100

Si / (Si + a-Si 3 N4 ) (wt %)

Figure 10.25 Effect of a-Si3N4 diluent content on degree of conversion (2) and a-phase content (1) for
controlled direct nitridation of Si. (Ito, T., 'Preparation of pure alpha-silicon nitride from silicon
powder,' J. Mater. Sci. Lett., 9, 19-20, 1990. Reproduced by permission of Chapman & Hall, London, UK.)

which help to moderate the exothermic nature
of the direct nitridation reaction.
A review of the relevant literature indicates
that the manufacture of high quality a-Si3N 4
by controlled direct nitridation follows a pro-
cess similar to that shown in the block flow
diagram given in Figure 10.26. As shown,
the direct nitridation process for high quality
a-Si3N4 is much more complex than might
be inferred by the simple reaction given in
equation 10.12. Various metals (e.g. Fe) are
known to be catalytic in the direct nitridation
process (Grieveson, Lumby and Stokes, 1974;
Ito, 1990). Their presence helps to disrupt the
protective Si3N4 layer that forms around the
silicon particles and also promotes the a to (3
phase transformation. As a result, the silicon
used for making a-Si3N 4 is typically of high
purity (Ito, 1990; Pompe et aI., 1985). As was
mentioned above, a-Si3N 4, which is generally
blended with the starting Si (Ito, 1990;
Schwier, 1983), acts as a diluent which
decreases the net exothermic effect of the reac-
tion. As was the case with AlN, the Si3N4
diluent also increases the bed porosity and
helps prevent coalescence of the metal which
can further restrict gas transport to the
unreacted metal.
The tight low temperature control that is
necessary to avoid temperature excursion
and (3 phase formation requires the primary
and secondary reaction steps to be for
260 Processes

Si
I alpha - Si 3 N4
I~
+ +
~~

+
Precursor Preparation

N2 and/o r NH3 ---+

+
Primary Reaction 3Si + 2N2(g) =Si3 N4

+
>1573 K

Intermediate Milling

N2 and/o rNH3---+
+
Secondary Reaction 3Si + 2N2(g) =Si3 N4
>1673 K
~~
Ultrafine Milling

Oversize
+
Classification

~
HF, HCI ---+ Acid Leaching --+ Waste Acid Solution

+
Filtration / Washing

+
( alpha - Si 3 N4 J Diluent Recycle
.....
Figure 10.26 Block flow diagram for controlled direct nitridation process for the manufacture of a-Si3 N 4 -

extended periods of time. It has been reported
(Ito, 1990) that a reaction sequence comprising
a 5 h heat treatment at 1553 K (1280 DC) fol-
lowed by an intermediate grinding step and
an additional 6 h at 1593 K (1320C) was
sufficient to complete the reaction. The inter-
mediate grinding step is needed to expose
unreacted Si metal prior to the secondary
heat treatment. A one-step batch operation
reportedly (Nakamura, Kuranari and Ima-
mura, 1990) requires up to 100 h of heat
treatment.
In order to control the particle size distribu-
tion and reduce the degree of agglomeration,
final grinding and classification steps are
used. The grinding step is typically carried
out using Si3N4 media (Nakagawa and Kato,
1990) to minimize metal impurity pickup. The
yield loss involved in obtaining a high grade
product after the multistep air classification
process (Nakagawa and Kato, 1990) may be
substantial and depends upon the tempera-
ture control achieved during the synthesis
reaction.
The final step in the direct nitridation
process is an acid leaching step to remove
metal impurities and surface oxides from
the milled product (Cambier et al., 1990;
Nakamura, Kuranari and Imamura, 1990).
Industrial grade silicon powders contain
substantial metallic impurities that, if left in
the Si3N4 product, would result in inferior
mechanical properties, especially at high tem-
perature. One alternative to post-reaction
leaching would be the addition of an Si
metal refining step in the front end of the
process (Nakamura, Kuranari and Imamura,
1990). This step, which would include a
fusion-solidification step followed by addi-
tional grinding and acid leaching, would add
to the cost of the overall process.
Reactor concepts
A variety of continuous reactors have been
developed for the direct nitridation of Si
including pusher furnaces, moving bed
Gas-solid reactions 261
furnaces, rotary kilns and fluidized beds
(Fukuoka and Fukuhira, 1990; Masanori,
Hirofumi and Mutsuo, 1991; Masanori et al.,
1993). Of these, the fluidized bed reactors
(Fukuoka, Shimizu and Fukuhira, 1990; Masa-
nori, Hirofumi and Mutsuo, 1991; Masanori
et al., 1993) are probably the most advanced.
One such reactor configuration is shown
schematically in Figure 10.27 (Fukuoka and
Fukuhira, 1990). A two-stage fluidized bed
reactor is used, one stage for carrying out pri-
mary nitridation and a second for completing
the reaction. The reactor is equipped with a
feeder-disperser mechanism that allows a
well dispersed Si feed to be metered through
a conduit into the bottom of the first fluidized
bed. The granulated feed is fluidized by N2
and/ or NH3 gas that passes at high velocity
through the disperser plate at the bottom of
the reactor. The first reactor is also equipped
with an exit conduit in which intermediate
product is entrained with the exhaust gas
and transferred from the first reactor into the
second. The second reactor is identical to the
first with the exception that the exhaust gas
passes through a particulate separation and
collection system. After the final product is
removed, the exhaust gas stream can then be
recycled back to either of the reactors, if
desired.
When using the reactor configuration
shown in Figure 10.27, the first reactor was
typically kept at a lower temperature (e.g.
1523 K (1250C than the second (e.g. 1673 K
(1400C. This was done so that the reactant
Si was partially nitrided at a temperature at
which the rate of the exothermic reaction
was not extremely rapid. In this way, the reac-
tion was essentially diluted in situ in a manner
analogous to that described previously in the
discussion regarding the AlN reaction. In
the examples given (Masanori, Hirofumi and
Mutsuo, 1991), the two fluidized beds were
approximately 0.08 m (3.2 in) in diameter and
0.3 m (11.8 in) in height. The feed material
was fed at a rate of 0.2kg/h (O.44Ib/h),
which corresponded to a residence time of
262 Processes
Si + Si3N4 Feed

Gas l Solid
Separator

Vent

.,; ri::~;;!~
..-.. .....
.. . . ...-
to '"
':.

Disperser .' .' :.: : .::., '.

Plate ---+

Figure 10.27 Schematic illustration of two-staged fluidized bed reactor for controlled direct nitridation of
Si3 N 4 (Adapted from Fukuoka and Fukuhira, 1990.)

approximately 2.5 h per reactor. Under these
conditions, the degree of conversion in the
first and second reactors was 50% and 95%,
respectively. The final product was 80% a-
Si3N 4. Further optimization with respect to
both conversion and yield of a-Si3N 4 should
be achieved by increased residence time at
lower temperatures or with the addition of
a-Si3N4 as a diluent.
A second variation of a two-stage direct
nitridation process (Fukuoka et al., 1993)
involved the substitution of a moving bed
reactor for the second fluidized bed shown
in Figure 10.27. In the example cited (Fukuoka
et al., 1993), a moving bed reactor 0.08 m
(3.2 in) in diameter and 0.5 m (1.6 ft) in height
was maintained at 1673K (1400C) and sup-
plied with an intermediate product from a
fluidized bed reactor. By increasing the
residence time in the moving bed reactor
(3.7h), a completely nitrided product with
87% a-phase was made.
Self-propagating direct nitridation
The discussions above regarding the direct
nitridation of Si might lead one to the conclu-
sion that this reaction is inherently very slow.
In fact, however, under the proper conditions
(temperature and pressure) this reaction is
extremely rapid and can take place in a self-
propagating combustion mode. The effect of
 Gas-solid reactions 263
100

,--
J
J 0
----------------------~
80 J
J

;g
:0
J

J
~ J
60 J
c: J
0 I
'c;;
.... I
Q) I
>
c:
0 I
I

0 40 I o Si
,
() I

,,
I Ti
Nb

I
20

0
0 100 200 300 400
Nitrogen Pressure (MPa)
Figure 10.28 Effect of nitrogen pressure on conversion of undiluted Si compacts in SHS mode. (Dunmead,
S.D., Munir, Z.A. and Holt, J.B., 'Gas-solid reactions under a self-propagating combustion mode,' Solid
State Ionics, 32-33, 474-81, 1989. Reprinted with kind permission of Elsevier Science-NL, Sara
Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.)

N2 pressure on the conversion of undiluted Si may be liberated simply by the formation

to Si3N4 in a self-propagating combustion
mode is shown in Figure 10.28 (Dunmead,
Munir and Holt, 1989). Until the N2 pressure
is greater than 50 MPa (494 atm), ignition does
not occur (the 50 MPa specimen only partially
ignited). At higher pressures, however, the
reaction does become self-propagating and
the conversion quickly jumps to greater than
92%. The exact pressure at which the Si3N4
reaction will become self-propagating varies
with the synthesis parameters (e.g. dilution,
purity of Si, density, etc.) and has been
found to range from 3.0 MPa (29.6 atm)
(Hirao et al., 1986; Lis et al., 1991) to 50MPa
(494 atm) (Holt, Kingman and Bianchini,
1985). Because of the limited degree of solid
solubility of nitrogen in Si, the only products
are a-Si3N 4, ,B-Si3N4 and free Si. This is as
compared to a system such as Ti-N in which
large degrees of solid solubility exist and heat
of the solid solution (Dunmead, Munir and
Holt, 1989). The effect of N2 pressure on the
a-Si3N 4 yield is shown in Figure 10.29 (Dun-
mead, Munir and Holt, 1989). After ignition
occurs, the amount of a-phase decreases
with increasing N2 pressure. This has been
attributed (Holt, Kingman and Bianchini,
1985) to an increase in the temperature of
combustion due to the increased N2 pressure.
As was the case with the controlled direct
nitridation reaction discussed above, the
addition of Si3N4 as a diluent is an important
process variable in the self-propagating varia-
tion of this reaction. X-ray diffraction patterns
of the SHS Si3N4 products made at 10 MPa
(98.7 atm) N2 pressure when diluted with
various amounts of a high a-Si3N 4 (98%) are
shown in Figure 10.30 (Hirao, Miyamoto and
Koizumi, 1986). Here, it can be seen that both
the degree of conversion and the a-phase
264 Processes
15

I
I
I
"0 I
I
CD I
:;: 10 I

-
I
CD I
"0 I
';'::
I
Z I
I
c:
,g I
I
I
I

i:i5 I
I
~ 5 I
a. I
<C I
I
I
I
I
I+-- No Ignition
I
I
I
I
I
o
o 100 200 300 400

Nitrogen Pressure (MPa)

Figure 10.29 Effect of nitrogen pressure on yield of o:-Si3N 4 from direct nitridation of Si in SHS mode.
(Dunmead, S.D., Munir, Z.A. and Holt, J.B., 'Gas-solid reactions under a self-propagating combustion
mode,' Solid State Ionics, 32-33, 474-81, 1989. Reprinted with kind permission of Elsevier Science-NL,
Sara Burgerhartstraat 25,1055 KV Amsterdam, The Netherlands.)

content increase as more diluent is added. The
type of Si3N4 diluent (i.e. a or (3) also plays an
important role in determining the phase com-
position of the final SHS product. The data
given in Table 10.7 (Hirao, Miyamoto and
Koizumi, 1986) indicate that Si3N4 formed
from the combustion reaction is primarily of
the same phase as that of the diluent that
was added. In the case where 0.4 moles of
high a-Si3N4 were added, the new product
(i.e. not added as diluent) synthesized was
approximately 80% a phase. If this product
was then used as the diluent in a subsequent
reaction with 0.4 moles of diluent, the product
would, in all likelihood, contain less a-Si3N4
than the product of the first reaction. If this
recycling of product as diluent is continued
indefinitely, ultimately the product will
comprise much {3-Si3N 4. Consequently, if the
ultimate goal of this work is to develop
a process by which to manufacture a high
a-Si3N4 content powder, then, from a process
point of view, a-Si3N 4 must be considered to
be a raw material.
The morphology of typical SHS Si3N4
products is shown in Figure 10.31 (Hirao,
Miyamoto and Koizumi, 1986; Lis et al., 1991).
The high (3-Si3N4 (95%) consists of large 50-
100 J-tm agglomerates compnsmg 1-5 J-tm
grains, as shown in Figures 1O.32(a) and (b).
This as-synthesized powder with a surface
area of 2 m 2 / g is relatively inert (Lis et al.,
1991) and must be milled to become sinterable.
After long milling times (>24h) the surface
area of the product was increased to 10m2 / g
and was sinterable. Such extensive milling
 Gas-solid reactions 265

a
aa

a 13 0.4SN

i 0.3SN

0.2SN

O.lSN

10 20 30 40 45

28/ Degree
Figure 10.30 X-ray diffraction patterns of SHS Si3N4 products made under nitrogen at 10 MPa (98.7 atm)
when diluted with various amounts of high a-Si3N 4. (Hirao, K., Miyamoto, Y. and Koizumi, M., 'Synthesis
of silicon nitride by a combustion reaction under high nitrogen pressure,' J. Am. Ceram. Soc., 69(4), C60-61,
1986. Reproduced by permission of the American Ceramic Society, Westerville, OH.)
procedures are likely to result in substantial By using high levels of a-Si3N 4 diluent, a sub-
contamination of the final product and will micron as-synthesized product was made.
add to the overall cost of a process based A recent variation (Merzhanov et al., 1991)
upon such technology. A smaller particle size of the combustion synthesis of Si3N4 appears
SHS Si3N4 product is shown in Figure to be very promising and involves the use of
10.31(c) (Hirao, Miyamoto and Koizumi, 1986). an ammonium halide additive to synthesize
Table 10.7 Phase composition data for SHS production of Si3N4

Starting powder mixture Combustion products

(wt%) (wt%)

Sample a-Si3 N 4 (3-Si3 N 4 Si a-Si3 N 4 (3-Si3 N 4 Si

0.2SN-a a 28.7 0.6 70.7 71.3 28.0 0.7

0.4SN-a a 51.5 1.1 47.4 87.2 12.8 0.0
0.2SN-(3b 5.6 23.7 70.7 13.2 82.6 4.2
0.4SN-(3b 9.9 42.7 47.4 18.2 81.4 0.4

aHigh a-Si3N 4 diluent - Ube SN E-10.

b High (1-Si3N 4 diluent - Denki Kagaku Industries SN-BS.
Source: Hirao, K., Miyamoto, Y. and Koizumi, M., 'Synthesis of silicon nitride by a combustion reaction under high
nitrogen pressure,' J. Am. Ceram. Soc., 69(4), C60-61, 1986. Reproduced by permission of the American Ceramic Society,
Westerville,OH.
266 Processes

I-------l
(a) 10.0 I'm

(b)

(c)

Figure 10.31 SEM of SHS Si3N4 powders. a) and (b), Lis, J., Majorowski, S., Puszynski, J.A. and Hlavacek,
Y., 'Densification of combustion synthesized silicon nitride,' Bull. Am. Ceram. Soc., 70(2), 244-50, 1991;
(c), Hirao, K., Miyamoto, Y. and Koizumi, M., 'Synthesis of silicon nitride by a combustion reaction under
high nitrogen pressure,' J. Am. Ceram. Soc., 69(4), C60-61, 1986. Reproduced by permission of the
American Ceramic Society, Westerville, OH.)

Figure 10.32 SEM of SHS high a-Si3N4 made by dilution with ammonium halides. (Photo courtesy of The
Dow Chemical Company, Midland, MI. Powder supplied by A.G. Merzhanov, Institute of Structural
Macrokinetics, Russian Academy of Sciences, Chernogolovka, Moscow, Russia.)
a high a-content product. Metallic Si was
admixed with ammonium fluoride and/or
ammonium chloride and ignited under ele-
vated N2 pressure (4-30 MPa (39.5-296 atm.
The ammonium halide additives served two
purposes during the synthesis reaction. First,
they acted as a diluent to decrease the com-
bustion temperature to a point at which a-
phase formation was favored. Secondly,
these additives were gasified in the combus-
tion front and then reacted with Si to form
intermediate products (presumably silicon
diimides) which tend to form a-Si3N 4 after
the wave has passed. This method has been
used to produce Si3N4 which contained
greater than 90% a phase and little free Si.
The mixed morphology of the product made
by such an ammonium halide route is shown
in Figure 10.32. The product tends to consist of
both acicular and equiaxed particles of Si3N 4.
This type of morphology does not typically
lend itself to being highly sinterable, but it is
likely that further improvements and varia-
tions of this type of technology could lead to
Gas-solid reactions 267
f------j
1.0 JSm
the direct synthesis of a high a-Si 3N 4 powder
that is sinterable. It is important to note
that halide contaminants are known to have
deleterious effects on the high temperature
properties of Si3N4 parts (Chapter 19). In
addition, the highly corrosive atmosphere
caused by the combination of ammonium
halides and high temperatures combined
with elevated gas pressures will require
more exotic materials of construction for the
reactor. Nevertheless, this technology is a
significant advancement in the understanding
and manipulation of SHS reactions to form
advanced materials.
Si3N4 property comparison
The final part properties of high performance
silicon nitride ceramics are mainly determined
by the powder quality (Schwier, Nietfeld and
Franz, 1989), sintering additives (Pyzik and
Carroll, 1994) and processing conditions.
Both the powder quality and the cost of
manufacture are, to a large extent, determined
268 Processes
by the powder synthesis route. As a result,
there is a balance between performance and
cost that must be addressed by the Si3N4
part manufacturer. This evaluation of the
relative cost to performance will vary by
application. For example, in an application
where exceptional performance is not
required, low cost may be the driver. In
other applications, however, cost may be
secondary to performance. As was discussed
earlier, there are three routes of Si3N4 synth-
esis that are used commercially: 0) direct
nitridation (Pompe et al., 1985; Ito, 1990; Lis
et al., 1991), (2) carbothermal reduction (Chap-
ter 3) of Si02 (Cochran et al., 1994; Komeya
and Inoue, 1994) and (3) thermal decomposi-
tion (Chapter 15) of silicon diimide (Iwai et al.,
1980, 1983; Yamada, 1994). The properties of
Si3N4 powders made by the various processes
are given in Table 10.8.
In general, because of the purity level of
readily available silicon metal, the powders
made by direct nitridation and SHS processes
tend to have higher metallic impurity contents
than either the diimide or carbothermally pro-
duced powders. In addition, these powders
also tend to have higher halogen contents
that result from the grinding and leaching
steps shown in Figure 10.26. The diimide
and SHS-2 powders also tend to contain resi-
dual Cl resulting from the presence of ammo-
nium chloride in the synthesis processes. To
some degree, the oxygen contents of most
ceramic powders depend upon the surface
area. Most commercial Si3N4 powders tend
to be in the range of 1.0-2.0 wt% 0. Because
of incompletely reacted Si02 , the carbo-
thermal powders tend to be at the upper end
of this range. The carbothermally produced
powders also tend to have higher carbon
contents that result from either incomplete
removal of the free carbon or co-synthesized
SiC. From a particle size perspective, the
diimide and carbothermal powders have as-
synthesized surface areas in the range
8-14m2 /g and do not require extensive
milling treatments. The direct-nitrided/SHS
materials, on the other hand, must undergo a
milling step (and subsequent acid leaching) to
reach this range of surface area. The data in
Table 10.8 show, however, that when done
correctly, milling is an effective method of
decreasing the particle size (increasing the
surface area). Overall, the data shown in
Table 10.8 demonstrate that there are tradeoffs
in properties that depend upon the selection
of the synthesis route. Again, the cost to
performance ratio that is needed will vary

Table 10.8 Comparison of selected powder properties of Si3N4 made by various routes

Method Manufacturer Surface a content Oxygen Carbon Total Fe, Other impurities
area (%) (wt%) (wt%) Ai, Ca (ppm)
(m 2/g) (ppm)
Cl F

Di-imide Ubea 10 97 1.2 0.05 75 43 <50

Carbothermal Dow Chemicalb 11.5 >98 2.0 0.4 <100 <3 <50
Direct nitridation H.C. StarckC 18-21 92 1.9 0.2 800 15 1100
SHS-1d SUNY Buffalo 2.0 (10.5) 5 0.5 (1.5) 0.1 (0.15) 1600 _e -e
SHS-2f ISMANg 4.12 85 1.2 0.27 584 1200 <50
a SN E-lO.
b XU 35556 (Lot # CSN-120J).
c LC12. .
d Data from Lis et al. (1991). Values in parentheses measured after 24h milling.
e Not reported.
f Measurements done at The Dow Chemical Company.
g Powder courtesy of A.G. Merzhanov.

according to the application of the ceramic
part.
SUMMARY
The reactions to form many advanced ceramic
materials are highly exothermic and can be
carried out in either self-sustaining or self-
propagating combustion modes. Reactions
of this type are referred to as combustion syn-
thesis reactions. They hold great promise as
industrial methods of producing advanced
ceramic materials because they offer sim-
plicity (both in unit operations and equip-
ment), rapid production rates, decreased
energy consumption and little to no environ-
mentally harmful by-products. Even though
these reactions have demonstrated great
promise, significant efforts are needed to
develop them into industrially viable
products for manufacturing non-oxide cera-
mic powders which are both cost and quality
competitive than those made by more conven-
tional routes.
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PART FOUR
GAS PHASE SYNTHESIS PROCESSES
Gas phase synthesis processes have been
developed for the manufacture of both fine
powders and films (Part Eight). These pro-
cesses typically can produce materials of
high purity at high yields without the compli-
cations normally associated with handling
precursor solids or liquids. Powder synthesis
reactions are typically fast and can be carried
out in seconds using thermal aerosol (Chapter
12), laser (Chapter 13) or plasma (Chapter 14)
type reactors.
OVERALL PROCESS
In gas phase synthesis processes, multiple spe-
cies that provide the different chemical moi-
eties for reaction are fed to a heating device
(e.g. thermal aerosol, laser or plasma reactor)
and reacted. In some instances, a single precur-
sor molecule (generally an organometallic com-
pound) may provide the different moieties.
The product of reaction is typically amorphous
or crystalline molecules and molecular clusters
comprising submicron or nanosized crystal-
lites. These clusters result in particles either
by nucleation or by uninhibited coagulation.
The particles are collected downstream by fil-
tration, electrostatic precipitation or cyclones.
Reaction temperature and residence time are
crucial for determining the level of conversion
of the reactants and the morphology of the
product. Sometimes, a secondary heating step
may be necessary for crystallizing amorphous
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
products. Downstream post-processing steps
may be used to remove carbon, oxygen or
other chemical species which may be present
from incompletely reacted precursors.
SAFETY ISSUES
Gas phase synthesis of non-oxide ceramics
involves high temperature reactions of corro-
sive and toxic materials. It is imperative that
the equipment and material being used
be able to withstand the demands of such
processes.
The most widely used precursors are gas-
eous metal hydrides and liquid or solid metal
halides. Silane (SiH4 ), in addition to most
metal hydrides, is pyrophoric. The metal
halides usually react violently with water
vapor and while heating them to elevated
temperatures, care should be taken that the
carrier gases for the halide vapors are fully
dried. The metal halides (e.g. BCl3, TiCI4 ) are
corrosive and easily hydrolyzed, yielding
hydrogen chloride (HCl) upon reaction with
H 2 , NH3 and H 2 0. The properties of these
precursors places additional demands on the
design of the process. Metal parts in contact
with the process streams must be cooled to
temperatures around 400-600 K (127-327C)
to reduce the corrosion problem (Heymer
and Harnisch, 1967).
The increasing use of organic and polymeric
materials as precursors for ceramics brings
274 Gas phase synthesis processes
with it the attendant problem of safety and
toxicity. For example, triethyl aluminum
(TEA), used in gas phase synthesis of AlN, is
pyrophoric and reacts explosively with water.
This necessitates additional precautions when
this or similar chemicals are used. Some of
the product powders, at high purity, can be
hazardous to handle. For instance, ultra fine
titanium boride (TiB 2 ) powder is pyrophoric
and ignites on exposure to air.
As with many reactor processes, there are a
number of hazards associated with thermal
aerosol, laser or plasma type reactors. High
temperature vessels need to be properly insu-
lated to reduce the potential for thermal burns.
Leaks or ruptures in the synthesis reactors
may result in the release of toxic or highly
flammable gases. Reactors need to be
designed so that any water leaks from cooling
jackets etc. are kept away from reactant metal
halides or other water-sensitive chemicals. Air
leakage into hot reaction vessels presents
hazards associated with catastrophic combus-
tion. Large reactors may also incorporate high
volumes of inert gas which, of course, may
represent an asphyxiation hazard. To mini-
mize the potential for serious chemical acci-
dents, adequate ventilation and the regular
assessment of reactor vessel integrity should
be incorporated into any synthesis reactor.
Area oxygen monitors should be used to
protect operating personnel from inert gas
asphyxiation. Portable monitors should be
available and used for situations where toxic
or flammable gases have been released.
High power lasers are used commercially in
a variety of marking and cutting applications.
Precautions to minimize the potential for elec-
trical and optical radiation exposure should
be considered. Generally, CO 2 and Nd-glass
lasers are equipped with 'light pipes' which
contain radiation within an opaque tube. Spec-
ular reflection from infrared window surfaces
can be reduced through the use of anti-
reflection (AR) coatings on all optics. Other
potential hazards are associated with handling
fine powders. The high surface areas typical of
laser-synthesized powders render them
extremely reactive. Thus, oxidation and
hydrolysis are rapid in these materials.
Similar considerations apply to plasma-pro-
duced fine powders. Two main hazards to
equipment and personnel must be taken into
account in plasma powder handling. The first
is the tendency for small particles to be pyro-
phoric and/or explosive, and the second
refers to the health risk to humans who acci-
dentally inhale the particles (Hodkin, Pollock
and Sutcliffe, 1976).
The high purity inert gaseous environments
used in many plasma processes tend to
enhance the danger of a pyrophoric reaction
or explosion after opening of the reaction
vessel to atmospheric air following the com-
pletion of a production run. Such events may
be avoided by glove-box treatment of the
products or by evacuation of the reaction
vessel after the production run. The latter
approach, described by Hodkin, Pollock and
Sutcliffe (976) suggests an evacuation of
the chamber to less than 0.133 Pa 00- 3 torr),
which causes all remaining gas-suspended
particles to either precipitate onto the chamber
walls or be drawn off into the vacuum system.
This evacuation also removes any poisonous
gas that might have been produced (e.g.
cyanogen). The chamber is subsequently
allowed to cool to room temperature, and
then back-filled with an inert gas to atmo-
spheric pressure. The chamber is then
opened to the ambient air. Since the oxidation
that occurs as the air infiltrates into the system
through the open door is unpredictable, a con-
trolled ignition may be performed by means of
an HF spark.
REFERENCES
Heymer, G. and Harnisch, H. (1967) US Patent
3,352,637.
Hodkin, D.J., Pollock, J.5. and Sutcliffe, P.w. (1976)
Powder Metall., 19, 12.
THERMOCHEMISTRY AND KINETICS
Richard C. Flagan
INTRODUCTION
The synthesis of ceramic materials from gas-
eous precursors has received considerable
attention in recent years, and many aspects
of the chemistry have been elucidated. Some
of the greatest advances have come in the
development of technologies for the chemical
vapor deposition of ceramic films, particularly
those that find uses in microelectronics
fabrication. An understanding of the chemis-
try begins with an examination of the gas
composition and equilibrium condensed
phases, and continues to the detailed treat-
ment of the gas phase and surface reaction
kinetics. The database on thermodynamics
properties for the chemical species of concern
in ceramic synthesis is far better developed
than that for the reaction kinetics. Unfortu-
nately, thermodynamics only describes the
potential to form a material. The kinetics
must be known to predict the chemistry quan-
titatively.
Non-oxide ceramics present special chal-
lenges, since few of the reactions involved in
the formation of carbides, nitrides and borides
have been studied in detail. Most of the
detailed understanding of the gas phase syn-
thesis of non-oxide ceramics has developed in
the study of chemical vapor deposition for
microelectronics applications. Thus, even
when one's primary interest is the synthesis
of ceramic powders by gas phase routes,
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
11
much of the background material will be
derived from chemical vapor deposition,
frequently from technologies developed for
the fabrication of microelectronic devices.
Chemical synthesis methods for non-oxide
ceramics can be divided roughly into two
approaches: (1) reactions of different species
that provide the different chemical moieties;
and (2) synthesis by design of precursors
(generally organometallic compounds) that
provide the different moieties in a single
precursor molecule. The former approach
dominates the literature on the synthesis of
ceramics from gas phase precursors, but
recent advances in the latter approach have
been substantial. Ceramic synthesis using
organometallics frequently involves reactions
that are essentially irreversible, such as the
pyrolytic decomposition of the precursor.
Many applications of organometallics have
focused on the development of polymeric pre-
cursors that can be formed into fibers or films
and then reacted in the condensed phase to
form the ceramic material. These approaches
are outside of the purview of this chapter.
Others have focused on the development of
precursors that can be used in the epitaxial
growth of thin films in microelectronics fabri-
cation. These materials allow considerable
control over the properties of the ceramic
material being produced and are, therefore,
of considerable interest for advanced non-
oxide ceramics. Furthermore, organometallic
276 Thermochemistry and kinetics
precursors allow synthesis of the ceramic
material at relatively low temperatures, mini-
mizing interdiffusion of previously deposited
layers.
The range of chemistries that have been
applied to the chemical vapor deposition of
non-oxide ceramics are vast, yet, with the
exception of the synthesis of silicon nitride
and silicon carbide, relatively little is known
about the detailed reaction mechanisms or
kinetics. Because of the fundamental impor-
tance of the silicon compounds to the semi-
conductor industry, considerable detail is
available regarding these special chemical
processes.
The reaction pathways are only part of the
problem in gas phase synthesis processes.
Homogeneous gas phase reactions eventually
lead to the formation of species with low equi-
librium vapor pressures. As these materials
accumulate in the vapor phase, their concen-
trations eventually exceed the equilibrium
level sufficiently that the vapors undergo a
spontaneous phase transition. If sufficient sur-
face area is present, the vapors may deposit
heterogeneously on those surfaces, be they
particles or macroscopic surfaces. In the
chemical vapor deposition (CVO) of semicon-
ductor structures, this heterogeneous deposi-
tion is sought, whereas in powder synthesis
reactors, deposition on seed particles may be
desirable, but deposition on the reactor walls
represents a loss of the product material. On
the other hand, once the vapor accumulates
past a critical point, particles may be formed
by homogeneous nucleation. Homogeneous
nucleation is a critical step in most powder
synthesis from the vapor phase. Herein lies
a major difference between the synthesis of
ceramic powders and chemical vapor deposi-
tion. CVO reactors are operated under con-
ditions that minimize particle formation.
Hence, while the CVO literature provides
considerable understanding of the gas phase
and surface reactions, little detailed study
of the particle inception process has been
performed.
The kinetics of ceramic powder synthesis
from the gas phase does not end with the
nucleation of the particles. The nuclei are
generally far smaller than the particles that
are sought for ceramic materials. The particles
grow by several mechanisms, including con-
densation, surface reactions and coagulation.
These processes strongly influence the proper-
ties of the product particles. Coagulation is the
growth by the attachment of two particles
when they collide due to Brownian motion,
turbulence or other mechanisms. Coagulation
at low temperatures will generate aggregate
particles, while such growth at very high tem-
peratures can produce fully dense particles.
At intermediate temperatures, aggregates
may sinter to form undesirable hard agglom-
erates. Growth by condensation or surface
reactions can also produce dense particles,
although this is difficult to achieve with refrac-
tory materials.
THERMODYNAMICS OF GAS
PHASE SYNTHESIS
Thermodynamic equilibrium models are valu-
able tools in the analysis of processes for the
synthesis of ceramic materials from the gas
phase, providing a clear indication of the
driving forces involved. Kinetic factors may
lead to large deviations from the thermo-
dynamic predictions. As will be discussed in
more detail later, the kinetic processes
involved in ceramic synthesis are well under-
stood only in a few very special cases. Even
when the kinetics are known, thermodynamic
concepts are used to estimate reverse reaction
rates and are employed in partial equilibrium
models.
In contrast to the limited kinetic data avail-
able for reactions of interest to vapor phase
synthesis, extensive thermodynamic property
databases have been generated that make
possible comprehensive thermodynamic
analyses. A priori thermodynamic predictions
can be readily used to assess the likelihood
that a particular chemical route will be

possible, to identify phases that are likely to
be produced, and to assist in the design
of preliminary experiments (Bernard and
Madar, 1990). Thermodynamic databases are
not without flaws, however. Care must be
taken in the selection of thermodynamic data
to be used in any analysis. Compilations of
thermodynamic data, e.g. the JANAF tables
(1986) and Barin, Knack and Kubaschewski
(1977), provide some level of critical evalu-
ations, but differences between the different
references are substantial. Bernard and
Madar (1990) show that varying the thermo-
dynamic parameters within the reported con-
fidence limits can lead to substantial changes
in the predicted equilibrium composition.
Furthermore, the compilations are incomplete,
with species that may be important to a parti-
cular problem completely lacking. If a species
is not included in the model calculations,
its presence or absence cannot be predicted.
For example, in an equilibrium analysis of
the Ti-Si-C-CI-H system using data from
the JANAF tables (1986) and from Barin,
Knack and Kubaschewski (1977), titanium
disulfide (TiSz) was missing from the data
sets, even though it appears quite prominently
in the Si-Ti phase diagram (Bernard and
Madar, 1990).
Equilibrium calculations can be performed
in two theoretically equivalent but computa-
tionally distinct ways: (1) using equilibrium
constants for individual reactions; or (2)
global Gibbs free energy minimization. The
former approach is most useful in examining
a single chemical reaction, for example,
in assessing the feasibility of a particular
chemical route. When large numbers of
species are considered, care must be taken to
ensure that all of the reactions specified are
linearly independent. Moreover, when rate
constraints to the equilibrium are imposed,
those too must be linearly independent from
all of the equilibrium relationships used. The
global or direct Gibbs free energy minimi-
zation eliminates these shortcomings, and is
the basis of most of the general purpose
Thermodynamics of gas phase synthesis 277
equilibrium codes that have been applied to
the chemistry of ceramics synthesis. The
Gibbs free energy is minimized subject to
constraints on the numbers of moles of the
various elements in the system, enthalpy or
temperature, and pressure. The constraints
on moles and enthalpy are addressed using
the method of Lagrange multipliers to solve
the constrained minimization problem. This
method, which is generally attributed to
White (White, Johnson and Dantzig, 1958) is
the basis of a number of general purpose
chemical equilibrium codes. Two that are
commonly employed in the calculation of
chemical equilibria in systems of interest for
ceramics synthesis are STANJAN (Reynolds,
1981) and SOLGASMIX-PV (Erikson, 1975).
The former code is designed explicitly for
use with thermodynamic data in the form of
the JANAF tables, although more general
forms of the algorithms have been developed
and incorporated in the general chemical
kinetics algorithm CHEMKIN (Kee and
Miller, 1986). SOLGASMIX-PV is written as a
very general equilibrium solver.
Chemical equilibrium is the thermodynami-
cally stable state of a system, but says nothing
about the feasibility of a proposed route to
achieve that state. If we examine a particular
chemical reaction, the distinction between the
thermodynamically favorable route and a
kinetically feasible route can be made clear.
An example of a highly favorable reaction
that is too slow to be of use in ceramic syn-
thesis at modest temperatures is the reaction
of silane with nitrogen to produce Si3N 4 ,
SiH4 + 2Nz ;::::': Si3N4 + 6H z,
(11.1 )
MiR (298K) = -807kJ!mol
The Gibbs free energy change for this reaction
is highly negative for all temperatures, but
the reaction does not proceed because of the
difficulty of breaking the nitrogen-nitrogen
bond,
N z ;::::': 2N, MiR (298K) = 947kJ!mol (11.2)
278 Thermochemistry and kinetics
A more practical route for Si3N4 synthesis is
the reaction of SiH4 with NH 3,
3SiH4 + 4NH3 ~ Si3N4 + 12H2,
(11.3)
~HR(298K) = -741kJ/mol
Again, the free energy change is highly nega-
tive and, hence, favorable at all temperatures.
Initiation of the reaction with ammonia is
more favorable than with N2 due to the
lower energy required to break the N-H
bond,
NH3~NH2+H,
(11.4)
~R(298K) = 431 kJ/mol
Once some radicals have been produced, the
energy barrier is reduced even further since
exchange reactions of the type
NH3 + H ~ NH2 + H,
(11.5)
~R(298K) = -5.1kJ/mol
are nearly thermally neutral.
Nitrogen can react at the high temperatures
of thermal plasma reactors or in the non-
equilibrium atmosphere of a low pressure
plasma, but at the temperatures of most ther-
mal or flame reactors, N2 is essentially inert.
Since N2 is often a cost-effective diluent for
powder synthesis reactors, calculations of
chemical equilibrium with this species present
could yield misleading results. One approach
is to eliminate nitrogen-containing products
from consideration. For example, if one were
calculating the equilibrium in the synthesis of
SiC, Si3N4 could be excluded from the species
considered in the equilibrium calculation,
essentially constraining the solution to one
that satisfies the anticipated results. A more
general treatment that would even be applic-
able to silicon nitride synthesis is to constrain
the equilibrium solution so that the reactions
of the inert species are not allowed.
Constrained equilibrium calculations are
generally performed in an ad hoc manner (e.g.
Spear and Dirkx, 1990), although more rigor-
ous approaches are available. In particular,
Keck (Keck and Gillespie, 1971; Keck, 1990)
has shown that kinetic constraints, such as
the mass transport constraint described
above, can be treated as passive resistances to
the establishment of chemical equilibrium,
much as element conservation constrains the
range of equilibrium compositions. Each of
the element constraints and the additional
kinetic constraints introduces a Lagrange
multiplier into the constrained Gibbs free
energy minimization problem. While the
generalized partial equilibrium approach has
not been applied to the synthesis of ceramic
powders, it has been demonstrated for a
number of other high temperature reacting
systems. The chemical equilibrium code
STANJAN has the capability of imposing
constraints on the equilibrium solution in this
manner.
REACTION KINETICS
The stoichiometric relations that are used to
describe the overall chemical process bear
little relationship to the way that a reaction
actually proceeds. For example in the forma-
tion of Si3N4 from SiH4 and NH 3, three SiH4
molecules and four NH3 molecules must
interact. This interaction occurs in a sequence
of chemical steps, each of which proceeds at
a finite rate.
Gas phase chemical reactions can only take
place when the molecules come close enough
together that sufficient energy can be
exchanged directly, leading to chemical
bonds being broken. For the small molecules
of interest for high temperature synthesis of
ceramics, centers of mass of the molecules
must approach one another within a few
angstroms. At low pressures, such close inter-
actions occur as discrete, short-lived collisions
between molecules. From the kinetic theory
of gases, the number of collisions per unit
volume per unit time between molecules of
type i with those of type j is
(11.6)

where Cij is the mean relative speed of the i
and j molecules, and Ni and N j are the total
numbers of molecules per unit volume of
gas. During collisions, the molecules are
close enough to interact for only a very short
time, on the order of 10- 12 _10- 13 s. At the
temperatures and pressures of interest, the
times between collisions are much longer
than the interaction time, on the order of
nanoseconds.
Collision between molecules is a necessary,
but not sufficient condition for a chemical
reaction to proceed. The molecules must
possess sufficient energy to react when they
collide. Expressed in terms of the energy per
mole, the fraction of the collisions that involve
energy greater than the required energy
per molecule Ea fraction is exp( -Ea/RgT)
where Rg is the universal gas constant. The
rate of reaction can thus be expressed in the
form
(11.7)
where
k(T) = ko ex p ( - R:~ ) (11.8)
The pre-exponential factor ko may depend
on temperature since the translational and
internal degrees of freedom of the molecules
influence the probability that reaction will
occur during any collision event. The activa-
tion energy of reaction may exceed the
enthalpy of reaction, tl.HR , when an activated
complex is an intermediate step in the reac-
tion. Thus, the enthalpy of reaction provides
an indication of the temperature dependence
of the rate of reaction, but the actual depen-
dence can be greater than that energy would
suggest.
Most elementary reactions are reversible,
i.e. they can proceed in both forward and
reverse directions. This is expressed in the
form
(11.9)
Reaction kinetics 279
The time rate of change of the concentration of
one of the products due to this reaction is
p(d[C]/P) = k+1[A][B]
dt rxn
- LdC][D] (11.10)
where the brackets indicate the species con-
centration (mol/m3 ). The rate expression is
given in terms of the number of moles per
unit mass, [C]/ p, in order that only changes
due to chemical reactions be considered in
the rate equation.
At chemical equilibrium, the forward and
reverse rates of any fundamental reaction
must balance, and the time rate of change of
all concentrations must be zero. Hence, we
may write
(11.11)
The concentration ratio is seen to be the
equilibrium constant expressed in terms of
concentrations. Thus, the ratio of the forward
to the reverse rate coefficients for an elemen-
tary reaction is equal to the equilibrium
constant Kc for that reaction. This principle
of detailed balancing is used extensively to
determine one of the rate coefficients from a
measurement of the other one.
Because molecular collisions in gases are
infrequent, short duration events, most funda-
mental reactions are bimolecular, i.e. they
involve collisions between only two molecules
leading to breakage and formation of chemical
bonds. Reactions that only form a bond pro-
duce a molecule with sufficient energy to
dissociate spontaneously:
k,
A+B ~AB* (11.12)
L,
If the excess energy of the excited state
molecule is not removed by collision with a
third body, M, it will eventually dissociate.
The energy extraction reaction may be written
(11.13)
280 Thermochemistry and kinetics
The lifetime of the activated complex AB* is
very brief so its concentration may be
estimated by assuming a quasi-steady state,
i.e. by setting d[AB*]/dt = O. The net rate of
formation of AB is then
p(d[AB]/P) kl k2 [A][B][M]
dt rxn Ll +k2[M]
LIL2[AB][M]
(11.14)
Ll +k2[M]
At low pressures, [M] = p/RgT is small so
Ll k2 [M] and
p(d[ABl/P) = ~k2[A][B][M]
dt rxn Ll
-L2[AB][M] (11.15)
In the low pressure limit, the forward reaction
is said to be a three-body recombination reac-
tion, and the reverse reaction is bimolecular.
In the high pressure limit Ll k2 [M] and
p(d[ABl/P) = kl[A][B]
dt rxn
(11.16)
The forward reaction now appears to be bi-
molecular while the reverse reaction is a
unimolecular decomposition reaction. The
pressure at which the transition from one
limit to the other occurs depends on the life-
time of the activated complex AB*. Molecules
with many internal degrees of freedom tend to
have long lifetimes in the activated state, so
the high pressure limit extends to lower pres-
sures than for smaller molecules.
A complete kinetic description of the gas
phase reactions leading to the formation of a
ceramic material is a set of microscopic reac-
tions and the corresponding rate coefficients.
The net rate of formation of species j by chemi-
cal reactions is the sum of the contributions of
the various reactions in the mechanism, i.e.
(11.17)
where Vij is a stoichiometric coefficient and ri
is the rate of reaction. Because of the relative
simplicity of gas phase reaction mechanisms
and the importance of a fundamental under-
standing to such technologies as combustion
and chemical vapor deposition, detailed
reaction mechanisms are now beginning to
be developed for a number of the gas
phase processes of interest for non-oxide
ceramics.
Surface reactions introduce another level of
complexity into the kinetic description of the
reaction mechanism. One must account for
the adsorption of a gas phase species on the
surface, and the reverse of that process,
desorption. Adsorption occurs on specific
sites on the surface and, therefore, depends
on the availability of such sites. Surface cover-
age must be assessed to determine the number
of available sites. The adsorbed species mayor
may not react, and the product may remain
on the surface or it, too, may desorb. The
properties of the surface molecules may
differ significantly from those of the bulk.
Surface reactions cover previously deposited
material, transforming a surface species to a
bulk species. As in the gas phase mechanism,
each of the microscopic processes is reversible,
so both forward and reverse rates must gener-
ally be considered. The condensed phase
introduces spatial heterogeneity into the
system regardless of whether one is treating
chemical vapor deposition on a macroscopic
substrate or the formation of ceramic particles
that may be uniformly dispersed throughout
the gas as fine aerosol particles. Comprehen-
sive modeling, therefore, requires treatment
of the gas phase convection and diffusion in
addition to the description of the effects of
chemical reactions. Conservation of mass
and momentum are written (Bird, Stewart
and Lightfoot, 1960)
~ + V' 0 pu = 0 (11.18)
au
Pat+puoV'u=-V'P-V'oT-pg (11.19)

where u is the gas velocity, T is shear stress
and g is the gravitational acceleration vector.
The species conservation equation is
aMY
p f + pu\l(MiYi)
= -\l(pDi\l(MiYi))
+ Ri - Si i = 1, ... , s (11.20)
where Mi is the molecular mass of species i, Yi
is the mass fraction of species i, Di is the
diffusivity and Si is the volume rate of loss.
The specification of the problem to be solved
is completed by stating the initial conditions
for p, u and Yi throughout the reactor
volume. Homogeneous gas phase reactions
are introduced through R i In chemical vapor
deposition (CVD) problems, the influence of
surface reactions on the gas phase species con-
centrations is treated by specifying the bound-
ary conditions at the surface of the deposition
substrate and reactor walls. This level of detail
has only recently been incorporated into
models of chemical vapor deposition of non-
oxide ceramics, namely in the modeling of
SiC CVD (Allendorf and Kee, 1991), and will
be addressed in the discussion of that
material. In powder synthesis, in addition to
specification of boundary conditions of the
macroscopic surfaces, the conditions at the
surfaces of the growing particles must be
taken into account. Since the scales associated
with the growing particles are much smaller
than the macroscopic scales, mean field
approximations can be applied to the coupled
problem, with the particles being treated as
sinks, Si' that are distributed throughout the
gas volume.
The focus here has been on detailed kinetic
mechanisms. Simpler descriptions of the reac-
tion rates have been developed for a number of
systems, wherein a global rate expression has
been derived that encompasses a number of
fundamental reaction steps. Unfortunately,
such global descriptions tend to be quite
specific to the system for which they were
determined, even for systems that only involve
Aerosol dynamics 281
gas phase reactions. A global description of a
powder synthesis process will require detailed
knowledge of the time evolution of the aerosol
particle size distribution in order that the
active surface area can be estimated. If that
information is not available, estimates of the
relative rates of surface and gas phase
reactions may be in error by many orders of
magnitude due to the large variations in
aerosol properties. Application of global
expressions derived from chemical vapor
deposition studies would be particularly
suspect because of the large differences in the
surface areas and transport processes involved
in deposition on a macroscopic substrate and
on aerosol particles.
AEROSOL DYNAMICS
The chemical reactions describe only part of
the synthesis of ceramic powders from gas
phase reactions. The process generally begins
with gaseous precursors and forms the con-
densed phase by homogeneous nucleation,
i.e. by the aggregation of vapor molecules to
form a thermodynamically stable particle.
Nucleation of refractory vapors usually pro-
duces large numbers of very small particles
in an extremely short time. Once the particles
are formed, vapor condensation on their sur-
faces will reduce the supersaturation, possibly
suppressing further nucleation. The particles
may also grow by surface reactions and by
coagulation.
The evolution of the aerosol is described in
terms of the particle size distribution function,
although chemical composition, phase and
particle morphology are also important
properties to be controlled and predicted.
One can describe particle size in terms of the
numbers of molecules that comprise indi-
vidual particles. This leads to a discrete
representation of the particle size distribution,
N g . While convenient for describing the
initial formation of particles from the vapor
phase, the discrete representation rapidly
becomes unwieldy as particle size increases.
282 Thermochemistry and kinetics
To describe particles larger than a few nano-
meters in size, one generally resorts to a
continuous representation of the size distribu-
tion. If the total number of particles per unit
volume of gas is N(t), the number with
masses between mp and mp + dmp is
dN = n(mpl t)dmp (11.21)
Aerosol models seek to describe the evolution
of n(mpl t) under the action of a number of
mechanisms:
dn(mpl t)/ p (dn(m p1 t)/ P)
P
dt
= P dt nucleation
( dn(mplt)/p)
+ p dt condensation
( dn(mplt)/p)
+ p dt surface reactions
( dn(mplt)/p)
+ p dt coagulation
(11.22)
In the discussion to follow, we briefly describe
some of the key mechanisms and the rate
expressions that have been derived to predict
the evolution of the aerosol. We then summar-
ize the discussion with a functional represen-
tation of equation 11.22 that is known as the
general dynamic equation for aerosols.
NUCLEATION
A supersaturated vapor is inherently unstable,
and tends to form the condensed phase either
by condensation onto existing surfaces or by
homogeneous nucleation. The rate of phase
transformation is determined by kinetic and
transport processes. Here we examine the pro-
cess of homogeneous nucleation or direct for-
mation of the condensed phase from the vapor
phase. The theory of homogeneous nucleation
traces its roots back to the work of Gibbs on
the thermodynamics of small clusters, and to
the early works of Becker, Doering, Volmer
and Zeldovich (Seinfeld, 1986). It still remains
a controversial area due to the many assump-
tions required in its derivation. The key
assumptions of the classical theory of homo-
geneous nucleation are as follows.
Clusters grow by monomer addition.
The rate of monomer arrival at the cluster
surface is that determined by kinetic theory,
(11.23)
where PI is the partial pressure.
A steady-state distribution of cluster sizes is
assumed.
The surface free energy a of clusters of all
sizes is assumed to be the same as that of
the bulk material. This so-called capillary
approximation is the most tenuous of the
assumptions in the classical nucleation
theory.
The evaporation rate is determined by noting
that, at equilibrium, the rate of formation of
clusters comprising g molecules by condensa-
tion on clusters of size g - 1 must equal the
rate of evaporation from clusters of size
g - 1. This application of detailed balancing
requires that the equilibrium cluster distribu-
tion be determined before the evaporation rate
can be determined. This is usually performed
for a so-called constrained equilibrium state,
i.e. the equilibrium among the clusters is
computed for a supersaturated state. With
the capillary approximation, the constrained
equilibrium cluster is
N~e = Nf exp(g In 5 - ::~i/3) (11.24)
where 5 is the saturation ratio pJ/pt Nf is
the number concentration of monomers at
full thermodynamic equilibrium and 51 =
(361l'vi)I/3 is the surface area of a monomeric
'particle' (where VI is the volume). Note that
many classical treatments use N'{ rather
than Nf although a careful thermodynamic
derivation yields the expression presented
above.

From equation 11.24, it is apparent that
there is a minimum in the constrained equili-
brium cluster distribution. That critical cluster
size is
* 327r0"3 V i
(11.25)
g = 3(kBTln5)3
where 0" is the surface free energy of bulk
material. Clusters smaller than g* are more
likely to evaporate than to grow, while
larger particles will tend to grow. Hence, g*
represents a kinetic bottleneck to new
particle formation. The net rate of passage of
particles through the region near g* is the
nucleation rate. The steady-state nucleation
rate is the product of the rate of monomer
arrival to the surfaces of clusters of the critical
size, the constrained equilibrium concen-
tration of critical sized clusters and a non-
equilibrium factor Z that accounts for
differences between the steady-state cluster
distribution and the hypothetical constrained
equilibrium distribution:
(11.26)
where {J is the monomer flux to the surface of a
growing cluster. With the assumptions of the
classical nucleation theory, but using the
constrained equilibrium cluster distribution
of equation 11.24, the steady-state nucleation
rate becomes
2 PIal ( O"SI ) 1/2 e
J = 3" (2mnl kB T) 1/2 7rkB T nl
40"3af ) properties of any ceramic materials syn-
( (11.27)
x exp - 27(kB T)3I n 2 5
This result differs from the traditional expres-
sion by a factor of 1/5.
PARTICLE GROWTH
Once particles have been formed by homoge-
neous nucleation, they grow by the combined
effects of vapor deposition and coagulation.
The nature of the particles produced depends
Aerosol dynamics 283
very strongly on the relative rates of these
processes and on the properties of the material
being synthesized at the reaction temperature.
The literature on aerosol dynamics is vast, so
the reader is referred to texts that present the
fundamentals of the subject (Fuchs, 1964;
Friedlander, 1977; Seinfeld, 1986; Flagan and
Seinfeld, 1988).
Most derivations of the dynamics of aerosol
systems make a critical assumption that is
only rarely valid for aerosol synthesis of
ceramic materials, namely that the particles
are spherical throughout the growth process.
This assumption is strictly valid only when
the process is operated at temperatures in
excess of the melting point of the product
material and the viscosity of the melt is suffi-
ciently low. At lower operating temperatures,
aggregate particles formed by collisions of
solid particles coalesce or sinter together at
finite rates. Since the particles are non-spheri-
cal, their diffusivities, collision cross-sections
and rates of mass transfer to their surfaces
can differ dramatically from the values for
dense spheres. The structures of aggregate
particles are determined by the competition
between coagulation and coalescence of the
particles. If the time scale for coalescence is
short compared to the time between collisions,
the particles will evolve as spheres. On
the other hand, extremely slow coalescence
will lead to the formation of low density
aggregates. Coalescence or sintering at inter-
mediate rates will lead to the formation of
hard agglomerates, severely degrading the
thesized from the resulting powders.
There is not necessarily a unique length
scale that will characterize the particle.
Indeed, there is considerable confusion about
what constitutes the particle size in refractory
powders that are synthesized from the vapor
phase. From the perspective of the ceramicist,
the size of the primary particles that form
the aggregate is most interesting, provided
the aggregates are weak enough that they do
not interfere with the consolidation of the
284 Thermochemistry and kinetics
powder. On the other hand, the dynamics of
particle growth are determined by the proper-
ties of the aggregate itself.
The dynamics of aerosols can be described
in terms of the evolution of the particle size
distribution, n(mp). The aerosol dynamics are
then described using the so-called general
dynamic equation for aerosols,
Dn(mp, t)/ P
P Dt
= [~ K(mp - v, v)n(mp - v, t)n(v, t)dv
p
-1
2. n(m p, t) Joo
m' K(mp, v)n(v, t)dv
p able effort has been invested into the develop-
+ S(m;, t)8(mp - m;)
8 tional demands.
+ - 8 (J(mp, t)n(mp, t)) (11.28)
mp
where the first term on the right-hand side
accounts for the formation of particles of
mass mp by agglomeration of particles of
smaller mass, the second term accounts for
the loss of particles of mass mp by coagulation
with particles of any other size, and m;
is a
lower bound to the particle size distribution.
The continuous representation of the particle
size distribution is an acceptable approxi-
mation only for particles sufficiently large
compared to the molecular mass. The
appearance of particles at that size from
below is generally represented using a
nucleation model, hence the source term
S(m;, t) (8(mp - m;) is the Kroenecker delta
function), although hybrid representations
that couple a discrete representation of the
smallest clusters with a continuous represen-
tation of the distribution of larger particles
have been developed (Gelbard and Seinfeld,
1978). The fourth term on the right-hand
side accounts for particle growth by vapor
deposition or shrinkage by evaporation,
with J(mp, t) describing the time rate of
change of the particle mass, i.e. the velocity
in mp-space.
Solution of the general dynamic equation
is performed with varying degrees of rigor
using a number of approaches and codes.
Discrete representations of the particle size
distribution, while most precise at the finest
scales, are ill-suited to the description of the
dynamics of an aerosol whose particles may
have masses ranging over 12 or more orders
of magnitude. The most rigorous of the
codes which numerically integrate over the
particle size distribution in continuous form
are very computer intensive due to the vast
range of sizes and time scales that enter most
aerosol dynamics problems (e.g. Gelbard and
Seinfeld, 1978). For these reasons, consider-
ment of approximate models that facilitate
detailed calculations while limiting computa-
The dynamics of an aerosol undergoing
coagula tiona 1 growth afford important sim-
plifications in many cases. If the collision
frequency function K(mp, m~) is symmetric,
the time rate of change of the total number
concentration can be shown to be
pdN/p =-~JooJoo
dt 2 a a
x K(mp, m~)n(mp)n(m~) dmp dm~
(11.29)
Under certain conditions, the Brownian
coagulation equation yields similarity solu-
tions that allow the complete size distribution
to be determined from knowledge of the total
number and mass concentrations of aerosol
particles. The particle masses mp are first
normalized by the mean particle mass mp =
oo '
/N where is the total aerosol mass per
unit volume of gas, and Noo
is the total
number of particles per unit volume. If the
coagulation kernel for particles of masses
mprJl and mprJ2 can be written as
K( m171 , mprJ2) = m~K( rJl, rJ2) (11.30)
the kernel is said to be homogeneous of degree
"I, and the coagulation equation may be solved

using similarity techniques (Lai et al., 1972;
Bunz, 1990).
To obtain the similarity solution, it is
assumed that the size distribution n(mp, t) is
proportional to a time-invariant, or self-
preserving, distribution 'l/J("l):
n(m t) = N~(t)'l/J("l)
p'
Substituting these variables into the coagula-
tion equation and integrating over all particle
sizes, the rate of change of the total number of
particles is
dNoo/p = _~ (~)'fN2
p dt 2 Ii N 00 00
where
Ii = f~ f~ K("ll, "l2)'l/J("l1)'l/J("l2) d"ll d"l2
and 'l/J("l) is obtained by solving the scaled
coagulation equation. Since Ii and 'l/J are
independent of time, equation 11.33 can be
solved analytically in the case of constant
aerosol volume and temperature. For , < 1
one finds
1
Noo(t) = (N~-l(o)+I;''f/'d)'F1
For large t, the time variation of the number
concentration reduces to
where the dynamic exponent z is related to the
degree of homogeneity by
1 tial equations.
Z=--
1-,
Originally derived for spherical aerosol par-
ticles, the theory of the self-preserving particle
size distribution has recently been extended
to describe the evolution of fractal aerosol
aggregates (Mountain, Mulholland and Baum,
1986; Matsoukas and Friedlander, 1991; Rogak
Aerosol dynamics 285
and Flagan, 1992). This similarity transforma-
tion allows one to transform the general
dynamic equation (GDE) into an ordinary
differential equation for the total number
of aerosol particles, with the mean size
being determined from that number and
knowledge of the total mass of aerosol
(11.31) particles.
The next level of sophistication is the trans-
formation of the GDE into a set of differential
(11.32)
equations for moments of the particle size dis-
tribution (Seigneur et al., 1986; Wu and Flagan,
1988; Pratsinis and Mastrangelo, 1989). These
models can faithfully reproduce many of the
results of the more precise numerical solutions
to the general dynamic equation, although
treatment of distributions containing more
(11.33)
than one peak, or mode, requires considerable
a priori knowledge about the nature of the
particle size distribution.
The sectional representation, introduced by
(11.34) Gelbard and Seinfeld (1980), is now exten-
sively used. The continuous particle size
distribution is approximated as a histogram,
with the number concentration being constant
within the size interval forming a section.
Transport of mass from one section to another
by coagulation, condensation, evaporation or
other processes is described by coefficients
that are determined by integration over the
(11.35) appropriate bounds in the exact general
dynamic equation. The coefficients are evalu-
ated so that aerosol mass is conserved exactly
and, in the limit of infinitesimal section
widths, the sectional model reduces to the
(11.36)
exact general dynamic equation. The use of
finite section widths reduces the integro-
differential GDE to a set of ordinary differen-
(11.37) A number of important extensions have
been made to the original sectional code.
One that may be critically important to the
modeling of the synthesis of non-oxide and
composite ceramic powders is the develop-
ment of the multi-component sectional code,
MAEROS (Gelbard and Seinfeld, 1980). With
the assumption that all particles within a
286 Thermochemistry and kinetics
section have the same composition, MAEROS Spherical particles
makes it possible to keep track of variations of
The collision frequency function K(mil mj) is
chemical composition with particle size. A
well known for spherical particles that are
second important extension is the develop-
either very large compared to the mean free
ment of the discrete-sectional representation,
path of the gas molecules, A, i.e. continuum
first by Wu and Flagan (1988) to describe
regime particles, or particles that are small
aerosol formation by kinetically controlled
compared to A, the so-called Knudsen or free
nucleation, and later by Rao and McMurry
molecular regime particles. The particle size
(1989) with the inclusion of the evaporation
can conveniently be characterized in dimen-
terms that play such an important role
sionless form as the Knudsen number,
in classical nucleation theory. These codes
Kn = AIa, where a is the particle radius. The
make it possible to describe the evolution of
continuum regime corresponds to small
particles from the molecular scale to the sizes
Knudsen numbers, Kn 1, while the free
of interest for ceramic powders, without
molecular regime corresponds to large Knud-
overly taxing computational resources. Of
sen numbers, Kn 1. Coagulation in the
these codes, MAEROS is the most robust
continuum regime is modeled as diffusion of
and extensively documented, being distribu-
the two particles until they approach the point
ted and supported by the Sandia National
that they contact one another. The collision
Laboratories.
frequency function is then proportional to the
An important assumption in the algorithms
product of the collision radius (which equals
for solving the general dynamic equation is
the sum of the radii of the two particles) and
that all particles of a given size have the
the pair diffusivity D12 = Dl + D2, i.e.
same composition. In the synthesis of non-
oxide ceramics, particle stoichiometry is a Kc(mil mj) = 47f(Di + Dj)(ai + aj) (11.38)
critical issue. If differences in the relative
From the perspective of coagulation, it is the
importance of the various mechanisms in
Knudsen number based upon the particle
different regions of the reactor lead to
mean free path, ld = 2D12/c12, that determines
variations in particle composition, the
the onset of deviations of the collision fre-
assumption of compositional uniformity will quency function from the continuum result.
not necessarily be valid. While some efforts Here, C12 = (ci + C~)1/2. The particle diffusivity
to a more general description of the composi-
is related to its aerodynamic drag through the
tion-size distribution have been reported Stokes-Einstein relationship,
(Kim and Seinfeld, 1992), a general purpose
code that allows description of the full D = 67fJ1i1 (11.39)
composition-size distribution has yet to be kBT
developed. Hence,
The phase of the aerosol particles has also
received limited attention. Kobata, Kusakabe
and Morooka (1991) have extended the
Kc(mil mj)
2kBT(
=- 1 1)
- 173 + 173 (mi
1/3
+ mj1/3 )
JL mi mj
discrete-sectional model of aerosol dynamics
(11.40)
to account for phase transitions within the
particulate phase. They modeled the anatase The coagulation frequency function for equal-
to rutile transformation in Ti0 2 synthesis by sized particles in this limit is independent of
reactions of TiCl4 and 02, providing a frame- particle size: Kc(m , m) = 8kBT 13JL.
work for the development of more general In the free molecular limit (Knd = ld/a 1),
descriptions of this crucial aspect of aerosol particles move along ballistic trajectories over
synthesis of particulate materials. distances that are larger than the particles in

question. The collision frequency then
depends on the relative thermal speed of the
particles and the projected cross-sectional
area:
Kfm(mi,mj) = 7r(al +a2fc12
c where C is the slip correction factor. The col-
= (~)1/6 (6kBT)1/2 (~+~)1/2 lision frequency function is estimated using
47r 2/3
Ppm m I ]
(11.41)
where Pp is the mass density of the particulate
material. For equal-sized particles in the free
molecular regime,
K(m, m) = 4(6kBT)1/2pp2/3 ml/6
= 8(6kBT / pp)1/2a1/2
Both the continuum and free molecular
collision frequency functions lend themselves
to the self-preserving size distribution analy-
sis. In the free-molecular limit, the order of
the collision frequency function with respect
to m is v = i. The total number of particles
decays with time according to
P dNoo/p = -~ (~)1/6(6kBT)1/2 Vl/6N:J,/6
dt 2 47r Pp
(11.42)
where V is the total volume of particles per
unit volume of gas. The self-preserving par-
ticle size distribution (SPDF) is approximately
log-normal and is frequently approximated as
such. For particles much smaller than the
mean free path of the gas molecules, the
SPDF has a geometric standard deviation of
approximately a g ~ 1.46 (Landgreb and
Pratsinis, 1989). This result is important since
it defines the limit to the uniformity or
monodispersity that can be achieved in aero-
sol synthesis in which the primary growth
mechanism is Brownian coagulation.
Coagulation of spherical particles at sizes
intermediate between the free molecular and
continuum regimes is well described by
a collision frequency function originally
Aerosol dynamics 287
derived by Fuchs (1964). In this regime, the
particle diffusivity must be modified to correct
for non-continuum aerodynamics,
(11.43)
the so-called flux matching method wherein
the flux of particles calculated using the con-
tinuum transport expression is matched to
that predicted for free molecular transport.
Figure 11.1 shows the collision frequency
function for particles of density 2300kg/m3
in atmospheric pressure air at 300 K (27C)
and 1500 K (1227C), expressed in terms of
the radii of the coagulating spherical particles.
The Brownian coagulation coefficient exhibits
its lowest value for particles of equal size. The
maximum value of K(rp, rp) occurs at
rp ~ 20nm at 300K (27C) and rp ~ 50nm at
1500 K (1227C). The increase in this transi-
tional size results from the increase in the
mean free path with temperature. The colli-
sion frequency is higher for particles of differ-
ent sizes than it is for similarly sized particles
because the large collision area of the large
particle is combined with the high diffusivity
of the small particle.
Aggregate particles
The assumption that particles remain spheri-
cal as they coagulate is reasonable for low
viscosity liquids, a condition that is frequently
invalid for the systems of interest for ceramics
synthesis. Rather than coalescing rapidly
after they coagulate, refractory materials
frequently retain the structures of the indi-
vidual particles that have coagulated, forming
low density aggregates. The structures of the
aggregates influence the rates of particle
growth, so an understanding of the aggrega-
tion process is essential to the prediction of
reactor performance.
Because hard agglomerates can dramati-
cally degrade ceramic materials, knowledge
288 Thermochemistry and kinetics
10-8~~rn~~~TT~m--.","no-'-'nTrra

300 K
1500 K

-
,....,
I/J
1 0- 11

-
C')

- C\I
.....E
10- 12

-
~

.....E
~
10- 13

. .
" '\"
..... -----.. .::1' "'.
III..
...... -.... ' .. , ....

............: ...:.....# ......... - ................ _ .... _ ..

1 0-1 6 L...-....L.-L...L.J...I...I.IJLL--.......I.-..L....L...LL.LI..LI..-----L--L-L...L..L..1.L.I.L.----L-1...JL...L.I..LW

10- 9 10- 7
rm2 (m)

Figure 11.1 Collision frequency function for coagulation of spherical particles of radius rm2 with smaller
particles of radius rmI' Particle density is 2300 kg/ m 3 . Calculations are performed for gas temperatures of
300K (27C) (solid curves) and 1500K (1227C) (dashed curves).

of the potential to form such detrimental par-
ticles is also critical to the control of the prop-
erties of the precursor powders. Aggregate
formation is almost unavoidable since it can
occur after the particles have been synthesized
during collection or handling. The difference
between readily dispersed aggregates and
hard agglomerates is frequently the tempera-
ture at which the particles aggregate. If the
aggregation takes place at the high tempera-
tures of the synthesis reactor, interparticle dif-
fusion will lead to the development of strong
bonds between the primary particles. On the
other hand, if aggregation can be suppressed
until the temperature has decreased suffi-
ciently, readily dispersed aggregates may be
formed. Other mechanisms such as vapor
deposition into the neck region between
aggregated primary particles may also contri-
bute to the formation of hard agglomerates.
Again, this is a process that will take place
primarily in the high temperature region of
the reactor.
The structures of these particles are deter-
mined by random sequence of aggregation
events, with relatively little rearrangement
taking place after the collision except by
solid-state diffusion or viscous sintering. In
the limit where such interdiffusion and other
post-aggregation rearrangements are negligi-
ble, the particle structures develop self-affine
forms that have been labeled mass-fradal
with the mass of the aggregate varying with
size as
(11.44)
where K is an empirical constant of order
unity. The fractal dimension is less than the
Euclidian dimension, i.e. for aggregate par-
ticles, Df < 3, so the particle density decreases
with increasing particle size. The primary
particle size is determined by the material
properties and the conditions of particle for-
mation. Below some critical size, the particles
coalesce so rapidly that the particles achieve
their theoretical density, but at larger sizes
Aerosol dynamics 289
coalescence proceeds more slowly than coagu-
lation, leading to aggregate formation. For any
particular system, the primary particle size is
relatively uniform, even though a broad range
of particle sizes may be present.
The coagulation rate for agglomerate par-
ticles differs from that for dense spheres for
two reasons: 0) the low density aggregates
experience larger aerodynamic drag forces
than do compact spheres, and hence diffuse
more slowly; and (2) the aggregate particles
present larger targets for collision. These
two factors have opposite influences on the
collision frequency. A number of models of
the collision frequency for aggregate particles
have been proposed. Mountain, Mulholland
and Baum (986) developed models for coagu-
lation in both the free molecular and con-
tinuum regime. Rogak and Flagan (992)
developed more general models that span
the range of Knudsen numbers and fractal
dimensions.
The resulting collision frequency function is
plotted in Figure 11.2 for aggregates with frac-
tal dimension 1.8 and primary particle radii
ranging from 1 nm to 100 nm. The trends in
each data set are similar to those observed
for spherical particles, i.e. (1) the collision
frequency function for equal-sized particles
approaches an asymptotic value at small
Knudsen number (large equivalent radius);
(2) the collision frequency function for equal-
sized particles peaks near the Knudsen
number of unity and then decreases with
decreasing particle size or increasing Knudsen
number; (3) the collision frequency function
for particles of different sizes increases with
increasing size difference.
The collision frequency function depends
on both the fractal dimension and on the size
of the primary particles that form the aggre-
gates. Particles with masses below ml are
dense, so the collision properties must
approach those of dense spheres as the size
approaches the primary particle size. As a
result, the collision frequency function for
equal-sized particles with a small primary
290 Thermochemistry and kinetics

10-8~~on~~'-TT~m--r. .,"nr-'-'nTrra

r1 = 100 nm
10- 9 r1 = 10 nm
r1 = 1 nm
nm
10- 10

-
..-0
C/)
10- 11

-
C')

-....-C\I
E
10- 12

-....
~
E

10- 13

rm1 = rm2

1 0- 1 6 1-...L-L..L...I...L.LlJLL...---L....L..L..LL.LI..LI..----'-...L...L~.L.LL.-__L_L..JL...LL.u..u
10- 9 10- 7
r m2 (m)
Figure 11.2 Collision frequency function for coagulation of aggregate particles of mass equivalent radius
rm2 with smaller particles of mass equivalent radius rmI. The particles are mass fractal with fractal dimen-
sion Df = 1.8 for rm > rv the primary particle radius. The material density is 2300kg/m3 . Calculations are
performed for a gas temperature of 1500 K (1227C).

particle size is more sharply peaked than that
for dense spheres. The densities of aggregate
particles decrease with decreasing primary
particle size. This increases the collision
cross-section of particles with fine micro-
structures, thereby increasing the collision
frequency function. Both experimentally and
using the self-preserving particle size distribu-
tion model, Matsoukas and Friedlander (1991)
showed that aerosol aggregates with fine
microstructures grow more rapidly than do
those with coarser microstructures (larger
primary particles), a clear result of this depen-
dence of the collision frequency function on
the primary particle size.
Aggregate particles form when the time
between coagulation events is smaller than
the characteristic time for coalescence. Since
aggregate particles coagulate more rapidly
than do dense particles, coagulation acceler-
ates once aggregates begin to form. Rogak
and Flagan (1992) modeled growth from
below the critical size for coalescence to
aggregation by arbitrarily assuming that all
particles below a specified size are dense
spheres, while all larger particles are aggre-
gates of the same fractal dimension. Their
results showed the broadening of the particle
size distribution that had previously been
measured by particle mobility in the aerosol
phase. Above the critical size, the particle
size distribution narrowed once again, rapidly
approaching an asymptotic form as predicted
using the self-preserving particle size distribu-
tion model.
Some progress has been made to predict
simultaneous coagulation and coalescence.
Koch and Friedlander (1990, 1991) character-
ize the particles in terms of their surface
areas and volumes. When two particles
collide, the total surface area is conserved as
is the total volume. Following the formation
of an aggregate, the surface area may decrease
toward that of a dense sphere by sintering.
Following the earlier work of Ulrich and Sub-
ramanian (1977), they assumed viscous sinter-
ing to be the primary coalescence mechanism,
Aerosol dynamics 291
and characterized the coalescence as a first-
order decay of the surface area,
da 1
dt ~ Tv (a - afinal) (11.45)
(where Tv is the characteristic time for viscous
sintering), as suggested by numerical simula-
tions of Hiram and Nir (1983). The influence of
aggregate structure on the coagulation fre-
quency function was neglected. The authors
did show, however, that the primary particle
size approaches an asymptotic value at large
time.
The structures of agglomerate particles will
not be uniform due to differences in their
individual coagulation and coalescence his-
tories. Xiong and Pratsinis (1993) added this
dimension to the simulation of agglomerate
evolution with a two-dimensional sectional
model in which both the particle volume and
surface area were followed. Using an early-
stage sintering model to follow structural
rearrangements of the agglomerates in this
model makes it possible to follow the evolu-
tion of the particle structure.
Flagan and Lunden (1995) examined the
transition from coalescent coagulation to
agglomeration in nanoparticle synthesis by
the gas evaporation method. They applied
the self-preserving particle size distribution
model for the free molecular regime, noting
that, because of the larger collision cross-
sections of agglomerate particles, agglomerate
growth quickly dominates once it starts. Thus,
the key to growth of dense particles by coagu-
lation is to quench sintering rapidly once
coalescence slows. Rapid cooling from a tem-
perature that leads to fast coalescence to one at
which coalescence is effectively stopped can
produce powders with few hard agglomer-
ates. They estimated this transition using the
early-stage sintering models.
Quantitative determination of the bounds
on the formation of hard agglomerates will
require a better understanding of the sintering
kinetics. Lunden (1995) examined the struc-
tural rearrangements of model agglomerates,
292 Thermochemistry and kinetics
primarily bispheres produced by coagulation
of spherical silicon particles, both experimen-
tally and theoretically. Neck growth was
shown to slow significantly after the early
stage for the surface diffusion mechanism
that dominates for this material, leading to
much longer times for complete coalescence
than the early-stage sintering models would
suggest. The sintering kinetics depend
strongly on the environment. In one of Lun-
den's experiments, trace amounts of oxygen
effectively stopped material transport by sur-
face diffusion, leading to much slower sinter-
ing by volume diffusion processes. Similar
observations have been reported in other
systems. Seto, Shimada and Okuyama (1995)
compared sintering rates for Ti02 agglo-
merates determined in a number of studies.
Most of the observations showed an onset of
agglomerate sintering at 1000 K (727C),
although Xiong, Akhtar and Pratsinis (1993)
reported substantial sintering at temperatures
below 500 K (227C). The differences between
the various studies can be traced to the precur-
sors examined. Seto, Shimada and Okuyama
(1995) and most of the other studies they
examined employed alkoxide precursors,
while Xiong, Akhtar and Pratsinis (1993)
burned TiCl4 . The presence of the halogen in
the reaction environment allowed sintering
to proceed by mechanisms that were not
significant for the halogen-free environment.
VAPOR DEPOSITION
The transport of vapor species to the surfaces
of aerosol particles depends on the size of
the aerosol particle relative to the mean free
path of the gas molecules, i.e. it depends on
the Knudsen number characteristic of vapor
diffusion to the particle,
(11.46)
where AAB is the mean free path of the vapor
molecules A in background gas B. Obviously,
the dependence on the mean free path
introduces some ambiguity in the description
of mass transfer to aggregate particles since
the particle can be characterized in terms of
multiple length scales. Restricting our atten-
tion to spherical particles for the time being,
we may examine the transport processes in
three domains of Knudsen numbers. For
particles much smaller than AAB, KnAB ~ 1,
the particles are in the free molecular regime
and the flux of vapor to the particle surface
is the product of the particle surface area
and the effusion flux,
[A]CA
N A,k = 47ra 2 -4-
(11.47)
When KnAB 1, the particle is said to be in
the continuum size regime, and mass transfer
to the particle's surface is described by the
diffusion equation. In this case the net molar
rate of transfer to the surface of a spherical
particle becomes
(11.48)
At intermediate Knudsen numbers, mass
transfer to spherical particles cannot be
rigorously derived. Instead, approximate
correction factors are used to calculate the
vapor flux from the continuum regime flux,
i.e.
(11.49)
A commonly used correction factor for
spherical particles is that proposed by Fuchs
(1964)
,B(KnAB) = 1 + KnAB 2 (11.50)
1 + 1.71KnAB + 1.33KnAB
To follow the gas phase reactions leading to
particle formation and growth, one must
include the effects of vapor deposition on
particle surfaces in the vapor phase species
conservation equations (equation 11.20). The
aerosol particles are distributed throughout
the gas volume. Hence, the aerosol can be
treated as a volumetric sink for condensible
reaction products or species that react on the
particle surfaces. If the species in question is

a major player in the high-order gas phase
reactions, the reactions local perturbations in
the gas composition near the surfaces of indi-
vidual particles may become important, but
these small scale fluctuations are not generally
treated in any detail. The total rate of loss of
species A per unit volume of gas to the
surfaces of aerosol particles is the sum of the
contributions of all particles, and is deter-
mined by integrating the product of the flux
and the particle size distribution over all
particle sizes:
SA = J~ NA(m,[AJ,t)n(m,t)dm (11.51 )
Aggregate particles
For the low density agglomerates produced
when a rapid burst of nucleation is followed
by coagulation without significant coales-
cence, most of the surface of the agglomerate
is exposed directly to its surroundings, so the
surface area available for mass transfer is very
close to the total surface area of the particle. If
the particles are much smaller than the mean
free path and the fractal dimension is below
about Df ~ 2, the vapor deposition rate will
be nearly that predicted if one assumes that
all of the surface area is equally accessible.
Indeed, on the other hand, denser agglomer-
ates will exhibit a lower available surface
area. Meakin et al. (1989) and Koch and Fried-
lander (1990) have explored the mass transfer
to particles of arbitrary fractal dimension
theoretically, estimating effectiveness factors
for mass transfer to agglomerate particles.
Few experimental data are available in
which the mass transfer has been measured
directly, and those measurements were made
on agglomerates with relatively low fractal
dimensions, on the order of 1.8 (Rogak et al.,
1991). Mass transfer and projected area
equivalent diameters were found to be very
close in that special case. No rigorously
derived or fully validated correction for
aggregate particles is available.
Reaction routes for vapor phase synthesis 293
PARTICLE DEPOSITION
The deposition of particles on macroscopic
surfaces is an important factor in determining
the efficiency of powder synthesis reactors
and the quality of films produced by chemical
vapor deposition. Particles can deposit by
Brownian diffusion, but in high temperature
reactors, thermophoretic deposition often
dominates. Thermophoresis is the migration
of small aerosol particles that is induced by
a temperature gradient. It causes particles
carried in a hot gas to deposit on a cool sur-
face. For small particles, Kn ~ 1, the thermal
dimensionless group
vTpT
Th = - J1(dT /dx) (11.52)
where VT is the thermophoretic velocity, is
essentially constant. Theoretical predictions
suggest a value of Th between 0.42 and 1.5,
and experimental measurements indicate
Th ~ 0.5 (Talbot et al., 1980; Flagan and Sein-
feld,1988).
In laminar flow aerosol reactors, thermo-
phoresis can cause substantial losses of the
product particles. In chemical vapor deposi-
tion on heated substrates, thermophore sis
may create a particle-free layer adjacent to
the surface, thereby protecting the film from
particulate contamination. If epitaxial films
are not required, thermophoresis can sub-
stantially enhance film growth rates in a
process known as particle-precipitation-
aided chemical vapor deposition (Komiyama
et al., 1987) or in the optical waveguide litera-
ture as modified chemical vapor deposition
(Nagel, MacChesney and Walker, 1982;
Weinberg, 1982).
REACTION ROUTES FOR VAPOR PHASE
CERAMIC SYNTHESIS
The predominant routes for the synthesis of
ceramic materials from vapor phase pre-
cursors are based upon the combination of
two or more reactants to produce the desired
294 Thermochemistry and kinetics
material. These association reactions typically
require high temperatures and may approach
the equilibrium ideal. The reactions that
produce ceramic materials from the specially
designed precursors are often essentially
irreversible. Of course, with the vast range
of chemistries employed, there is a continuum
of operating conditions and degrees of
reversibility.
The key requirement for the synthesis of the
ceramic material from the vapor phase is a
precursor for each chemical moiety and that
is sufficiently volatile to allow adequate
throughput rates in available reactor systems.
The volatility required varies dramatically
with the technology being employed. For
chemical vapor deposition of thin films, rela-
tively low partial pressures can yield adequate
film deposition rates whereas powder syn-
thesis reactors require substantial precursor
partial pressures to be economical. Metal
halides generally have the volatility required
for use as ceramic precursors. Reactions with a
reductant such as H 2, Na etc. have long been
used to produce high purity metals from such
precursors as SiCl4 , TiCl4 , BCl3 etc. Reaction
schemes have been developed to produce
carbides, nitrides, borides and other ceramic
materials from such halides. Sub halides
(SiHCl3 , SiH2Cl2 etc.) also see extensive use.
These compounds introduce an additional
dimension of control over the reactions that
lead to chemical vapor deposition. This
aspect is particularly important in the fabrica-
tion of semiconductor microelectronic devices
since excessively high temperatures can lead
to interdiffusion of successively deposited
layers and degradation of device perfor-
mance.
Numerous review papers have summarized
the vast array of chemical pathways to non-
oxide ceramics from vapor phase precursors
(e.g. Kato, Hojo and Watari, 1984; Wachtman
and Haber, 1986; Sheppard, 1987; Stinton,
Besmann and Lowden, 1988; Chorley and
Lednor, 1991). In the discussion that follows,
representative reaction pathways for the
synthesis of specific ceramic materials are
discussed, along with the extent of available
data on the detailed kinetics. We begin with
the best documented systems, SiC and Si3 N 4 ,
and then turn our attention to other non-oxide
ceramic materials.
SILICON CARBIDE
As one of the major non-oxide ceramics of
importance for both structural and electronic
materials, both chemical vapor deposition and
the gas phase synthesis of powders of SiC
have received considerable attention since
the early part of this century (e.g. Pring and
Fielding, 1909). Detailed thermodynamic
analyses of SiC synthesis have been reported
for high temperature plasma synthesis of
powders (Chang and Pfender, 1987) and for
chemical vapor deposition (Kingon, Lutz and
Davis, 1983a, b; Fischman and Petuskey, 1986).
In addition, a detailed kinetic model has been
developed for the chemical vapor deposition
of SiC by the reaction of SiH4 and propane
(Allendorf and Kee, 1991).
Silicon carbide thermochemistry
The primary routes proposed for the synthesis
of SiC are based upon the reactions of SiH4 or
chlorosilanes with hydrocarbons and hydro-
gen. A variety of hydrocarbons have been
used as the carbon source. From a thermo-
dynamic point of view, the particular hydro-
carbon selected is not important. The relative
numbers of moles of the elements Si, C, Cl and
H determines the equilibrium state. The
production of elemental chlorine is thermo-
dynamically unfavorable. In the system
SiCI4 /CCI4 , the only condensed phase
formed at temperatures of 1000 K (727 DC)
and 2000 K (1727 DC) was graphite (Kingon,
Lutz and Davis, 1983a, b). Addition of hydro-
gen, either in the form of H2 or hydrocarbon
precursors other than CCl4 allowed HCl to
form and made (1-SiC a thermodynamically
favorable product at chemical equilibrium.

Using JANAF data (1986) which indicate a
lower value of the free energy of ,a-SiC than
for a-SiC at all temperatures, Kingon, Lutz
and Davis (1983) found that the only SiC
phase present at any of the equilibrium con-
ditions calculated was ,a-SiC. ,a-SiC has been
observed as the primary product in a
number of vapor phase syntheses, induding
thermal plasma synthesis (Kong and Pfender,
1987), gas evaporation (Ando and Uyeda,
1981) and laser synthesis (Fantoni et al., 1990).
The change in the equilibrium chemistry for
the synthesis of ,a-SiC can be seen by examin-
ing the free energy changes for the overall
reactions, as summarized in Table 11.1. Indi-
cated in this table are the values of the
enthalpy of reaction and the free energy
change for reaction at 298 K (25 DC), as well
as the temperature at which the free energy
change equals zero (Tc> and the enthalpy of
reaction at that temperature. For the reactions
of SiH4 , disilane and tetramethylsilane, no TG
value is given since ~GR < 0 at all tempera-
tures. As noted above, reactions leading to
Cl2 as a major product are thermodynamically
unfavorable except at very high temperatures.
The reactions of SiH4 with various hydro-
carbons leading to the production of ,a-SiC
and HCl have a negative ~GR at all tempera-
tures and are, therefore, thermodynamically
Reaction routes for vapor phase synthesis 295
favored. For the chlorosilane reactions, the
temperature at which ~GR = 0 increases
with increasing Cl/Si ratio. Additional equili-
bria are relevant, namely the etching of ,a-SiC
by HCl to produce C(s) and volatile silicon
species, primarily SiCl4 . The equilibria for
these etching reactions are also indicated in
the table.
Silicon carbide reaction mechanisms
and kinetics
While the reactions leading to SiC are thermo-
dynamically favorable, most are endothermic,
so energy must be supplied to maintain the
temperatures required for reaction. Even the
exothermic SiH4 reactions require elevated
temperatures to achieve useful reaction rates.
The understanding of the reaction mechan-
isms used to synthesize silicon carbide is
incomplete, but is better developed than for
other non-oxide ceramics. The level of under-
standing results from the importance of many
of the important reactions of hydrocarbons
to combustion processes and those of SiH4
to chemical vapor deposition of silicon.
Allendorf and Kee (1991) have developed a
detailed mechanism for the reactions of SiH4
with propane (C 3 H s ). The gas phase reaction
mechanism is presented in Table 11.2 to

Table 11.1 Overall reactions for the synthesis of silicon carbide from vapor phase precursors

Reaction ~HR (298K) ~GR (298K) Tc ~HR (Tc)

(kllmol) (kllmol) (K) (kllmo/)

SiCl4 + Cl4 ~ SiC(jJ) + 4Cl2 142.9 162.0 2694 156.3

SiCl4 + CH4 ~ SiC(,B) + 4HCl 287.5 214.0 1140 290.7
HSiCl3 + CH4 ~ SiC(,B) + 3HCI + H2 317.4 272.2 1901 322.7
H 2SiCl2 + CH4 ~ SiC(,B) + 2HCl + 2H2 151.8 98.5 793 165.9
SiH4 + CH4 ~ SiC(,B) + 4H2 -28.9 -73.2 ~G<O
Si(CH3 )4 ~ SiC(,B) + 3CH4 -11.2 -75.0 ~G<O
SiCl4 + ! C 2H 2 + ~ H2 ~ SiC(,B) + 4HCI 99.3 58.6 753 92.5
SiCl4 + !C2H 4 + H2 ~ SiC(,B) + 4HCl 186.5 129.1 977 182.3
l
SiCl4 + C 3 Hs + ~ H2 ~ SiC(,B) + 4HCI 247.3 196.9 1648 211.5
!Si2H 6 +!C2H 4 ~ SiC(,B) +~H2 -65.0 -79.0 ~G<O
296 Thermochemistry and kinetics
Table 11.2 Gas phase reactions involved in the synthesis of silicon carbide from vapor phase precursors

No. Reaction No. Reaction

l. C 3H S ~ CH3 + C 2H S 44. C 2H 3 + CH ~ CH 2 + C 2H 2
2. CH3 + C3HS ~ CH4 + i*C 3H7 45. CH2 +M~CH2+M
3. CH3 + C3HS ~ CH4 + n*C 3H7 46. CH2 + CH4 ~ CH3 + CH3
4. H + C3HS ~ H2 + i*C 3H7 47. CH2 + C 2H 6 ~ CH3 + C 2H S
5. H + C3HS ~ H2 + n*C 3H7 48. CH2 + H2 ~ CH 3 + H
6. i*C3H7 ~ H + C3H6 49. CH2 + H ~ CH 2 + H
7. i*C 3H7 ~ CH3 + C 2H 4 50. CH2 +CH2 ~C2H2 +H+H
8. n*C3H7 ~ H + C3H6 5l. CH 2 + C 2H 2 ~ H 2CCCH + H
9. n*C 3H7 ~ CH3 + C 2H 4 52. CH 2 + C 2H 2 ~ H 2CCCH + H
10. i*C3H7 + C 3H S ~ n*C 3H7 + C 3H S 53. C 2H 2 +M ~ C 2H+H+M
11. C 2H 3 + C 3H S ~ C 2H 4 + i*C 3H7 54. C 2H 4 + M ~ C 2H 2 + H2 + M
12. C 2H 3 + C3HS ~ C 2H 4 + n*C 3H7 55. C 2H 4 + M ~ C 2H 3 + H + M
13. C 2H S + C 3H S ~ C 2H 6 + i*C3H7 56. H+H+M~H2+M
14. C 2Hs + C 3HS ~ C 2H 6 + n*C3H7 57. H+H+H2 ~ H2 +H2
15. C3H6 + H ~ CH2CHCH2 + H2 58. SiH4 ~ SiH2 + H2
16. C3H6 + CH 3 ~ CH 2CHCH2 + CH4 59. Si~ ~SiH3+H
17. C3H6 + C2HS ~ CH2CHCH2 + C 2H 6 60. Si2H 6 ~ SiH4 + SiH2
18. C 3Hs + CH2CHCH2 ~ i*C 3H7 + C 3H6 6l. Si~ + H ~ SiH3 + H2
19. C3HS + CH2CHCH2 ~ n*C 3H7 + C 3H 6 62. SiH4 + SiH3 ~ Si2H S + H2
20. CH2CHCH2 ~ C 3H4 + H 63. SiH4 + SiH ~ Si2H 3 + H2
2l. C3H6 ~ CH2CHCH2 + H 64. SiH4 + SiH ~ Si2Hs
22. C 3H 6 ~ C 2H 3 + CH3 65. SiH2 ~ Si+H2
23. CH2CHCH2 + H ~ C 3H4 + H2 66. SiH2 + H ~ SiH + H2
24. CH2CHCH2 + CH3 ~ C 3H4 + CH4 67. SiH2 + H ~ SiH3
25. CH3 +CH3(+M) ~ C 2H 6(+M) 68. SiH2 + SiH3 ~ Si2HS
26. CH3 +H(+M) ~ CH4(+M) 69. 5iH2 + Si2 ~ Si3 + H2
27. CH4 +H ~ CH3+H2 70. SiH2 + Si3 ~ Si2H 2 + Si2
28. CH3 +H ~CH2 +H2 7l. H 2SiSiH2 ~ Si2H 2 + H2
29. CH2 +H~CH+H2 72. Si2~ ~ H 3SiSiH + H2
30. CH+C 2H ~ C 3H2 +H 73. H 2 + SiH ~ SiH3
3l. CH+CH2 ~C2H2 +H 74. H 2 + Si2 ~ Si2H 2
32. CH+CH3 ~C2H3 +H 75. H 2 + Si2 ~ SiH + SiH
33. CH+CH4 ~C2H4 +H 76. H 2 + Si3 ~ Si + Si2H 2
34. C 2H 6 + CH 3 ~ C2HS + CH4 77. SizHs ~ Si2H 3 + H2
35. C 2H 6 + H ~ C2HS + H2 78. Si2H 2 + H ~ Si2H 3
36. C 2H 4 + H ~ C 2H 3 + H2 79. H + Si2 ~ SiH + Si
37. CH2 + CH3 ~ C 2H 4 + H 80. H 3SiSiH + Si~ ~ Si3HS
38. H +C2H 4(+M) ~ C 2H s (+M) 8l. SiH2 + Si2H 6 ~ Si3HS
39. C2HS + H ~ CH3 + CH 3 82. SiH3 + Si2HS ~ Si3H S
40. H 2 + C 2H ~ C 2H 2 + H 83. H 3SiSiH ~ H 2SiSiH2
4l. H +C2H 2(+M) ~ C 2H 3(+M) 84. SiH4 + CH3 ~ SiH3CH 3 + H
42. C 2H 3 + H ~ C 2H 2 + H2 85. SiH4 + CH2 ~ SiH3CH 3
43. C 2H 3 + C 2H ~ C 2H 2 + C 2H 2 86. SiH2 + CH4 ~ SiH3CH3

Sources: 1-83, Allendorf and Kee (1991); 84-86, Tachibana et al. (1992).

illustrate the level of detail involved in
modeling the kinetics of CVD. It involves 83
fundamental reaction steps, including the
reactions of lower hydrocarbons, including
C 2H 6 , C2H 4 , C2H 2 and CH4 .
Allendorf and Kee (1991) specified rate
coefficients for each of the individual reactions
to complete the gas phase kinetic model. The
rate coefficients were obtained from a variety
of fundamental kinetics studies. Many of the
values were experimentally measured, while
some, such as the unimolecular decomposition
of SiH4 , were predicted theoretically using, for
example, the RRKM method. The gas phase
reaction mechanism includes reactions of
the hydrocarbon species (reactions 1-57 in
Table 11.2) and those involved in the thermal
decomposition of SiH4 (reactions 56-83 in
Table 11.2). None of the identified gas phase
reactions leads to the formation of the
silicon-carbon bond, although the hydro-
carbon and SiH4 reactions are coupled through
the reactions of Hand H2 which play critical
roles in both mechanisms.
Thus, the gas phase reaction mechanism
presents only part of the story. Surface reac-
tions are required to complete the description.
Unlike the gas phase reactions, few thermo-
dynamic and kinetic data are available for
the surface reactions. The surface species
considered by Allendorf and Kee (1991) are
summarized in Table 11.3. In the surface
reaction mechanism, surface species are
indicated by (s), e.g. Si(s) denotes surface
silicon. Since surface species can be over-
coated by subsequent reactions, the notation
(b) is introduced to describe the species in
the bulk of the material, i.e. those below the
surface layer. They assumed that deposition
occurs on dangling bond sites on the SiC
surface. The number of such sites is estimated
to be 6.5 x 1014 /cm2 and is assumed to be
conserved. Gas phase molecules that are
transported to and stick on the surface are
assumed to be surface species. Surface species
that are covered by subsequent surface reac-
tions are converted to bulk species. Hydrogen
Reaction routes for vapor phase synthesis 297
residing on the surface is denoted (Si)H or
(C)H, depending upon whether it is bound
to silicon or carbon. The correct stoichiometry
is guaranteed in their model by allowing
silicon to deposit only on carbon, and carbon
to deposit only on silicon. This constrains
the product composition, precluding the
formation of either graphite or elemental
silicon in the condensed phase. The appear-
ance of silicon and graphite lines in x-ray
diffraction spectra of gas-phase-synthesized
SiC powders clearly demonstrate that this
is an oversimplification. Nonetheless, this
model represents an important first step in
the understanding of the kinetics of non-
oxide ceramic synthesis from gas phase
precursors.
Even though the reaction mechanism pro-
posed by Allendorf and Kee (1991) includes
119 separate reactions, it is undoubtedly
incomplete. For example, Tachibana et al.
(1992) have performed quantum chemical
calculations that suggest that the reactions
of SiH4 with methyl (CH3 ) or methylene
(CH 2) or the reactions of methane with
silylene (SiH2) (Table 11.2) have low energy
barriers to reaction, i.e. flH R84 = 35.6kJ/mol,
flHR85 = -524kJ/mol and flH R86 = -205kJ/
mol. Hence, they are likely to proceed with
sufficiently high rates to contribute to SiC
formation. These reactions would allow the
formation of the silicon-carbon bond in the
gas phase, even though Si-Si bond formation
is favored.
Silicon carbide is a promising material for
advanced semiconductor applications, stimu-
lating interest in specially designed, single-
source precursors that might improve the
control of the Si-C stoichiometry and, at
the same time, lower deposition tempera-
tures. Larkin and Interrante (1992) report
promising results from 1,3-disilacyclobutane,
with nearly stoichiometric (",,2 atm% excess
silicon being produced at a deposition tem-
perature of 1083 K (810C), and stoichiometric
SiC resulting from depositions at 1218 K
(945C) and 1328 K (1055C. In a related
298 Thermochemistry and kinetics
Table 11.3 Surface reactions in the Si-C system

No. Reaction

87. H + Si(s) ~ (Si)H + Si(b)

88. H + C(s) ~ (C)H + C(b)
89. 2(Si)H + 2Si(b) ~ 2Si(s) + H2
90. 2(C)H + 2C(b) ~ 2C(s) + H2
91. CH4 + Si(s) ~ C(s) + Si(b) + 2H2
92. CH3 + Si(s) ~ CH(s) + Si(b) + H2
93. CH2 + Si(s) ~ C(s) + Si(b) + H2
94. CH2(S) + Si(s) ~ C(s) + Si(b) + H2
95. CH + Si(s) ~ CH(s) + Si(b)
96. C2HS + 2Si(s) ~ C(s) + CH(s) + 2H2 + 2Si(b)
97. C2H 4 + 2Si(s) ~ 2C(s) + 2H2 + 2Si(b)
98. C2H 3 + 2Si(s) ~ C(s) + CH(s) + 2Si(b) + H2
99. C2H 2 + 2Si(s) ~ 2C(s) + 2Si(b) + H2
100. i*C3H7 + 3Si(s) ~ 2C(s) + CH(s) + 3Si(b) + 3H2
101. n*C 3H7 + 3Si(s) ~ 2C(s) + CH(s) + 3H2 + 3Si(b)
102. C3H6 + 3Si(s) ~ 3C(s) + 3H2 + 3Si(b)
103. C3~ + 3Si(s) ~ 3C(s) + 3Si(b) + 2H2
104. H 2CCCH + 3Si(s) ~ 2C(s) + CH(s) + H2 + 3Si(b)
105. CH2CHCH2 + 3Si(s) ~ 2C(s) + CH(s) + 2H2 + 3Si(b)
106. C3H2 + 3Si(s) ~ 3C(s) + H2 + 3Si(b)
107. SiH2 + C(s) ~ C(b) + SiH2(s)
108. Si~ + C(s) ~ C(b) + SiH2(s) + H2
109. SiH3 + C(s) ~ C(b) + SiH(s) + H2
110. SiH + C(s) ~ C(b) + SiH(s)
111. Si + C(s) ~ C(b) + Si(s)
112. Si2HS + 2C(s) ~ 2C(b) + SiH(s) + SiH2(s) + H2
113. Si2H3 + 2C(s) ~ 2C(b) + SiH2(s) + SiH(s)
114. Sh + 2C(s) ~ 2C(b) + 2Si(s)
115. Si2H6 + 2C(s) ~ 2Si(s) + 2C(b) + 3H2
116. H 3SiSiH + 2C(s) ~ 2C(b) + 2SiH2(s)
117. H 2SiSiH2 + 2C(s) ~ 2C(b) + 2SiH2(s)
118. Si2H 2 + 2C(s) ~ 2C(b) + 2SiH(s)
119. Si3 + 3C(s) ~ 3C(b) + 3Si(s)
120. 2CH(s) ~ 2C(s) + H2
121. 2SiH(s) ~ 2Si(s) + H2
122. SiH2(s) ~ Si(s) + H2

Source: Allendorf and Kee (1991).

development, Li et al. (1994) used laser pyro-
lysis of diethoxydimethylsilane to produce
ultrafine (Dp < 30 nm) SiC powders.
Many of the efforts on chemical vapor
deposition of SiC have focused on chloro-
silanes. Reaction of silicon tetrachloride with
C3HS and H2 deposits ,B-SiC at temperatures
in excess of 1300 0c. Methyl-substituted chlor-
osilanes lower the required reaction tempera-
tures. Dichlorodimethyl silane reactions with
H2 lead to SiC deposition at temperatures
of 700C to 1000 0c. Methyltrichlorosilane
reactions deposit SiC at intermediate tempera-
tures. Although the kinetics of these systems
are less well understood than those for the
Si-H-N system, mechanistic models have
 Reaction routes for vapor phase synthesis 299
Table 11.4 Overall reactions for the synthesis of silicon nitride from vapor phase precursors

Reaction ~HR (298K) ~GR (298K) TG ~HR(Td

(klima/) (klima/) (K) (kJlmal)

3SiCl4 + 2N2 + 6H 2 r" Si3N4(S) + 12HCl 112.9 54.6 618 93.4

3SiCl4 + 4NH3 r" Si3N4(S) + 12HCl 296.5 120.1 498 299.9
3H2SiC12 + 4NH3 r" Si3N4(S) + 6HCl + 6H 2 -110.9 -226.2 ~G<O
3SiH4 + 4NH3 r" Si3N4(S) + 12H2 -652.8 -741.4 ~G<O
3SiH4 + 2N2 r" Si3N4 + 6H2 -836.4 -806.9 ~G<O

been proposed (Cagliostro and Riccitiello The silene radical (SiH3) is produced by the
1993). SiH4 decomposition reactions that were sum-
marized in the SiC production mechanism.
Amidogen radicals (NH 2) are produced by
SILICON NITRIDE
the pyrolytic reactions of NH3 which have
Ammonia is usually used as the nitrogen been studied extensively because of their
source in Si3N4 synthesis. Silane or chloro- importance in air pollution control systems.
silanes can be used as the silicon source,
although the chlorosilanes have the potential
Table 11.5 Gas phase reactions of the Si-N-H
disadvantages of introducing halide contami- system
nants into the product material and the
production of corrosive reaction by-products. Na. Reaction
A comprehensive thermodynamic analysis of
the synthesis of silicon nitride from SiH4 and 123. SiH 4 + NH3 r" SiH3NH2 + H2
chlorosilanes has been presented by Kruis et al. 124. NH2 + SiH3 r" SiH2NH2 + H
125. NH2 + SiH2(NH 2) r" SiH2(NH 2 h + H
(1992). Table 11.4 summarizes the overall 126. SiH2 + NH3 r" SiH3NH2 + H
reactions for the synthesis of Si3N4 from 127. SiH3NH2 r" SiHNH2 + H2
SiCl4, H 2SiCl2 and SiH4 using both N2 and 128. SiH3 + NH3 r" SiH3NH2 + H
NH3 as nitrogen sources. All of the reactions 129. SiH3 + NH3 r" SiH2NH 2 + H2
indicated are thermodynamically favorable at 130. NH3 + M r" NH + H2 + M
quite low temperatures, with the SiH4 and 131. NH2 + M r" NH + H + M
dichlorosilane reactions being favored at all 132. NH + M r" N + H + M
133. NH3 + H r" NH2 + H2
temperatures. 134. NH2 + H r" NH + H2
The mechanism of synthesis of Si3N4 by 135. NH + H r" N + H2
the reaction of SiH4 with NH3 is thought to 136. N2H + NH r" N2 + NH2
proceed via amino-silane complexes. In one 137. NH + NH r" NH2 + N
of the earliest papers on this process, 138. NH + NH r" N2H + H
Prochazka and Greskovich (1978) postulated 139. N2H2 + NH2 r" N2H + NH3
that the reaction of SiH4 with NH3 (reaction 140. N2H + NH2 r" N2 + NH3
141. NH2 + NH2 r" NH3 + NH
123 in Table 11.5) was the starting point 142. NH + NH2 r" N2H2 + H
for Si3N4 formation. More recent studies by 143. NH +N r" N2 + H
Koseki and Ishitani (1992), Sommerer and 144. N2H + N r" NH + N2
Kushner (1992) and Tachibana et al. (1992)
suggest that the reactions of reactive inter- Sources: 123, Prochazka and Greskovich (1978); 124, 125,
Sommerer and Kushner (1992); 126, 127, Koseki and
mediates and radical species (Table 11.5) are Ishitani (1992); 128, 129, Tachibana et al. (1992); 130-144,
important. Hanson and Salimian (1984).
300 Thermochemistry and kinetics
Some of the key reactions reported by Hanson
and Salimian (1984) are summarized in Table
11.5. These reactions include the successive
abstractions of hydrogen and the reactions
that lead to the formation of the very stable
nitrogen-nitrogen bond which effectively
removes the nitrogen from the pool of reactive
species.
The detailed reaction mechanisms for the
synthesis of Si3N4 from chlorosilanes and
NH3 are not fully understood. Morosanu
(1990) suggests that the key reaction when
SiH2Cl2 is employed is the production of SiCl2
by homogeneous, gas phase decomposition of
SiH2C12. The SiCl2 then adsorbs on the surface
where it reacts with adsorbed NH3. Details of
the reaction mechanism and the corresponding
kinetics remain to be developed.
NON-OXIDE CERAMICS FROM
HALOGEN PRECURSORS
A wide range of non-oxide ceramics have
been synthesized from vapor phase halide
precursors. Table 11.6 lists some of the
routes that have been explored for such
synthesis. As in the synthesis of SiC and
Si3N 4, halogen precursors are thermodynami-
cally favored at reasonable temperatures as
long as hydrogen is included among the reac-
tants to promote the formation of HCI and
HBr rather than Cl2 and Br2. The temperature
required for aluminum nitride synthesis by
reaction of AICl 3 with NH3 is particularly
low, i.e. the reaction is thermodynamically
favored at temperatures above 648 K (375C).
This and other aluminum halide reactions
have long been applied to the synthesis of
this material (Pauleau et ai., 1980; Huseby,
1983; Kimura et ai., 1988). Extensive thermo-
dynamic analyses of this formation process
have been reported by Nickel, Riedel and
Petzow (1989), and Hashman and Pratsinis
(1992).
Titanium nitride can be synthesized at
similarly low temperatures, although the
literature on this material is far less extensive
than that on AlN. Buiting and Reader (1990)
report on the production of TiN films by low
pressure chemical vapor deposition from
mixtures of TiCI4, NH 3, H2 and Ar at
temperatures as low as 725 K (452C),
although the films deposited at temperatures
below about 775 K (502C) contained several

Table 11.6 Reactions for the synthesis of various non-oxide ceramics from vapor phase halide precursors

Reaction ~HR (298K) ~GR (298K) Tc ~HR(Tc)

(kJlmol) (kJlmol) (K) ( Jlmol)

AlCl 3 + NH3 ~ AlN(s) + 3HCl 110.2 75.5 648 125.3

4BCl3 + CH 4 + 4H2 ~ B4C(S) + 12HCl 540.1 420.8 1377 524.9
4BCl3 + !C2H 4 + 5H2 ~ B4C(S) + 12HCl 439.0 336.0 1335 415.1
BCl3 + NH3 ~ BN(s) + 3HCl 648.9 562.4 2219 639.1
! B2H6 + NH3 ~ BN(s) + 3H2 502.9 414.5 1579 514.2
TiCl4 + CH 4 ~ TiC(s) + 4HCl 284.7 215.9 1195 290.1
TiBr4 + CH4 ~ TiC(s) + HBr 295.2 225.4 1227 300.8
TiCl4 + ! N2 + 2H2 ~ TiN + 4HCl 56.3 36.6 937 49.5
TiCl4 +NH3 +!H2 ~ TiN(s) +4HCl 53.0 102.2 615 103.9
TiCl4 + 2BCl3 ~ TiB2 + 5Cl2 1227.0 1289.0 ~G>O
TiCl4 + 2BCl3 + 5H2 ~ TiB2 + 5HCl 366.5 274.4 1288 337.1
TiCl4 + B2H6 ~ TiB2 + 4HCl + H2 73.4 -21.5 229 70.7
ZrCl4 + 2BCl3 + 5H2 ~ ZrB2 + 10CHl 429.6 339.3 1572 392.6
ZrCl4 + CH 4 ~ ZrC + 4HCl 378.3 310.8 1602 384.0
ZrCl4 + NH3 + ! H2 ~ ZrN + 4HCl 1259.0 1154.0 ~G>O

atomic percent chlorine. Films produced at
923K (650C) contained less than 1 atm%
chlorine. The reaction of TiCl4 with N2 is
thermodynamically favored at temperatures
as low as 937K (664C), but the rates of
reaction are likely to be much lower than
those using more reactive NH3 as
the nitrogen source. There are, however,
indications that ultrafine titanium particles
produced from the vapor phase are extremely
reactive to N2 (Benton and Kragh, 1991).
Comprehensive reaction mechanisms have
not yet been developed for the synthesis of
titanium nitride although some investigations
have been reported. Nakanishi, Mori and
Kato (1990) postulate that TiC~, H2 and N2
are adsorbed on the surface. Abstraction of
chlorine from TiCl4 by hydrogen atoms,
TiCl4 + H ~ TiCl3 + HCl (11.53)
TiCl3 + H ~ TiCl2 + HCl (11.54)
TiCl2 + H ~ TiCI + HCl (11.55)
TiCI + H ~ Ti + HCI (11.56)
lead the way for production of N, NH, NH2
and NH3 on the surface and surface reactions
that lead to the formation of TiN. It was sug-
gested that the most probable rate controlling
step is the production of the reactive nitrogen
species on the surface. The proposed model
did not consider the complex gas phase chem-
istry, much of which is included in the reac-
tion mechanism that was discussed above for
the synthesis of SiC and Si3N 4
Titanium diboride formation from TiCl4
and BCl3 is thermodynamically favored at
moderate temperatures as long as hydrogen
is present. Titanium diboride formation
from TiCl4 and B2H6 is favorable even below
ambient temperature.
Boron carbide (B 4 C) and boron nitride (BN)
production require higher temperatures
than do the silicon, aluminum or titanium
compounds. In the synthesis of BN, the ther-
mal instability of diborane (B 2H 6) leads to a
reduction in the temperature at which the
Reaction routes for vapor phase synthesis 301
reaction becomes thermodynamically favor-
able to values accessible by a variety of reactor
technologies. The reaction of BCl3 with NH3
requires temperatures in excess of 2200 K
(1927C) and is, therefore, limited to plasma
reactors or other systems that can sustain
such high temperatures.
Zirconium diboride (ZrB 2) and carbide
(ZrC) are thermodynamically favored from
ZrCI4 , but zirconium nitride is not.
SINGLE-SOURCE PRECURSORS
The needs of the microelectronics industry for
low temperature routes for the synthesis of
stoichiometric non-oxide ceramics has cata-
lyzed a number of developments of specially
designed single-source precursors. Organo-
metallic compounds have long been used for
chemical vapor deposition of AlN. For
example, Manasevit, Erdmann and Simpson
(1971) employed the reaction of trimethyl-
aluminum and NH3 to produce aluminum
nitride (AlN) via the overall reaction
AI(CH3h + NH3 ---+ AlN + 3CH4 (11.57)
The temperature required for that reaction
was 1573 K (1300C), high enough to limit
the application of the method even though
epitaxial deposition was achieved. Interrante
et al. (1986) developed precursors containing
both Al and N through studies of inter-
mediates produced in the reaction of alkyl-
aluminum and NH 3. A particularly volatile
product was [(CH3)2Al(NH2)h which is a
six-membered ring in a chair conformation.
Boyd et al. (1989) developed organometallic
azides, notably [R2AlN 3h, R = Me, Et.
Pyrolysis of these compounds at 670-870 K
(397-597C) resulted in the deposition of
uniform amorphous films of AlN on Si(lOO)
substrates.
Fix, Gordon and Hoffman (1990) describe
the synthesis of titanium nitride (TiN) at low
temperatures by vapor phase decomposition
of Ti(NR2)4 compounds in the presence of
excess HNR~. Specifically, they employed
302 Thermochemistry and kinetics
Ti(NMe2)4 and Ti(NEt2)4 in conjunction with
excess NH3 at deposition temperatures
ranging from 373 K to 673 K (100-400 DC).
Without the added NH 3, no deposition was
observed at temperatures below 573 K
(300 DC), and only powdery deposits were
obtained at that temperature. With the com-
bined reactants, smooth, non-porous deposits
were produced. Some carbon was incorpo-
rated into the deposits at deposition tem-
peratures above 573 K (300 DC). A similar
approach was applied to the synthesis of
AlN films by Gordon, Hoffman and Riaz
(1991) through the use of hexakis(dimetha-
mido)dialuminum, A12(NMe2)6, at tempera-
tures in the range 473-523 K (200-250 DC) and
at ambient pressure.
These are but a few of the many studies of
the specially designed single-source pre-
cursors for the chemical vapor deposition of
non-oxide ceramics. The thermochemistry
and kinetics of these processes for synthesiz-
ing non-oxide ceramics are much less well
understood than for some of the more conven-
tional routes since the primary efforts in this
arena have been devoted to the synthetic
chemistry and the understanding of the
nature of the role of precursor structure in
determining the properties of the deposited
material. Most present applications of
organometallic precursors are for chemical
vapor deposition of thin films, primarily for
microelectronic applications, although some
ventures into powder synthesis by such
routes have been reported. Notably, Adjaottor
and Griffin (1992) produced AlN powders
by the gas phase reaction of Al(C 2H sh with
NH 3
SUMMARY
Non-oxide ceramics are produced by a
vast array of chemical processes. The
thermochemistry of these processes is well
understood in many cases, but the kinetics
have been studied to a much smaller degree.
Chemical equilibrium provides an indication
as to the feasibility of a proposed chemical
pathway to a material, but the kinetics of
both gas phase and condensed phase pro-
cesses must be understood to design and
control the synthesis.
Because of the low densities involved, the
chemical mechanisms and kinetics of vapor-
phase synthesis of ceramics can be understood
on a microscopic basis. Molecular interactions
are limited to collisions of short duration, with
long intervals between collisions. As a result,
the reaction rates are determined by the fre-
quency of collisions of the reacting molecules
and the energetics of those collisions. Increas-
ingly, kinetic descriptions of the reaction
process are being developed that describe
the evolution of the many intermediate
species that are masked by the usual overall
description of the reaction stoichiometry. A
complete description of the kinetics of such
reactions requires writing and solving a rate
equation for each of the species involved.
This once formidable task is now handled
quite efficiently using robust chemical kinetic
codes such as CHEMKIN. Codes have also
been developed to model the coupling
between the gas phase chemistry and the sur-
face chemistry involved in chemical vapor
deposition, although the level of detail in the
models of the surface reactions is generally
much lower than that for the gas phase
reactions, and with the macroscopic transport
equations. Such models are used routinely
to simulate chemical vapor deposition of
semiconductor materials, and models are
now being developed to describe the chemical
vapor deposition of ceramic materials as
well.
The synthesis of particles from vapor phase
precursors, either intentionally in the syn-
thesis of powders or unintentionally in
chemical vapor deposition processes, intro-
duces an additional dimension to the kinetics.
The nucleation of the condensed phase, either
solid or liquid, and the subsequent growth of
the resulting particles must also be modeled.
Aerosol particles grow by a combination of

gas-to-particle conversion processes (conden-
sation and surface reactions) and coagulation.
The dynamics of the aerosol are coupled
directly to the gas phase chemical kinetics.
The aerosol particles act as distributed sinks
or sources for gas phase species. Coagulation
frequently leads to the formation of low density
aggregates when solid particles are formed. At
high temperatures the aggregates may sinter to
form hard agglomerates. Most of the theory of
aerosol dynamics has been developed for
particles that remain spherical throughout
their evolution, but a number of important
features of aggregate aerosols have been eluci-
dated in recent years due to interests in their
fractal-like structures. Efficient and robust
codes for the simulation of aerosol dynamics
have been developed, e.g. MAEROS. These
models have been thoroughly tested for the
special case when the particles remain spherical
throughout their evolution. Models of aerosol
aggregation have been developed, but they
have not yet been validated against carefully
designed experiments. Descriptions of phase
transitions in the particulate phase and simul-
taneous coagulation and sintering have
been incorporated into some models, but
no attempts at validation have yet been
reported.
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THERMAL AEROSOL PROCESSES
M. Kamal Akhtar and Sotiris E. Pratsinis
OVERVIEW
Gas phase powder synthesis refers to the
production of particles by gas phase (aerosol)
processes. These processes have received
increased attention in materials processing
since they do not involve the tedious steps
and large, environmentally burdensome,
liquid volumes of wet chemical processes. In
addition, the time scales of aerosol processes
are much shorter than those involving solid-
solid reactions. Furthermore, these processes
can produce materials of high purity at high
yields. Industry can provide several success
stories of implementing aerosol processes
in production of particulate commodities
(carbon blacks, pigmentary titania, fumed
silica) and optical fibers (Pratsinis and Mas-
trangelo, 1989). Though few of these processes
are currently used for non-oxide powder syn-
thesis, there is a strong likelihood that aerosol
processes will also be used in large scale man-
ufacture of non-oxides.
Depending on the phase of the raw
materials, aerosol processes can be classified
into two routes. Powders are made at high
temperatures either by reacting gases and
vapors (gas-to-particle conversion route) or
by transforming precursor particles/ droplets
to the desired product (particle-to-particle
conversion route). The characteristics of the
product powders made by each route are
distinctly different! A wide spectrum of
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
12
energy sources are used to provide the high
temperatures needed during gas-to-particle
conversion. Flame reactors employ the com-
bustion of hydrocarbons or hydrogen (H 2 )
and chlorine (Cl2 ) in diffusion or premixed
flames. Furnace reactors employ externally
heated metallic or ceramic tubes through
which the precursor gases are flowing. Laser
or plasma reactors utilize the energy of lasers
or of highly ionized gases, respectively. The
theoretical and experimental developments
in gas phase and particle-to-particle processes
for powder and film generation are detailed
by Gurav et al. (1993).
This chapter presents the fundamentals of
aerosol processes as they apply to gas phase
synthesis of non-oxide powders by conven-
tional thermal processes while the next two
chapters cover the use of lasers (Chapter 13)
and plasmas (Chapter 14). Specifically, the
gas-to-particle conversion route is examined
in some detail because it has been employed
in synthesis of non-oxides such as aluminum
nitride (A1N), silicon nitride (Si3N 4), boron
nitride (BN), silicon carbide (SiC), boron car-
bide (B 4C), titanium carbide (TiC), tungsten
carbide (WC) and titanium diboride (TiB 2 ),
in flames and electrically heated flow reactors.
Furthermore, the particle-to-particle con-
version route is examined because of its
increasing use and success in producing SiC,
BN and Si3N4 by spray pyrolysis and droplet
phase reactions. Finally, it should be noted
308 Thermal aerosol processes
that many of these processes are variations of
similar ones developed for the synthesis of
oxide particles with the added caveat of pre-
venting oxygen contamination from all process
stages.
FUNDAMENTALS
GAS-TO-PARTICLE CONVERSION
A schematic of the gas-to-particle conversion
route (Xiong and Pratsinis, 1991) is shown in
Figure 12.1. Precursor vapors or gases react at
high temperatures to form molecules and
molecular clusters of intermediate and even-
tually the product species. These clusters
result in particles either by nucleation or by
uninhibited coagulation. As the gas stream
leaves the high temperature zone and is
cooled, particles grow by surface reactions
and/ or coagulation. During transport, par-
ticles can be removed from the process
stream by diffusion and thermophoresis to
the reactor or tube walls. Eventually, the
particles are collected by filtration, electrostatic
precipitation or cyclones. Typically, this route
results in agglomerate particles that comprise
several primary particles. The residence time
and process temperature play a key role in
determining the extent of particle sintering
and, eventually, powder morphology and
crystallinity. Sometimes, additional post-
processing may be required to remove excess
carbon, oxygen or other species so that high
purity non-oxide powders can be produced.
Precursor gases
The precursor system for non-oxide powder
synthesis must satisfy two functions: (a) it
should be able to produce the product
powder at acceptable purity and yield and
(b) the precursors should be inexpensive and
convenient to use. Thermodynamic analyses
of various chemical pathways (e.g. for SiC
and Si3N4 by Kingon, Lutz and Davis (1983)

Mixture of
Precursor Gases

Radicals and Ultrafine Aggregates and

Molecular Primary Agglomerates of
Clusters Particles Solid Powder

~.~--------------~. ~.~------------~.-

Chemical Reaction and
Primary Particle Growth
by Collision and
Full Coalescence
Formation of Irregular
Particles by Collision
and Partial Coalescence
During Gas Cooling and
Particle Deposition

Figure 12.1 Schematic of the processes involved in the production of ceramic powders via the gas-to-
particle conversion route. (Xiong, Y. and Pratsinis, S.E., 'Gas phase production of particles in reactive
turbulent flows,' J. Aerosol. Sci., 22(5), 637-55, 1991. Reprinted with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX51GB, UK.)

and Kingon et al. (1983); for AIN by Hashman
and Pratsinis (1992 are useful in selecting
precursors. In addition, thermodynamics
indicate the feasibility of obtaining products
of the desired purity at high yield while the
kinetics of the reaction dictate reactor design
and operation as discussed in Chapter II.
Regarding the second function, precursor
gases and vapors are required for the metallic
(e.g. silicon (Si), titanium (TO, tungsten (W
and non-metallic (e.g. boron (B), carbon (C),
nitrogen (N elements forming the non-oxide
powder. In principle, every compound can be
introduced into the gas phase if sufficient
energy is provided. Few metal-containing com-
pounds, however, exist in the gaseous state at
room temperature. Metal vapors, their halides
and organometallic compounds are the most
common precursors for the metallic element
of the non-oxide powder. Precursors for the
non-metallic element are more easily found in
the gas phase, though gaseous compounds are
more expensive than their counterparts in a
condensed phase (e.g. boron trichloride (BCl3)
gas vs solid boron oxide (B20 3.
Once the most desirable precursors have
been identified, a system that will supply
them to the reactor must be designed. This is
of course trivial for precursors that are gases
under normal conditions (silane (SiH4 ),
ammonia (NH3), BCI3) but can be a serious
undertaking for solids. Vapors are readily
obtained from liquids (e.g. silicon tetrachlor-
ide (SiCl4 ), titanium tetrachloride (TiCl4 by
bubbling through the liquid an inert gas
(argon (Ar), helium (He or even a reactant
gas (NH3, methane (CH 4 that does not
react with the liquid at this temperature.
Solid precursors are most commonly intro-
duced into the reaction zone by either passing
an inert carrier gas (e.g. Ar, He) over a heated
refractory boat containing the solid precursor
(e.g. aluminum (AD, aluminum chloride
(AICl3), tungsten hexachloride (WCl 6 or
suspending solid particles in flow streams
(e.g. C-B203 particles, Weimer et al., 1991).
This is a rather delicate operation that requires
Fundamentals 309
careful design to avoid solid precipitation and
clogging of the manifold and reactor.
Chemical reaction and particle formation
Gas phase reaction between precursor gases
results in a number of species including radi-
cals, intermediates and the product. A com-
plete description of the chemistry is rarely
obtained, although this information would
be useful. The time scale of chemical reactions
is usually much shorter than the reactor resi-
dence time. Thus, a global reaction depicting
the reactants (gases X and Y) and products
(powder V and by-product gas W) is fre-
quently employed for reactor design (mass
and energy balances):
X(g) + Y(g) --4 V(s) + W(g) (12.1)
The thermodynamics of the reaction system
determine if the product molecules and
clusters will form particles by homogeneous
nucleation or by coagulation. If the clusters
are thermodynamically stable, no evaporation
takes place and particles are formed by coagu-
lation. Molecular clusters are unstable when
they grow or shrink by condensation or eva-
poration, respectively. In the case of these
unstable clusters, particles are formed by
homogeneous nucleation: balanced conden-
sation and evaporation of molecules to and
from clusters of the product species (Rao
and McMurry, 1989). A common criterion for
determining the importance of nucleation and
coagulation is the thermodynamically critical
radius of the product species. More specifi-
cally, if that radius is smaller than the radius
of a single molecule of the product species (rl),
then coagulation determines particle forma-
tion. In this case, the following criterion is
satisfied (Ulrich, 1971; Pratsinis, 1990):
2/,Vl
kBTrl -
< In (K CXCy )
eq Cw
(12.2)
where /' and VI are the surface tension and
molecular volume of the species V, Keq is
the equilibrium constant for reaction 12.1 at
310 Thermal aerosol processes
temperature T, and cx, Cy and Cw are gas
phase reactant and product concentrations.
Usually the importance of coagulation and
nucleation can be depicted in design diagrams
of process temperature and reactant conver-
sion (Xiong and Pratsinis, 1991).
Non-oxide ceramics (borides, nitrides and
carbides) have low equilibrium vapor pres-
sures and, hence, coagulation tends to control
particle formation. In general, homogeneous
nucleation is of limited importance for
ceramic particle formation by gas phase
chemical reactions. Nucleation is the domi-
nant mechanism for particle formation by
cooling of superheated vapors (condensation,
e.g. formation of iron particles in plasmas,
Girshick and Liu, 1989).
Particle growth
In particle formation from gas phase reactions,
chemical reaction rates are usually very high.
Growth of these particles takes place by coagu-
lation (particle-particle collision). Neglecting
the spread of particle size distribution and
particle morphology, one can calculate the
equivalent solid sphere diameter, dp' from the
expressions for aerosol coagulation. When d p is
much larger than the mean free path of the gas
(Chapman and Cowling, 1970):
A= 0.4~9PC (12.3)
where c is the average velocity of the gas
molecules:
(12.4)
and m is the molecular mass of the gas, then dp
is given by the classic coagulation theory in
the continuum regime (Friedlander, 1977):
dp = dpo (1 + N okc t)1/3 (12.5)
where t is the residence time and kc is a con-
stant for coagulation in the continuum regime:
kc = 4kBT (12.6)
3J.L
and No and dpo are the initial particle concen-
tration and diameter, respectively.
When dp is much smaller than A, then dp
is given by coagulation theory in the free
molecular regime, neglecting the spread of
the particle distribution:
d5/2 _ d5/2 10 (6kBT)1/2 V t
p-po+ vol (12.7)
7r Pp
where V vol is the total volume of powder per
unit volume of gas and Pp is the density of the
powder.
Increasing residence time gives approxi-
mately t1/ 3 increase in diameter because,
when two particles collide, their volume
doubles, but diameter goes up by a factor of
21/3. Increasing the temperature results in a
T1/6 and T1/3 increase in particle diameter in
the free molecular and continuum regimes,
respectively. In the free molecular regime, the
kinetic energy of the particles (Ek = mel /2,
where v is the particle velocity) equals their
own thermal energy (ET = 3kBT /2) according
to the equipartition theorem. As a result, the
particle velocity (or collision frequency) and
the corresponding particle volume increase
as T1/2. In the continuum regime, particles
move and collide by the motion and energy
of the gas medium. This energy is proportional
to kBT. As a result, when particles collide, their
diameter is proportional to T1/3 in the con-
tinuum regime (d p A).
In general, particles that grow by Brownian
coagulation reach asymptotic distributions,
the so-called self-preserving size distribution
(Friedlander, 1977). These distributions
remain invariable with time when the particle
size and concentration are scaled with the
average particle volume. For an initially
monodisperse aerosol, it takes a time tSF to
reach the self-preserving distribution. In the
free molecular regime, this time, tSF , is (Land-
grebe and Pratsinis, 1990)
4
tSF - (12.8)
- (6kBT)1/2 N5/6(3VvOI)1/6
Pp 0 47r

In B4 C particle synthesis by carbo thermal
reduction of soot-boron oxide powders in an
aerosol flow reactor (Run 38-24 by Weimer et
al., 1991), the self-preserving distribution was
obtained within half a microsecond, assuming
that initially 1 nm B4 C clusters were formed.
The reactor residence time was 1 s.
The geometric standard deviation for the
number self-preserving size distribution
(SPSD) is about 1.46 while that for the mass
SPSD is about 1.3 (Landgrebe and Pratsinis,
1989; Xiong and Pratsinis, 1991). These asymp-
totic distributions place a lower limit on the
reduction of the polydispersity of particles
grown by coagulation. If more detail is
required, the full distribution of the equivalent
solid sphere diameter of non-oxide powders
can be calculated by solving the population
balance equation for coagulation in both free
molecular and continuum regimes using
computer codes (Gelbard, Tambour and
Seinfeld, 1980; Landgrebe and Pratsinis,
1990).
Particles can also grow by vapor transport
and chemical reactions. This is particularly
useful in film deposition. Precursor molecules
may undergo a phase change on the particle
surface (e.g. condensation or physical vapor
deposition) or may react with the particle sur-
face to form another species (chemical vapor
deposition). In general, low temperatures
and pressures (or low reactant concentrations)
favor growth by surface reaction rather than
by coagulation. This has been demonstrated
in the synthesis of AlN particles and films
(Komiyama et al., 1987).
In general, the rate of change of particle
diameter, dp ' at temperature T by vapor trans-
port in the free molecular regime is given by
(Friedlander, 1977):
dd p _ 2VI (PI - Pd) F (12.9)
dt - (27rmkBT)I/2 1
where VI is the volume of the transported
molecule in the particle phase, PI is the partial
pressure of the gas or vapor far from the
particle and Pd is the partial pressure at the
Fundamentals 311
particle surface obtained from the equilibrium
vapor pressure over a flat surface using the
Kelvin equation (Friedlander, 1977). FI is
the Fuchs-Sutugin factor for bridging the
free molecule with the continuum regime
(Warren and Seinfeld, 1985).
In the continuum regime, the rate of change
of particle diameter is (Friedlander, 1977)
dd p = 4DvI (PI - Pd) F2 (12.10)
dt dpkBT
where D is the diffusion coefficient of the gas
or vapor and F2 is the Fuchs-Sutugin factor
for bridging the continuum with the free
molecule regime (Fuchs and Sutugin, 1971).
For practical applications, it is useful to
define the characteristic time for evaporation
or condensation. This is the time required to
halve the particle diameter by evaporation or
double it by condensation. In the free
molecular regime and with Pd = Pe' the
characteristic time for particle growth is
(12.11)
where Pe is the equilibrium vapor pressure
over a flat surface.
In the continuum limit and for Pd = Pe' the
characteristic time for particle growth is
(12.12)
Frequently, ceramic powders are made by
reacting precursor particles with gases or
vapors. If the rate of reaction is faster than
the rate of vapor transport to the particle
surface, then the previous analysis of evapora-
tion/ condensation describes the rate of par-
ticle growth. If, however, the rate of chemical
reaction is slower than that of vapor transport,
then particle growth is determined by the
chemical reaction rate.
Two distinct cases of slow reaction with
respect to transport are important: surface
and volume reaction. In the first case, the
312 Thermal aerosol processes
product species is formed at rate rs (molecules/
cm2 s) and for a first-order reaction
(12.13)
where ks is the surface reaction constant. The
rate of change of particle diameter is
ddp 2ks PIVl
(12.14)
dt kBT
and the characteristic time for particle growth
by surface reaction (time needed to double the
particle diameter) is
(12.15)
The second case is that of rapid vapor
transport and dissolution followed by slow
reaction at rate ry (mol! cm3 s) in the particle
volume. For a first-order reaction
(12.16)
where H is Henry's constant and ky is a first-
order reaction rate constant. The rate of
change of particle diameter is
dd p rydpMW
(12.17)
dt 3pp
where MW is the molecular weight of the
product.
The characteristic time for particle growth
by volume reaction is
3ln 2(r ykB T)
(12.18)
Tev = kyHp1MW
It should be emphasized that surface or
volume reactions work in series with vapor
transport during particle growth.
Particle morphology
Powders made by the gas-to-particle conver-
sion route are usually agglomerates of fine,
non-porous, primary particles. Temperature,
reactor residence time and chemical additives
affect the particle size, extent of agglomeration
(or aggregation) and, consequently, powder
morphology. Short reactor residence times
and rapid quenching of the product stream
lead to agglomerates of fine primary particles.
Sintering additives can also be effective in
altering the morphology of non-oxides as
they have been shown in the synthesis of
oxide powders (Akhtar, Pratsinis and Mas-
trangelo, 1992). Typically, the number of
primary particles forming an agglomerate
particle range from a few up to several hun-
dred, varying in size from 1 to 500 nm. If the
rate of collision is faster than that of sintering
(or coalescence, or fusion) then non-spherical
(or agglomerate, or aggregate) particles are
formed; on the other hand, if the sintering
rate is faster than the particle collision rate,
then regularly shaped, monolithic particles
are formed. Though the collision rate between
particles can be relatively easily estimated
from aerosol coagulation theory, the sintering
rate depends strongly on the material, primary
particle and crystallite size, and temperature.
Unfortunately, very little information is
available about the sintering rate of non-oxide
materials so a priori predictions about the
morphology of these powders are limited.
Further issues need to be considered for a
more detailed description of the particle
morphology. The previous analysis on particle
growth gives only the equivalent solid sphere
diameter of these agglomerates.
Recently, a new approach has been devel-
oped for the description of powder morphol-
ogy using the mass and surface area of
agglomerates (Koch and Friedlander, 1990;
Xiong and Pratsinis, 1993). The surface area a
of an agglomerate particle changes with time
by sintering as
da 1
- = --(a -af) (12.19)
dt Tf
where Tf is the characteristic time for sintering
and af is the surface area of a completely fused
sphere of the same mass as the particle. The
characteristic time is defined as the time
necessary to reduce by 63% the excess
agglomerate surface area over af. With the

agglomerate surface area from this analysis
and the agglomerate mass from coagulation,
a quantitative description of particle morphol-
ogy can be obtained and compared to experi-
mental data (e.g. specific surface area or
primary particle size).
It should be noted that particle morphology
may affect the rate of particle growth by
coagulation. In the free molecular limit,
agglomerates collide much faster than spheres
of the same mass since they have more surface
area for collisions. In the continuum limit
(d p A), the enhanced collisional surface of
agglomerates does not play a major role
because agglomerates experience enhanced
drag by the medium.
Powders can be characterized by numerous
methods; most notably by electron microscopy,
optical, electrical and density measurements,
electron diffraction and other techniques (e.g.
review by Pratsinis and Kodas, 1992). Powder
morphology is frequently characterized quanti-
tatively by the specific surface area of the
powder and the average size of the agglomer-
ate particles and primary particles therein. It
is also common to use some fractal dimension
to describe the morphology of agglomerates.
For example, a mass fractal dimension Df = 3
denotes a solid morphology. More recently,
computational schemes have been devised
that describe the dynamic evolution of
Fundamentals 313
irregular particles by deterministic (particle
volume and surface area distributions of B4 C
agglomerates by Xiong, Pratsinis and Weimer
(1992 and Monte Carlo methods (Akhtar,
Lipscomb and Pratsinis, 1994).
In ceramic applications, it is common to
distinguish between 'hard' and 'soft' agglom-
erates. These are empirical terms referring to
the ease of break-up of agglomerates. 'Soft'
agglomerates are those that are held together
by weak physical (van der Waals) forces,
while 'hard' agglomerates are held together
by stronger chemical bonds (e.g. partially
fused). Caution should, however, be exercised
when using the terms 'soft' and 'hard' because
they are also used to denote the strength of
chemically bonded particles. In the latter
case, the 'bond' strength is only a function of
the intensity of the grinding process employed
to break-up particles.
The gas-to-particle conversion route is most
suitable for the synthesis of single component,
high purity powders of small particle size,
high specific surface area and controlled
particle size distribution. The major disadvan-
tage associated with this route is that it results
in agglomerates that can lead to problems in
consolidation and sintering during fabrication
of large ceramic parts. In addition, it presents
difficulties in the synthesis of multicomponent
powders due to differences in vapor pressure,

V/ ///////////~~////I
o0
o~
Solvent lntraparticle 0 0 Particle

"'O: 0 0 0 """"'M
Solution Droplet Generation Deposition
of Precursors E..... 0 00 and
Collection

17I77T///777/T/1//7///1
Figure 12.2 Schematic of the processes involved in the particle-to-particle conversion route. (Kodas, T.T.,
'Generation of complex metal oxides by aerosol processes: superconducting ceramic particles and
films,' Angew. Chern. Int. Ed. Adv. Mat., 28, 794-806, 1989. Reproduced by permission of VCH
Verlagsgesellschaft mBh, Weinheim, Germany.)
314 Thermal aerosol processes
nucleation and growth rates of the various
components that can lead to non-uniform
product composition.
P ARTICLE-TO-PARTICLE CONVERSION
The particle-to-particle conversion route refers
to the conversion of liquid or solid particles
to the desired product powder. This route
includes processes such as droplet phase
reaction and aerosol decomposition or spray
pyrolysis which is similar to spray drying
described in Chapter 21, though higher tem-
peratures are employed here. This is a highly
promising route, though little work has been
done to date for aerosol synthesis of non-
oxides, in contrast to that with oxide powders
(Kodas, 1989).
A schematic of this route is shown in Figure
12.2. A solution or slurry is atomized or solid
precursor powders are suspended in a carrier
gas. Solvent evaporation and solute precipita-
tion take place from the atomized droplets at
low temperatures. Then, the airborne particles
are pyrolyzed or reacted with a gas at
higher temperatures in a flame or furnace to
yield the product powder. The powder is
removed from the process stream by con-
ventional means (baghouse filters, cyclones).
The particle size distribution is primarily
determined by the precursor solute or slurry
concentration and the atomization or suspen-
sion process. Particles obtained from this route
are generally porous, amorphous, unagglo-
merated and have a monolithic, spherical
morphology.
Liquid and solid precursors
The success of the particle-to-particle con-
version route relies heavily on finding the
appropriate precursors and solvents. The
stumbling block to the success of this route
is the selection of a precursor for the metallic
element of the non-oxide powder. The few
successful attempts described in the litera-
ture involve the use of polymeric ceramic
precursors (polysilane, polycarbosilane for Si
in SiC and Si3N4 and polyborazinylamine for
Band N in BN). The challenge actually
appears to be in the chemistry for synthesis
of these ceramic polymers! The solvent for
atomization may also require rather demand-
ing processing conditions (e.g. supercritical,
Matson, Petersen and Smith, 1987). For
example, liquid NH3 at 238 K (-35C) is the
solvent of choice for synthesis of BN by the
particle-to-particle route (Lindquist et al.,
1991). With increasing research into the syn-
thesis of polymeric precursors for ceramic
materials, it is conceivable that spray pyrolysis
(in the presence / absence of a reactant gas)
could become a viable means for production
of non-oxide powders. Multicomponent and
composite powders can also be made by the
particle-to-particle conversion route. For
instance, in the synthesis of Si3N4 by spray
pyrolysis of tris(dimethylamino)silane in H 2 ,
the remaining free carbon can be converted
to SiC and lead to a nitride/ carbide composite
(Shen and Chang, 1987).
The direct use of solid metal or oxide
powders as precursors for non-oxide powders
has also been investigated. Carbothermal
reduction techniques using suspended pre-
cursor solid oxide particles are discussed in
Part Two of this book. In addition, Hotta et al.
(1987) and Kimura et al. (1989a) synthesized
AIN by reacting ammonia (NH3) and nitrogen
(N2 ) with suspended aluminum particles in
an electrically heated vertical flow reactor.
Chemical reaction and particle morphology
The particle-to-particle conversion route
involves, first, the suspension of precursor
solid or liquid particles in gases. The sus-
pension or atomization process for liquid
precursors can be carried out using a variety
of atomizers depending on the rheological
characteristics of the liquid or the required
size of the atomized droplets. Lefebvre
(1989) reviewed the available atomization
and spray characterization techniques. In

general, atomization results in broad droplet
size distributions. When solid precursors are
involved, the suspension process does not
affect the product particle size unless it prefer-
entially suspends particles of a certain size
(e.g. just the fines). In addition, there are
limited options for suspension of solids (e.g.
fluidized beds and various screw-feeders)
without assistance of a liquid phase carrier
(atomization of slurries).
The suspended solid or liquid particles are
heated at high temperatures and the solvents,
if present, evaporate while the remaining par-
ticles are converted to the product by in-situ
solid or gas phase reactions. For quantitative
estimates of the required time for solvent
evaporation, equations 12.9-12.12 can be
used. The size of the product particles is pro-
portional to that of the suspended particles.
Take the simplest possible case: drying of a
solution droplet. An atomizer generates drop-
lets of size ds and solute volume concentration
y%. When all the solvent evaporates and in the
absence of chemical reactions, the equivalent
solid sphere diameter of the product (solute)
particles is
(12.20)
This simple analysis does not, however, pre-
dict the formation of solid or porous particles.
For the latter, detailed calculations are
required in which the droplet energy and
mass balances should account for evaporation
and crystallization (Leong, 1987). Detailed
models for the spray pyrolysis process have
been developed. Droplet evaporation and
solute precipitation was modeled by Xiong
and Kodas (1993). Jayanthi, Zhang and Mes-
sing (1993) modeled solid particle formation
and determined droplet shrinkage and solute
diffusion to be rate controlling.
Though several modifications of this method
have been developed and extensively used in
the past (e.g. spray drying, spray pyrolysis
and freeze drying), spray pyrolysis has more
frequently been employed in the synthesis of
Design and operation 315
non-oxide ceramics. During spray pyrolysis,
the transport of volatile material through the
particle surface affects the morphology of the
particles and results in the formation of
porous or hollow particles. The preparation of
SiC from Si-C-based polymers and Si3N4 from
Si-N-based polymers has been demonstrated
and progress has been made towards obtaining
B4C and BN ceramics (Narula, Paine and
Schaeffer, 1986; Lindquist et al., 1991) from
appropriate polymeric precursors (Rice, 1990,
p. 500). The ceramic mass yield from a polymer
must be between 50 and 80% for such a process
to be viable and in order to synthesize objects
with controlled porosity (Rice, 1990, p. 500).
Usually the exact stoichiometry of the desired
ceramic or polymeric precursor is difficult to
obtain, resulting in an excess of one constituent
or a mixture of products (e.g. carbon in Si3N4
synthesis by Shen and Chang, 1987). Very
recently, condensation-reaction techniques
(Matijevic, 1986) have been used for synthesis
of Si3N4 powders (Zimmermann, Partch and
Matijevic, 1991).
A major advantage of the particle-to-particle
conversion route is that it can be easily scaled
up. A limitation of this route is that hollow and
porous material is easily formed. As it has been
shown in the synthesis of oxide particles, it is
possible to control the porosity of powders by
changing the precursor solute concentration
and the reactor temperature profile (Zhang,
Messing and Borden, 1990), by post-processing
at high temperatures (Ortega et al., 1991) and
by introducing seed particles (nuclei) in the
solution (Kodas, 1992).
DESIGN AND OPERATION
One of the most important aspects of gas phase
powder synthesis is the design and operation
of the thermal units that will create the high
temperatures to drive gas or particle phase
reactions for the synthesis of non-oxide
powders. Conventional thermal processes
include flame and externally heated reactors.
In flames, particles come in direct contact
316 Thermal aerosol processes
with the heating source (combustion reactants
and flue gases). In externally heated reactors,
an electric source or combustion flue gases
heat the precursors through a refractory or
metal tube (reactor). Clearly, flame reactors
make the maximum use of the heating
energy but may contaminate the product
powder. Externally heated reactors can
produce high purity material at the expense
of energy and material (particle loss by deposi-
tion on the reactor walls).
EXTERNALLY HEATED REACTORS
Typically, there is a need for maintaining high
purity conditions during the synthesis of non-
oxide ceramics. The closed environment of an
externally heated reactor offers significant
advantages. As a result, these reactors are
the 'workhorses' for synthesis of non-oxide
ceramics. These reactors are tubular, made of
thermally stable refractory material usually
quartz, mullite, alumina or graphite and are
heated either resistively or inductively.
These reactors provide for operation under
well defined stoichiometries, temperatures
and residence times.
Two of the key problems associated with
externally heated reactors are the loss of
product powder by deposition on the reactor
walls and the formation of hard agglomerates
that make powder sintering and consolidation
difficult.
In their patent on gas phase manufacture of
submicron boride, nitride and carbide par-
ticles from the halide vapor of the selected
metal, Lamprey, Culbertson and Ripley
(1966) emphasized the need for the reaction
zone to be as far removed from the reactor
walls as possible. If the reacting vapors are
exposed to the reactor walls while the pow-
ders are synthesized, plate-like deposits are
formed on the walls. These deposits reduce
the quality of the product and may even clog
the reactor. One of the ways of mitigating and
possibly preventing deposits to the reactor
walls is to sheath the incoming reactant gas
streams in an inert gas by using concentric
nozzles at the reactor inlet (Weimer et al.,
1991). This ensures that the reactants mix
some distance downstream in the reactor
and do not clog the inlet tubes. A method
developed for redirecting thermophoretic
deposition of exothermic reaction products
away from the reactor wall and to flowing
particles is to flow an admixed inert powder
with the feed particles through the reaction
tube (Weimer et al., 1993).
To prevent extensive agglomeration and
further growth of the agglomerates to super-
micron size, the submicron powders formed
in the reaction zone need to be removed
from the hot and possibly still reacting gase"s.
Fast and effective quenching will cool the par-
ticles and prevent further growth. One
method is to expose the product particles to
a large volume of inert gas like Ar or cool
the gases entraining the particles by sudden
expansion (Lamprey, Culbertson and Ripley,
1966; Weimer et al., 1991). Another effective
technique to limit particle growth is to limit
the length of the reaction zone and rapidly
withdraw the submicron particles from the
reactor.
FLAME REACTORS
Flame reactors are attractive for particle
generation as they are easy to construct and
operate compared to plasma and laser reac-
tors. They only involve bringing in contact
fuel and oxidant. Usually oxygen serves as
the oxidant in flame reactors, but this may
not be acceptable in manufacture of non-
oxide ceramics as oxygen and oxides severely
affect the performance of these ceramics.
Hence, gaseous precursors in premixed or
diffusion flames of hydrogen (H2 , fuel) and
chlorine (Cl 2, oxidant) are preferred.
Influenced by processes used in production
of HC1, an Hz-C12 flame reactor was used to
synthesize Si3N4 (Sa to, Terase and Kijimuta,
1983) and tungsten (W), WC and W 2C
particles (0.04-0.1 jLm) from WC1 6 and CH4

(Zhao, Revankar and Hlavacek, 1990). The
adiabatic temperature of these flames is in
the region of 3300 K (3027 DC) though typical
operation temperatures range from 1000 to
2000K (727-1727 DC). The reactant feed
system (burner) can involve several concentric
tubes through which reactant or inert gases
flow. This geometry provides some flexibility
in reactor operation. A unique characteristic of
flame reactors is the short residence time in
the high temperature region and its limited
control. As a result, the flame-produced pow-
ders are typically agglomerates of fine, rela-
tively narrowly distributed, primary particles.
The temperature profile, additives and resi-
dence time determine the crystallinity, phase
composition and extent of aggregation. For
example, increasing the temperature or the
residence time in the high temperature zone
can increase the grain size and crystallinity.
If the precursor gases are very reactive, then
the inlet feed tubes can be clogged by deposi-
tion of product powders. A diffuser screen
can be placed between the gas inlet tubes
and the reaction zone, thus keeping the
reaction confined to the flame side of the
screen and reducing the likelihood of fouling
of the inlet tubes (Lamprey, Culbertson and
Ripley, 1966).
The primary advantage of flame reactors is
that their scale-up has been demonstrated in
production of carbon blacks, fumed silica
and titania. Precursors and additives (to
modify powder phase composition, mor-
phology and size) can be easily introduced.
High product purity can be obtained from
these reactors as gaseous precursors are
available at high purities. The foremost dis-
advantage of powders made in flames is that
the agglomerates are often hard to break up
(or grind) and have a broad equivalent solid
sphere particle size distribution. In addition,
powder contamination by chlorine or oxygen
can be a serious drawback.
Flame reactors can also be used to make
pure or composite non-oxide powders by
pyrolyzing precursor solid or liquid particles
Applications 317
(e.g. Zachariah and Huzarewicz, 1991) in
the synthesis of superconducting powders
by spray pyrolysis. The latter technique
has not been applied yet to the synthesis of
non-oxide powders. Finally, an interesting
variation of synthesis of non-oxides in flame
reactors is the production of mixtures of
carbon-oxide powders which are heat treated
after collection to yield the non-oxide ceramic.
Murakawa et al. (1987) synthesized a mixture
of silicon dioxide (Si02) and carbon powders
from the gas phase reaction of SiC4 and heavy
oil in an air-propane flame. The mixture of
powders was heated in an N2 atmosphere at
2073 K (1800 DC) resulting in high quality SiC
powder.
APPLICATIONS
The increased emphasis on and demand for
high purity non-oxides has led to vigorous
exploration of novel routes for their manufac-
ture. Tungsten carbide (WC) is the non-oxide
material with the highest production volume
and value as it finds widespread application
in drill bits and other wear and hardness
applications. However, AlN, Si3N4 and SiC
promise to find widespread application in
the future. In the following section, thermal
processes for aerosol synthesis of some of
the most significant non-oxide powders are
discussed.
ALUMINUM NITRIDE
Currently, aluminum nitride (AIN) receives a
lot of attention because of its good electrical
resistivity and high thermal conductivity.
These properties along with a thermal
expansivity close to that of silicon (Si), make
AlN an ideal substitute for alumina (A120 3)
as a substrate for multichip modules.
Aluminum nitride (AlN) powder is made on
a large scale by direct nitridation of Al metal
or carbothermal nitridation of A120 3. The fact
that the exceptional properties of AlN are
obtained only:. at high purity, makes aerosol
318 Thermal aerosol processes
manufacturing processes potentially quite
attractive. Both gas-to-particle and particle-
to-particle conversion routes have been devel-
oped for AlN synthesis. Aerosol processes
involving nitridation of Al and AI-containing
compounds are reviewed in this chapter.
AIN by particle-to-particle conversion
Hotta et al. (1987, 1988) synthesized AlN in an
alumina flow reactor (2.8 cm (1.1 in) internal di-
ameter (10), 100cm (",3.3ft) long) by nitriding
suspended AI particles with N2 at 1623-1823 K
(1350-1550 e) (Figure 12.3). Hollow spherical
0
and fibrous AlN particles were obtained which
were relatively unagglomerated. The powders
were mainly AlN, though some unreacted Al
remained, especially when shorter residence
times were employed. The AlN particles
ranged from 4 to 12 pm, but this range was
reduced to the primary particle size of 0.1-
0.2 p,m through minor milling. Hollow particles
were obtained because AlN rapidly coated the
unreacted molten aluminum, which expanded
more than the surrounding AlN, causing
fissures in the particle surface through which
the Al vapor escaped. There was extensive
deposition on the walls of the reactor and the
product powder had to be scraped repeatedly
from the reactor walls with a hot tungsten
wire in order to establish a continuous process.
This could be explained by the exothermic
nitridation reaction that heated the particles
above the reactor temperature. As a result,

Powder
Collection

1Il'-
c: O
--'0
EIIl
~~

(c)

Nitrogen

Figure 12.3 Schematic of the apparatus used to produce aluminum nitride by nitridation of floating
aluminum particles in nitrogen gas: (a) flow meter; (b) silicon carbide filter; (c) aluminum powder.
(Hotta, N., Kimura, 1., Tsukuno, A., Saito, N. and Matsuo, S., 'Synthesis of AIN by the nitridation of floating
Al particles in N2 gas,' Yogy-Kyokaishi, 95(2), 274-78, 1987. Reproduced by permission of The Ceramic
Society of Japan, Tokyo, Japan.)

particle deposition took place by thermophor-
esis to the reactor walls.
Kimura et al. (1989a) lowered the above
process temperatures and used an N r NH3
mixture instead of N2 for nitridation. The con-
version of Al to AlN increased with tempera-
ture, but at all temperatures (1423-1573K;
1150-1300C) showed a maximum conversion
with 5 vol% NH3. Hotta etal. (1995) showed that
the nitriding temperature could be reduced by
about 200 K by using N2 as the floating gas for
Al powder and injecting an N r NH3 gas mix-
ture at the center of the heating zone.
Recently, Weimer et al. (1993, 1994) demon-
strated that AlN particles having a desirable
surface area of 3 m 2/ g could be produced
by reacting the atomized Al particles with
N2 at higher process temperatures of 1873 K
(1600C). The powders were subsequently
pressureless sintered into high thermal con-
ductivity parts.
Shintaku (1986) produced AlN powder by
the direct nitridation of aluminum droplets.
Using pressurized N 2, molten aluminum
Applications 319
was atomized into N2 gas that was kept at
1073K (800C). The AlN produced had a
maximum purity of 60wt% AIN (the remain-
der being aluminum). It was spherical with an
unagglomerated morphology and an average
size of 0.I-O.2/-Lm. Further processing (heating
at elevated temperatures under an N2
atmosphere) was required to obtain pure
AlN powder.
AIN by gas-to-particle conversion
Synthesis routes involving only the basic
elements are most attractive since, in principle,
the possibility of product AlN contamination is
reduced. Thus, Taylor and Lenie (1960) made
AlN by vaporizing Al metal in an N2 atmo-
sphere between 2073 and 2273 K (1800-
2000C). Pratsinis et al. (1995) synthesized
AlN particles from the gas phase reaction
between NH3 and Al vapor between 1573
and 1873K (1300-1600C). A schematic of the
apparatus used is shown in Figure 12.4. The
introduction of dilution gas at the reactor

Dilution Gas

3Zone Furnace

Filter

Figure 12.4 Apparatus employed in the synthesis of aluminum nitride from the vapor phase reaction
between aluminum and ammonia. (Pratsinis, S.E., Wang, G., Panda, S., Guiton, T. and Weimer, A.W.,
'Aerosol synthesis of AlN by nitridation of aluminum vapors and clusters,' J. Mater. Res., 10(3),512-20,
1995. Reproduced by permission of The Materials Research Society, Pittsburgh, PA.)
320 Thermal aerosol processes
25 30 35 40
Figure 12.5 XRD patterns for AlN synthesized from the gas phase reaction between vaporized aluminum
and ammonia at different temperatures.
outlet freezes the chemical reaction and particle
growth so that fine, submicron particles are
obtained. X-ray diffraction (Figure 12.5)
showed aluminum contamination only at
higher temperatures and low residence times.
Scanning electron micrographs showed that
the powders were spherical but extensively
agglomerated with a primary particle diameter
of 0.0711m and agglomerates about 0.4 JLm in
size (Figure 12.6).
Thermodynamic analyses have shown that
formation of AlN by nitridation of AlCl3
vapor with NH3 in H2 is one of the most advan-
tageous AlN manufacturing routes for obtain-
ing high purity powder (Hashman and
Pratsinis, 1992). Kimura et al. (1988a,b, 1989b)
investigated this process in an externally
heated mullite reactor (3.5 cm (,...,1.4 in) ID and
60 cm (,...,2 ft) long) at temperatures between 993
and 1463K (720-1190C). They found that
increasing reactor temperature resulted in a
narrower particle size distribution and shifted
1873 K
45 50 55 60 65 70
26(Degrees)
it towards smaller sizes. This was reasoned to
be the result of enhanced nucleation of AlN at
higher temperatures. The average particle size
decreased with increasing flow rate (decrease
in residence time). X-ray diffraction (XRD) ana-
lysis of these powders revealed only AlN.
Scanning electron microscopy (SEM) showed
that spherical particles were formed at tem-
peratures of 1373 K (1100C) or higher, as
opposed to a mixture of rod-shaped and sphe-
rical particles at lower temperatures. Extensive
particle deposition occurred on the walls of the
reactor.
Heymer and Harnisch (1967) also made AlN
by mixing AICl3 and NH3 gases with H2 that
had been heated in an electric arc to 3073 K
(2800C). Light, finely divided, submicron
powders of AIN were produced having a
wurtzite lattice structure. The process yield,
calculated on the basis of AICl3 feed, was
97.5%. Matsuwara and Miue (1986) produced
AlN powders from AICl3 and NH3 too, but

Figure 12.6 Scanning electron micrographs of gas phase synthesized AIN powders in the AI-NHrAr
system at 1673 K (1400C).
synthesized the halide in situ to reduce powder
contamination. Aluminum (AI) metal was
reacted with HCl gas and the product AlCl3
vapor was reacted with NH3 farther down-
stream between 873 and 1273K (600-1000C).
Scanning electron micrographs showed that
the powder particles were spherical with an
average diameter of 0.7/Lm and only AlN was
found by XRD. The metallic impurities were
less than 0.2 wt% and the oxygen content was
less than 0.5 wt%. Kim and Lee (1985) and Greil
et al. (1994) made AlN particles of diameters
ranging from 0.1 to 0.5 /Lm using the AlClr
NH3 system in an Ar atmosphere (Figure
12.7) and an N2 atmosphere, respectively.
They found that the degree of crystallinity of
the particles increased with increasing reaction
temperature or secondary calcination. Spheri-
cal particles were formed at 873 K (600C)
and the particles became rod shaped above
1273 K (1000 C).
Applications 321
Besides AlCl3, other halides have been used
for the synthesis of AlN, but have met with
limited success compared to that of AlCl3, e.g.
AlBr3 (Pauleau et al., 1980), AlF (Slack and
McNelly, 1976; Huseby, 1983) and AlCl
(Sood, Southam and Raghavan, 1989).
Organometallic precursors have also been
used for synthesis of AlN. Adjaottor and Grif-
fin (1990) used triethyl aluminum (Al(C2H s h)
vapor and NH3 in an electrically heated quartz
aerosol reactor. The heated length of the reactor
was 60 cm (",2 ft). Triethyl aluminum (TEA)
was supplied by bubbling N2 through a gas
washing bottle containing TEA. The NH3 gas
was introduced directly into the reactor
where temperature was maintained between
973 and 1373K (700-1100C). The powders
produced at the lower temperature were
amorphous, while the ones produced at the
higher temperature showed broad diffraction
peaks indicative of crystalline AlN. Similar
322 Thermal aerosol processes
Electric Furnace
~ IV;;~~
.
.; (a) (b)
:: V/////////g////j
Ammonia
Argon
Figure 12.7 Schematic of the apparatus used in the synthesis of aluminum nitride powders from alumi-
num chloride and ammonia vapors: (a) potassium hydroxide; (b) barium oxide; (c) sponge titanium; (d)
flow meter; (e) calcium chloride; (f) phosphorus pentoxide; (g) activated copper; (h) aluminum chloride.
(Adapted from Kim and Lee, 1985.)
experiments (Kubo et al., 1995) were carried out
using trimethyl aluminum Al(CH3h) and tri-
isobutyl aluminum (Al(i-C4H 9)3) as organo-
metallic precursors in addition to triethyl
aluminum (Al(C2H s h). The reported surface
areas of 95 m 2/ g, 175 m 2/ g and 145 m 2/ g
corresponded to calculated primary particle
sizes of 19nm, 11 nm and 13nm, respectively,
for the AlN synthesized from Al(CH3h, Al(i-
C4H 9)3 and Al(C4H sh.
Hiai et al. (1989) and Wakimura and Hiai
(1991) also used TEA to make AlN in a flow
reactor between 1073 and 1173 K (800-900C)
and residence times between 0.9 and 1.3 s. The
specific surface area of the powders was
between 140 and 200m2/g and transmission
electron micrographs showed that the
particles were unaggregated and spherical.
An elemental analysis of the powders
showed silicon content of 24 ppm and
0.9wt% oxygen. The sintering properties of
these powders were studied and their thermal
conductivity was also measured (200 W / m . K
for powders sintered at 2073 K (1800 C.
Tsuchida et al. (1989) prepared AlN powders
from the gas phase reaction of triisobutyl alu-
minum (Al(i-C4H 9h) and NH3. The aluminum
(d) Alumina Tube
rrr:rTT777-rT;'7T.rTTTI
Manometer
Quartz Tube
precursor was mixed with a stream of H2 and
NH3 at 473 K (200C) and the reaction was car-
ried out between 873 and 1273 K (600-1000 C)
in an externally heated alumina tube:
Al(i-C 4H9h + NH3
----> (i-C 4H 9 hAl. NH3 (12.21 )
(i-C 4H 9 hAl. NH3
----> AlN + 3(i-C4HlO) (12.22)
The powders produced at the lower tem-
peratures were amorphous, though the
degree of crystallinity increased at the higher
temperatures. Transmission electron micro-
scopy (TEM) showed that the AlN powder
consisted of aggregates of spherical primary
particles (0.025 {.tm at 1373 K (1100C)) and
that the particle diameter decreased with
increasing temperature. In their experimental
conditions, the authors list a constant gas flow
rate for all experiments conducted between
873 and 1673K (600-1400C). This would
lead to reduced residence times at higher
temperatures that may explain the significant
decrease in particle diameter observed with
increasing reactor temperature.

Finally, it should be noted that routes
involving organometallic compounds may
lead to carbon contamination as in carbo-
thermal reduction. Additional processing
may be required to burn off excess carbon.
Bachelard and Joubert (1989) stated, however,
that oxygen contamination is difficult to pre-
vent because AlN is easily oxidized by water
and the powder cannot be isolated from H 20
during carbothermal processing.
SILICON NITRIDE
Silicon nitride (Si3N 4) is manufactured com-
mercially by a variety of processes: carbo-
thermal nitridation of Si02, gas phase
reactions with ammonia (NH3), an imide
process and by direct nitridation of silicon
(Si) powders (Schwier, Nietfeld and Franz,
1989). The final product characteristics
depend on the sintering activity and micro-
structure of the product powder. The choice
of the manufacturing route depends on the
end application of Si3N 4. Silicon nitride finds
use in turbocharger gas rotors, ball bearings
and rotors, passivating layers in semiconduc-
tor substrates and as a hard coating material
(Zimmermann, Partch and Matijevic, 1991).
Si3N4 by gas-lo-particle conversion
Heymer and Harnisch (967) patented a pro-
cess for the synthesis of Si3N4 by gas phase
reaction between SiC4 and NH3. In this
process, Ar, H 2, N2 or a mixture of these
gases was heated to 2773 K (2S00 C) in an
electric arc and introduced into a reactor that
was at 473 K (200C). This gas mixture was
mixed with gaseous SiC4 and NH3 forming
Si3N 4 :
3SiC14 + 8NH3 -+ Si3N4 + 4NH4Cl + 8HCl
(12.23)
To obtain crystalline Si3N4 at high yields, it
was necessary to rapidly mix the reactant
gases with the hot gas. The hot reaction
mixture was cooled to slightly above the con-
Applications 323
densation temperature of ammonium chloride
(NH4Cl) and the powders were removed in a
cyclone. The low temperature of the reactor
walls (473 K, 200C) prevented corrosion of
the reactor by HCl and NH4Cl. Another
advantage of this process is that NH3 is not
preheated to high temperatures, thus there is
no decomposition and subsequent high con-
sumption of that raw material. The powders
obtained in this process were very fine and
x-ray diffraction analysis revealed that 80%
were a-Si3N4 and 20% were ,B-Si3N4.
Prochazka and Greskovich (1978) syn-
thesized amorphous Si3N4 in an aerosol flow
reactor by the gas phase reaction between
silane (SiH4) and NH3 at temperatures between
823 and 1193K (SS0-920C). The amorphous
Si3N4 was converted to the crystalline form
by heating at 1673 K (1400 C). The reactant
gases, along with diluent Ar, were introduced
into a 3.8 cm O.S in) ID silica tube with a heated
length of 2Scm (",lOin). The powders were
collected by using an electrostatic precipitator.
After each run, the Si3N4 powders were
washed out of the tube and collector with
benzene. The two main parameters which con-
trolled the reaction between SiH4 and NH3
were the temperature and the NH3/Si~
ratio. There was no significant reaction below
773K (SOOC). When the NH3/SiH4 ratio was
<10, the powders were brownish orange, indi-
cating the presence of free silicon. At a ratio
> 10, the product powders were white or light
tan. The product yield increased with increas-
ing temperature with the theoretical yield
being approached at 923 K (6S0 C). The
specific surface area of the powders varied
from 8 to 24 m 2/ g, but was unaffected by the
NH3/SiH4 ratio. However, the specific surface
area clearly decreased with increasing tem-
perature indicating that sintering occurred.
Transmission electron microscopy (TEM)
showed that the powder comprised aggregates
of spherical primary particles with a diameter
of 0.1 j.tm.
Self-sustaining flames in the SiHcNH3
system were used to make Si3N4 (Calcote
324 Thermal aerosol processes
and Felder, 1990). The flat one-dimensional
flame provided a small residence time. The
swift quenching of the product led to fine,
unagglomerated powders. More recently,
Janiga, Sin and Figusch (1991) prepared
Si3N4 by reacting SiH4 and NH3 in a flow
reactor between 873 and 1673 K (600-1400 DC)
without any post-processing. At low tempera-
tures mostly silicon was obtained, though as
much as 10% 0:-Si3N4 was obtained at 1673 K
(1400C). Figure 12.8 shows micrographs of
the product powder at 1073 K (800C) (a)
and at 1673K (1400C) (b). In both cases,
highly agglomerated powders are obtained
which are typical of gas-to-particle conversion
processes. The primary particle (grain) size
ranged from 0.05 to 0.2/-tm which is in the
same size range as the powders synthesized
by Prochazka and Greskovich (1978) under
similar conditions.
The reaction between vapor silicon and NH3
avoids the complications due to the presence of
chlorides. Miura et al. (1984) vaporized silicon
and passed this vapor along with NH3 through
a convergent-divergent nozzle. The turbulent
mixing during passage and the rapid cooling
enable ultrafine particles of Si3N4 to be
produced.
Si3N4 by particle-fo-particle conversion
The spray pyrolysis technique for synthesiz-
ing Si3N4 powders was first used by Mizutani
and Liu (1990). Polysilazanes were syn-
thesized from trichlorosilane and methyldi-
chlorosilane. The polysilazane was dissolved
in benzene, diluted with acetonitrile and
ultrasonically atomized in N 2, H 2, NH3 and
Ar (Figure 12.9). The droplets were introduced
into an externally heated, vertical alumina
tube (4.2cm (",1.7 in) ID). The pyrolysis
Figure 12.8 Scanning electron micrographs of silicon nitride powders synthesized at (a) 1073 K
(BOODC); (b) 1673K (1400 DC). (Janiga, J., Sin, K.P. and Figusch, V., 'Synthesis of silicon nitride powder
by gas-phase reaction,' J. Eur. Ceram. Soc., 8, 153-60, 1991. Reprinted with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK.)
temperature ranged from 873 to 1273 K (600-
1000 DC). The solid powders were collected on
a filter heated by a ribbon heater at 373 K
(100C). The powders produced at lower
temperatures were agglomerated since they
were made of undecomposed precursors;
those produced above 973 K (700C) were
spherical with a broad size distribution indi-
cative of the precursor polysilazane droplet
sizes. The particle size ranged from 0.1 to
2/-tm and increased as the polysilazane
concentration in acetonitrile increased. The
as-produced powders were amorphous, but
0:-Si3N 4 was obtained by calcination in N2
and H2 while a mixture of 0:- and ,B-Si3N4
was obtained in Ar.
Tris(dimethylaminosilane) was used as a
precursor in the pyrolytic synthesis of Si3N4
(Shen and Chang, 1987). The reaction was
conducted in an inductively heated alumina
tube (2.86cm (",1.1 in) ID, 30.5cm (1 ft) in
length). The pyrolysis temperature ranged
from 973 to 1923 K (700-1650 DC) and the
pressure from 800 Pa (6 torr) to atmospheric.
Hydrogen (H2) was used as the carrier gas
and tris(dimethylaminosilane) was intro-
duced as a vapor or injected directly as a
liquid. All the powders were amorphous to
x-ray diffraction and some contained up to
10wt% of SiC.
Zimmermann, Partch and Matijevic (1991)
generated submicron droplets of methyl-
dichlorosilane (MDS) by bubbling Ar through
an MDS pool at 238 K (-35C) and, sub-
sequently, condensing the droplets in a
laminar flow condenser at 198 K (-75C)
(Figure 12.10). The MDS droplets were reacted
downstream with NH 3, also at 198 K (-75 DC).
A white powder consisting of silazane and
NH4Cl was obtained. The powder was
heat treated at 1723 K (1450 DC) after removal
Applications 325
326 Thermal aerosol processes

t
)'~ilter
Ribbon Heater I I

-
SiC
Furnace

Gas (I)
Ultrasonic
Aerosol
Generator
--"li
-

"-

Gas (II)

1:3 Polysilazane +
acetonitrile

Figure 12.9 Schematic of the apparatus used to produce silicon nitride from the spray pyrolysis of
polysilazanes. (Mizutani, N. and Liu, T., 'Synthesis of spherical Si3N4 powders by spray pyrolysis of
polysilazane: in Ceramic Transactions, 12: Ceramic Powder Science III (eds C.L. Messing, S. Hirano
and H. Hausner), pp. 59-73, 1990. Reproduced by permission of the American Ceramic Society,
Westerville, OH.)

of the NH 4Cl. X-ray analysis of the calcined BN by gas-to-particle conversion

samples showed the presence of both the
0:- and j3-Si3N4. The powder was made of
spherical particles 0.5 f.1m in diameter.
BORON NITRIDE
Hexagonal boron nitride (BN) shows the most
promise for applications in x-ray masks, elec-
tronics for high temperature active devices
and insulators, the handling of molten
metals and friction-reducing coatings (Pouch
and Alterovitz, 1990).
Boron nitride was synthesized by a gas-to-
particle conversion route first by Heymer
and Harnisch (1967). In a process similar to
that used in the synthesis of AIN and Si3N 4,
boron trichloride (BCl3) and NH3 were
mixed with N2 that was heated to 3073 K
(2800 C) in an electric arc. This resulted in
the formation of BN:
BC13 + 3NH3 ...... BN + 2NH4Cl + HCl (12.24)
About 40% of the energy supplied to the
N2 was transmitted before and during the

(c)
(d)
(b)
(e)
(a)
(f)
.~
c: c:
o sively agglomerated. Kim and Jeung (1990)
E ~
<C
(9)
~ synthesized BN powders between 1373 and
Figure 12.10 Schematic of the aerosol generator for
the synthesis of silazane, a precursor for silicon
nitride: (a) drying column; (b) flow meters; (c)
boiler containing MDS; (d) cold condenser; (e) mani-
fold for NH3 intake; (f) reaction tube; (g) thermal
impact depositor. (Zimmermann, c.}., Partch, R.E.
and Matijevic, E., 'Synthesis of a silazane polymer
by chemical reaction in an aerosol: a precursor for
silicon nitride,' J. Aerosol Sci., 22(7), 881-86, 1991.
Reprinted with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane,
Kidlington OXS 1GB, UK.)
reaction to the cooling liquid of the anode and
the reactor walls. The reactor walls were main-
tained at a temperature of 573 K (300C) by
cooling with N 2. The low wall temperature
prevents corrosion of the reactor by HCI
and NH4 Cl. It is essential to mix the reacting
gases rapidly in order to produce crystalline
powders at high yields. The BN produced by
this process was partially amorphous and
partly crystalline hexagonal BN as determined
by x-ray diffraction. The product was stoichio-
metric and the yield was about 95% with
respect to BCl3 feed.
Kim and Ko (1990) synthesized BN from
BCl3 and NH3 between 973 and 1673 K
Applications 327
(700-1400C) (Figure 12.11). In this process,
controlled amounts of reactant gases and dilu-
ent Ar were introduced into an externally
heated mullite tube (4.4cm (rv1.7in) ID,
100 cm (3.3 ft) long). Crystalline hexagonal BN
was obtained only at temperatures above
1373 K (1100C). The particle size of BN
decreased with increasing reactor temperature,
though the crystallite size, as determined by x-
ray line broadening, increased with increasing
temperature. Shorter residence times at high
temperatures explain the decrease in overall
particle size, while high temperature facilitates
crystallite growth within an aggregate by
sintering. Scanning electron micrographs
indicated that the primary particles were
spherical (diameter ~ 0.1 j.tm), though exten-
thermally decomposed similar vapor phase
1723K (1100-1450C) to obtain whiskers.
BN by particle-lo-particle conversion
The use of polymeric precursor poly(bor-
azinylamine) for the synthesis of BN particles
by spray pyrolysis has been demonstrated by
Lindquist et al. (1991). The polymer was dis-
solved in NH3 and droplets of this solution
were generated with a collision nebulizer in
an ultrapure N2 atmosphere. These droplets
were fed into a quartz pyrolysis tube (10 cm
(rv4in) ID, l.5m (rv5ft) long) at 1273K
(1000C). The residence time in the pyrolysis
tube was approximately 10 s. The BN powders
were cooled and collected on nylon filters.
These powders were amorphous to x-ray
diffraction and their density was found to
be about half of theoretical. Scanning electron
micrographs revealed that the powder
particles were hollow and spherical with
cracks on the surface, which are typical of
droplet-generated particles (Figure 12.12(a.
A broad size spectrum of round BN particles
was obtained with an average diameter of
O.5j.tm. Upon calcining at 1673K (1400C),
dense crystalline BN particles with a faceted
328 Thermal aerosol processes
Alumina Tube

Electric Furnace

Argon

Boron Glass Wool Filter

Trichloride and
Exhaust

Ammonia
Figure 12.11 Experimental apparatus for the synthesis of boron nitride from the high temperature reaction
between boron trichloride and ammonia: (a) phosphorus pentoxide; (b) activated copper; (c) silica gel;
(d) flow meter; (e) three-direction flask. (Adapted from Kim and Ko, 1990.)

plate-like structure were obtained (Figure
12.12(b.
SILICON CARBIDE
There is substantial interest in making sub-
micron particles of silicon carbide (SiC) to
facilitate the sintering of this covalent ceramic
for high temperature applications. SiC has
potential use in wear and oxidation resistant
coatings and as a diffusion barrier to prevent
escape of fission products from the surface of
fuel particles used in high temperature gas-
cooled reactors (Allendorf and Kee, 1991).
The first reference to the successful produc-
tion of carbides by a vapor phase reaction was
by Latham (1967). In this method, SiCLt was
vaporized and heated to a temperature of
813 K (540C) and mixed with methane (CH4 )
at 672 K (399C) in a graphite reactor (10 cm
(,-A in) 10, 122 cm (4 ft) long) encased in a stain-
less steel shell. The temperature in the reaction
zone was maintained at 1810 K (1537C) and a
finely divided SiC powder was obtained.
Murakawa et ai. (1987), Yoda et al. (1988)
and Murakawa and Nakajima (1991a,b) syn-
thesized homogeneous mixtures of finely
divided silicon dioxide (Si0 2) and carbon
powder in fuel-rich hydrocarbon flames and
obtained SiC by further heating the powder
mixture. The precursor mixture of Si02 and
C was obtained by spraying a mixture of
SiCl4 and heavy oil into an air-propane
flame (Figure 12.13). The reaction vessel was
a cylindrical tube (30cm (",1ft) 10, 3m
('" 10 ft) long) lined with a refractory material
and heated between 1023 and 1773K (750-
1500C). The fine aerosol mixture of Si02
and C was collected in a bag filter (Figure
12.14(a. The powders were then mixed with
a tarry binder, molded into tablets and heated
at 2073 K (1800C) for 30 min in an N2 atmo-
sphere to obtain ;3-SiC. The excess carbon was
oxidized and the excess Si02 was melted and
treated with hydrofluoric acid (HF). The
specific surface area of the SiC powders was
between 10 and 15 m 2 / g with the aggregate
size ranging between 0.35 and 0.65 Jim
(Figure 12.14(b. The primary particles form-
ing the aggregate were in the size range 0.02 to
0.1 {lm. The authors found that the carbon-to-
metal ratio in the mixed powder should be
between 3.5 and 8 to obtain uniform particles
of small average diameter. Large ceramic
 Applications 329

(a) (b)
Figure 12.12 (a) Scanning electron micrographs of aerosol generated amorphous BN powder synthesized
at 1273 K (1000 C) and (b) scanning electron micrographs of BN powder calcined at 1873 K (1600 C) illus-
trating the formation of plate-like crystals of BN within the original particles. (Photos courtesy of RT.
Paine, University of New Mexico, Albuquerque, NM.)

parts with near theoretical density can be
obtained by pressureless sintering.
The SiHcCHcH2 system for the synthesis
of SiC was investigated by Pai et al. (1989).
The reaction was conducted in an externally
heated alumina tube between 1473 and 1673K
(1200-1400 C). Hollow, round, agglomerated
particles 0.05 p,m in diameter were formed. At
temperatures below 1673K (1400 C), excess
silicon (SO was present in the particles while
at temperatures above 1673 K (1400 C) j3-SiC
was obtained. Detailed TEM of the particles
showed that excess Si was present as a crystal-
line phase in the cores of the particles while
excess carbon existed in the amorphous phase
within the shells of hollow particles. Xu and
Ding (1991) also synthesized SiC using the
SiHcCHcH2 system. Aggregated powders
of j3-SiC with primary particle size in the
range 9.9-16.1 nm were obtained. The particle
size increased with increasing reactor tempera-
ture and pressure, but remained unaffected by
changes in the SiH4 /CH4 ratio.
Natsume, Miura and Oota (1986) syn-
thesized SiC by reacting Si vapor with CH4
in an inert gas medium. The molten Si bath
was at a temperature between 2073 and
2273 K (1800-2000 C). Argon (Ar) was used
as the carrier gas and CH 4 as the reactant
gas. Fine SiC powder with an average particle
diameter of 50 nm was obtained.
Silicon carbide (SiC) powders were also
prepared by gas phase pyrolysis of tetra-
methylsilane (Si(CH3)4) in a tubular flow
reactor (Wu and Readey, 1987). The reactor
was an alumina tube (4.5 cm (1.8 in) 10)
placed in a furnace capable of reaching 2246 K
(1973 C). Argon (Ar) carrier gas was bubbled
through liquid tetramethylsilane (TMS) to
introduce it into the reactor. The reaction was
330 Thermal aerosol processes
Heavy Oil
Propane
Figure 12.13 Schematic of the apparatus used to obtain mixtures of powders from aerosol routes. (Mura-
kawa, N. and Nakajima, M., 'Synthesis of SiC from fine Si02 -C mixed powders,' Nippon Seramikkusu Kyokai
Gakujutsu Ronbunshi, 99, 704-19, 1991. Reproduced by permission of The Ceramic Society of Japan,
Tokyo, Japan.)
presumed to proceed by the following steps:
Si(CH3 )4 -+ 3CH4 + SiC(g) (12.25)
SiC(g) -+ SiC(s) (12.26)
The reaction may not actually proceed by these
steps but the thermodynamics indicate that
decomposition is favored over the employed
temperature range between 1073 and 1773 K
(800-1500 C). The particle size decreased with
increasing reactor temperature. The powders
produced below 1373 K (1100C) were found
to be amorphous by x-ray diffraction, but
those produced at higher temperatures were
of the ,8-SiC crystalline form. Transmission
electron microscopy (TEM) showed aggregates
of spherical primary particles between 20 and
400 nm in diameter (Figure 12.15).
A combustion-driven aerosol synthesis
route for producing SiC has been proposed
(Gerhold and Inkrott, 1995). Silicon carbide
(SiC) was synthesized by injecting mixtures
of a carrier gas and a silicon compound
(Si(CH3 )4, SiH4 ) into hot gas downstream of
a fuel-rich hydrocarbon-oxygen flame. The
burned gas from the combustion zone is
both the heat source and a conveying gas
(CO and H 2 ) for SiC synthesis. The gas
temperature for SiC synthesis was in the
range 1773-1923K (1500-1650C). Amor-
phous Si02 was also produced. Bando and
Tanabe (1993) sprayed silicon and silicon
oxides into a hydrocarbon-rich reduction
flame. Vapor phase reaction between the sili-
con vapor and carbon-containing radicals
yielded silicon carbide.
Myashita and Yasutake (1992) formed
mixed aerosols of Si02 and carbon by introdu-
cing halogenated silicon compounds and
toluene into a hot gas stream. The aerosol
was mixed with amines (mono ethanolamine)
and heated to form high purity SiC powder.
BORON CARBIDE
Boron carbide (B4C) is used for armor plating,
in blasting nozzles, as mechanical seal faces
and in cutting and grinding tools. It is well
suited for these applications because of its
high hardness. Boron carbide is also used in
the control and shielding of nuclear reactors
as its high boron content imparts it with a
high cross-section for neutron absorption; in
addition it is chemically inert and stable
under irradiation.
 Applications 331

I---------l 0.1 Jim

(a)

(b) L..:.....1IIo...~~aIoUl.lo!o::;;;a,jlIijL!

Figure 12.14 Micrographs of (a) precursor mixed carbon-silica powders and (b) SiC powders after heating
the precursor powders at 2073 K (1800 DC). (Murakawa, N. and Nakajima, M., 'Synthesis of SiC from fine
Si02-C mixed powders,' Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi, 99, 704-19, 1991. Reproduced
by permission of The Ceramic Society of Japan, Tokyo, Japan.)
332 Thermal aerosol processes

Figure 12.15 Microstructure of SiC powder synthesized at 1123 K (850 DC) and subsequently heat treated at
1073 K (800 DC) in air. (Wu, H. and Readey, D.W., 'Silicon carbide powders by gaseous pyrolysis of tetra-
methylsilane,' in Ceramic Transactions, 2: Silicon Carbide '87 (eds J.D. Cawley and c.E. Semler), pp. 35-46,
1987. Reprinted by permission of the American Ceramic Society, Westerville, OH.)

The gas phase synthesis of ultra fine B4C
has been accomplished via laser pyrolysis
(Knudsen, 1987) and from radio frequency
plasma-heated gases (MacKinnon and
Reuben, 1975). These two routes are discussed
in detail in Chapters 13 and 14, respectively.
Weimer et ai. (1991) used the rapid carbo-
thermal reduction route to make B4C. In this
process, a uniform solid mixture of calcined
corn starch and boron oxide was obtained
from a slurry and milled to particles less
than 45 /-lm. These particles were suspended
in Ar and fed into a 0.14m (5.5 in)
10 x 1.68 m (5.5 ft) long graphite flow reactor
which was maintained at temperatures
between 2073 and 2573 K (1800-2300C).
Additional Ar flow was used as a sheath to
reduce thermophoretic losses to the reactor
wall. The precursor particles contain carbon
and boron oxide in stoichiometric amounts
that convert to B4C according to
7C(s) + 2B 2 0 3 (1, g) ~ B4C(S) + 6CO(g)
(12.27)
As the particles enter the reactor they are
heated to temperatures above the boiling
point of boron oxide, 2133 K (1860 DC). Above
temperatures of 1733 K (1460 DC), liquid boron
oxide is reduced to gaseous boron oxide in the
presence of carbon (Lamoreaux et ai., 1987):
C(s)+ B2 0 3 (1) ~ B2 0 2 + CO (12.28)
5C(s) + 2B20 2 (g) ~ B4C + 4CO (12.29)

The rapid heating rate (105 K/s, Weimer et ai.,
1992) promotes rapid volatilization of B2 0 3
and release of carbon monoxide (CO) from
the precursor particles, forcing particle
rupture. The particles of B4 C thus obtained
are chemically homogeneous, supporting
the hypothesis of complete particle rupture
and subsequent rapid reaction between boron
and carbon, leading to B4 C clusters which grow
to macroscopic particles by coagulation, as
shown schematically in Figure 12.16. Rapid
cooling in an expanded cooling zone at the
end of the reactor stops particle coalescence.
The B4 C particles obtained from this process
had surface areas ranging from 12 to 32 m 2 / g.
Higher reactor temperatures led to powder
with lower surface area due to increased
crystal growth and agglomeration at higher
temperatures (compare Figures 3.6(d) and
3.6(c. The similarity between the laser and
rapid carbothermally produced powders
(Figure 12.17) strongly suggests that signifi-
o o 0
o Precursor Particles
0
000 00
o 0 00 0 DO 0 0
Carbon Clusters
o 0 00 0 0 0 stituent in electrodes for oxy-electric cutting
00 0 Boron Oxides and Suboxides
o
Boron Carbide Clusters
Boron Carbide Aggregates
ejO Product Boron Carbide Powders
Figure 12.16 Formation and growth of B4C par-
ticles along the reactor. (Xiong, Y, Pratsinis, S.E.
and Weimer, A.W., 'Modeling the formation of
boron carbide particles in an aerosol flow reactor,'
AIChE f., 38(11),1685-92, 1992. Reproduced with
permission of the American Institute of Chemical
Engineers, New York, NY. All rights reserved.)
Applications 333
cant reaction involved gas phase species and
that both systems are characterized by rapid
heating rates, minimized reaction times at
high temperatures and rapid cooling rates.
This also indicates the importance of tempera-
ture and heating rates in determining the
mechanism of particle formation and powder
characteristics.
For slowly heated homogeneous precursors,
the reaction most likely takes place via a classi-
cal nucleation-growth mechanism (Weimer et
ai., 1992) due to reaction proceeding through
a liquid boron oxide path (phase change). The
reaction rate is controlled by heat transfer
resistance through the precursor mass. As the
ultimate temperature approaches the boiling
point of boron oxide (,-...,2133 K; ,....,1860 C),
more of the reaction occurs through gaseous
boron suboxides.
TITANIUM CARBIDE
The hardness of titanium carbide (TiC)
coupled with its resistance to high tempera-
tures and corrosive chemical atmospheres
makes it an attractive material for applications
in pumps for transporting molten materials. It
is also used in rocket components, as a con-
of steel and as thermocouple material for use
in reducing and neutral atmospheres (Kosola-
pova, 1971).
The gas phase synthesis of TiC can be
pursued following the same techniques
employed for SiC. Latham (1967) mentioned
that replacing SiCl4 with TiCl4 resulted in
the formation of TiC powders.
Yoda et ai. (1988) reported the synthesis of
TiC from solid precursors that were obtained
from gas phase aerosol processes. Air,
propane, TiCl4 and xylene were fed into the
reactor (same as the one described for SiC)
which was heated to a temperature of 1773 K
(1500C). The aerosol formed in the furnace
(titanium dioxide and carbon particles) was
cooled and collected in a bag filter. The
powder mixture was heated to 2273 K
334 Thermal aerosol processes

w (~

Figure 12.17 Micrographs of B4C powders made via the (a) rapid carbothermal process and (b) laser
pyrolysis (x150000). (Weimer, A.W., Moore, W.G., Roach, RP., Haney, CN. and Rafaniello, W., 'Rapid
carbothermal reduction of boron oxide in a graphite transport reactor,' AIChE J., 37(5), 759-68, 1991.
Reproduced with permission of the American Institute of Chemical Engineers, New York, NY. All rights
reserved.)

(2000 DC) for 1 h in an Ar atmosphere by a high TUNGSTEN CARBIDE

frequency heating furnace. The excess carbon
was burned off at 973 K (700C). The resulting
TiC powder had a specific surface area of
10.2 m 2/ g. An x-ray diffraction pattern
revealed that the TiC powder was of the
cubic form.
Titanium carbide (TiC) can also be prepared
by heating a mixture of TiCl4 , H2 and CH4
to reaction temperatures of about 1573 K
(1300C). This reaction takes place slowly
and only small amounts of TiC are formed.
Svanstrom (1974) found that the addition of
seed particles greatly accelerated the reaction
rate. For instance, by using tungsten chloride
as a seeding agent, the yield of TiC was
increased from 5% to 92% based On TiCl4
feed. Titanium tetrachloride (TiCl4 ), CH4 , H2
and WCl 6 were present in the molar ratio of
1: 1 : 5: 0.009.
Tungsten carbide (WC) finds use as a refrac-
tory material for high temperature appli-
cations such as turbine engines and in the
aerospace industry (Zhao, Revankar and
Hlavacek, 1990). Tungsten carbide (WC)
was synthesized by the gas phase reaction
between tungsten hexachloride (WCl6 ) and
CH4 (Lamprey, Culbertson and Ripley,
1966). The solid WCl 6 was fed into a halide
vaporizer by a screw-feed mechanism. The
screw-feeder was cooled by a water jacket to
prevent premature vaporization of the halide.
The halide vapor was preheated to between
673 and 1773K (400-1500C) and introduced
into the reaction zone. A sheath of Ar
surrounded this gas stream. Methane (CH4 ),
similarly preheated, was introduced into
the reactor. The contact between the two

preheated gases promoted a spontaneous
reaction resulting in fine WC powders with
an average diameter of 0.02 j.lm.
Zhao, Revankar and Hlavacek (1990) syn-
thesized WC and W2C from the gas phase
reaction of WCl6 and CH4 in an H r Cl2
flame. Spherical particles in the size range
20-60 nm were obtained. The particles
became larger at longer residence times,
but lost their spherical shape and became
irregular.
TITANIUM DIBORIDE
Titanium diboride (TiB 2) is particularly useful
in the dispersion hardening of aluminum.
Lamprey, Culbertson and Ripley (1963)
made TiB2 by co-reducing the halide vapors
of titanium (TiCl4 ) and boron (BCl3) with
sodium vapor. The synthesis reaction was
carried out in a horizontal, tubular steel-
coated reactor. The reactant gases were intro-
duced through three concentric nozzles at one
end of the reactor. A mixture of TiCl4 and BCl3
vapors was introduced into the reactor
through the inner nozzle, Ar through the
middle nozzle and sodium vapor through
the outermost. The Ar sheaths the halide
vapors (TiCl4 and BCl3) and prevents the
clogging of the nozzle by immediate powder
formation. The incoming gases were pre-
heated so that a spontaneous reaction could
take place resulting in the formation of TiB2
particles. The temperature in the region
adjacent to the reaction zone was maintained
below 1473 K (1200C) to arrest the further
growth of submicron particles. At 1173 K
(900C), a uniform product powder was
formed with an average particle diameter of
0.1 j.lm. The product particles, by-products
and unreacted materials were collected in a
condenser and the powder was recovered by
leaching with a mixture of acetone and water.
A uniform black powder (specific surface area
of 13.7 m 2 / g) was obtained which was pyro-
phoric on exposure to air. X-ray diffraction
analysis showed only TiB 2.
Applications 335
Svanstrom (1974) describes a process where
it is possible to obtain TiB2 from the gas phase
reaction between TiCI4 , BCl3 and H 2. Molyb-
denum penta chloride (MoCls) can be used as
a seed-forming material. The use of nucleating
agents in this process reduces the amount of
material lost to the reactor walls.
OTHER MATERIALS AND COMPOSITE
PARTICLES
In their patent, Lamprey, Culbertson and
Ripley (1966) claim that their process is
capable of synthesizing submicron powders
of borides, carbides, nitrides and silicides of
the metals of Group VB and VIB and the
ferrous metals of Group VIII of the periodic
table. They give examples of the production
of colombium nitride, colombium carbide,
tantalum boride, vanadium silicide and
tantalum nitride. Thus, it seems possible
to produce molybdenum disilicide using
molybdenum penta chloride as the starting
material. Lamprey, Culbertson and Ripley
(1966) synthesized mixtures of tungsten and
molybdenum carbide from the gas phase
mixtures of tungsten and molybdenum
halides in the presence of methane and H 2;
similarly a mixture of colombium nitride and
carbide was produced from a gas phase mix-
ture of colombium penta chloride, methane,
NH3 and H 2. Konig and Fister (1995) demon-
strated the ability to synthesize nitrides,
carbides, borides and silicides of B, AI, Si, Ti,
Zr, Hf, V, Y, Ta, Nb, Mo, W, La and the
ferrous metals of Group VIII of the periodic
table. Use of laminar flow and mixing of
preheated reactant gases resulted in fine
particles with a narrow size distribution.
For instance, titanium nitride with specific
surface area of 115 m 2/ g (d p = 10 nm) was
obtained from the reaction between TiCl4 ,
NH3 and H 2.
For controlled deposition of films and
particles, the particle precipitation-aided
chemical vapor deposition (PP-CVD) has
been used to make TiN (Dekker et al., 1993).
336 Thermal aerosol processes
Alumina Tube

SiC Resistance Furnace

MulliteTube

rr==~~~~~~~===11I-!ThermOCouPle
NH3 + H2 ~ =====:=:::IF= - - - -

Si(CH 3)4 + BCI3 + H2 ~ ======[J~;;;;;;;;;;;;(~a;;);;;;;;;-_....J.

Collecting
Flask
Figure 12.18 Experimental apparatus for the synthesis of silicon carbide-boron nitride composite
particles. (Hojo, J., Aratani, M. and Kato, A., 'Vapor phase synthesis and sintering of SiC-BN composite
particle,' in Ceramic Transactions, 22: Ceramic Powder Science IV (eds. S. Hirano, G.L. Messing and
H. Hausner), pp. 121-26, 1991. Reproduced by permission of the American Ceramic Society,
Westerville, OH.)

Deposits with controlled porosity were
obtained by changing the reaction tempera-
ture and the method of mixing of the reactants
(TiC14, NH3, N z and Hz). Heterogeneous reac-
tion between TiCl4 and N z on the substrate
surface resulted in films of TiN while the gas
phase homogeneous reaction between TiC14
and NH3 led to TiN particle formation.
Hojo, Aratani and Kato (1991) synthesized
composite SiC and BN powders from the gas
phase reaction between tetramethyl silane
(Si(CH3)4), BC13 and NH3 in an Hz atmosphere
(Figure 12.18). The reactant gases were intro-
duced separately into an alumina reactor
heated to 1473 K (1200C). The NH4Cl was
removed from the powders by heating to
673 K (400C) in N z. Electron micrographs
showed that the particles were aggregates
with spherical primary particles between
0.05 and 0.1 J.lm in diameter. Energy disper-
sive x-ray spectroscopy (EDS) detected
boron, nitrogen and carbon in small areas,
though it was difficult to obtain information
on individual primary particles. Hojo, Maeda
and Kato (1987) have also synthesized compo-
site powders of SiC-Si3N 4 from gas phase
reactions.
The particle-to-particle route has been
increasingly used to make composite particles.
The precursor mixed aqueous solution is spray
dried to obtain precomposite powder which is
then thermally converted to the desired phases
in a tube furnace. Luo, Strutt and Gonsalves
(1994) used this technique to make nanostruc-
tured chromium silicide--silicon carbide and
molybdenum silicide-silicon carbide composite
particles. Nanostructured tungsten carbide-
cobalt (WC-Co) powders are being made
commercially using a similar technique (Kear
and McCandlish, 1993). An aqueous solution
of ammonium metatungstate and cobalt nitrate
is spray dried in a reducing atmosphere to
yield tungsten-cobalt particles. These particles
are then gas phase carburized to WC-Co. Iron-
molybdenum carbide dispersions in iron were
also synthesized using a similar technique
(Sadangi, Kear and McCandlish, 1994).
Nanostructured Si(N, C) powders were
synthesized by thermal decomposition at
1273 K (1000C) of aerosol of a silazane pre-
cursor ([CH3SiHNH]n, n = 3 or 4). The rapid
condensation of the decomposition products
as they exit the reactor leads to the formation
of nanoparticles (Xiao et al., 1993).

SUMMARY
A spectrum of gas phase processes for the
synthesis of commercially significant non-
oxide ceramic materials has been presented.
Gas phase synthesis routes to non-oxide
ceramic powders can be classified into gas-
to-particle conversion and particle-to-particle
conversion routes. In gas-to-particle conver-
sion, aggregated, dense, spherical particles
('hard' agglomerates) are formed with grain
size ranging from 0.05 to 0.5 pm. The proper-
ties of various non-oxide ceramic powders
formed via this route are summarized in
Table 12.1. In particle-to-particle conversion,
Summary 337
mostly porous, unaggregated particles are
formed and the grain size ranges from 0.1 to
1 pm. A summary of the powder properties
obtained from particle-to-particle conversion
is presented in Table 12.2.
The major process and product criteria for
selecting an aerosol process are availability
of precursors, powder morphology, purity,
degree of agglomeration, ease of powder pro-
cessing operations (sintering, consolidation),
simplicity of process design and cost. The
major challenge remains to manufacture
finely divided, unagglomerated powders of
high purity at low cost in commercially signi-
ficant amounts. This will help to attain the

Table 12.1 Gas-to-particle conversion

Precursors Temperature Aggregate/ Specific Purity/phase

(K (DC)) primary particle surface area composition
diameter (/l-m) (m 2 /g)

AIN AI, N 2, NH3 900-2273 0.05-1 1-40 0.5 < O2 < 8 wt%
(627-2000)
AIN AICI3, NH3 800-3073 0.1-0.7 Wurtzite lattice, 97.5%
(527-2800)
AlN AI(C 2H s )3, NH3 873-1373 0.013-0.025 20-145 Amorphous, 0.9 wt% O 2
AI(i-C 4H 9h, NH3 (600-1100) 0.011 175 (Hiai et a/., 1989);
Al(CH3)3' NH3 0.019 95 18.8wt% O2
(Tsuchida et al., 1989)
SiCI4, NH3 873-2773 0.05-0.2 80% a- and 20% ,a-Si3N4
(600-2500)
SiH 4 , NH3 823-1193 0.1 8-24 Amorphous
(550-920)
BN BCl3, NH3 3073 0.1 Hexagonal BN above
(2800) 1373 K (1100 DC)
SiC SiCl4, CH4 1810
(1537)
SiC SiH4 , CH 4 , H2 1473-1673 0.05 ,a-SiC, excess Si
(1200-1400)
SiC Si02, C, N2 1023-1773,2073 0.02-0.1 10-15 ,a-SiC
(750-1500, 1800)
B20 3, C 2073-2573 1-1.5 12-32 Crystalline
(1800-2300)
TiC TiCl4, CH4 973-2273 10.2 Cubic TiC
(700-2000)
WC WCl6 , CH4 673-1773 0.02-0.06 We, W 2C
(400-1500)
TiCl4 , BCl3 1173 0.1 13.7 Titanium diboride
(900)
338 Thermal aerosol processes
Table 12.2 Particle-to-particle conversion

Precursors Temperature Aggregate/primary Purity/phase

(K(OC)) particle diameter
(p,m)

AIN AI, N 2 , NH3 1423-1823 0.1-0.2 60wt%AIN

(1150-1550) (Shintaku, 1986)
Si3N4 Polysilazanes, N 2 , NH3 873-1273 0.38 Amorphous, crystallize on
(600-1000) calcination
Si3N4 Tris(dimethylaminosilane) 973-1923 Amorphous
(700-1650)
Si3N4 Methyldichlorosilane 1723 0.5 a- and ,B-Si3N4
(1450)
BN Poly(borazinylamine) 1273 0.5 Amorphous
(1000)
WC-Co Ammonium meta tungstate, 1473-1773 0.1 N anocrystalline
cobalt nitrate (1200-1500)

goal of low temperature, pressureless sinter- excessive agglomeration while maintaining

ing for production of dense ceramic objects.
The physicochemical phenomena involved in
gas-to-particle conversion are reasonably well
understood, so basic engineering principles
can be applied in the design and operation
of aerosol processes; hence, powders of con-
trolled size and high purity can be obtained
from these processes.
In the preparation of ceramic powders,
the mean particle size and the spread of the
distribution are important characteristics of
the product. Good sinterability demands
unagglomerated particles in the submicron
and micron size range and a controlled,
often narrow, size distribution (Rice, 1990).
For instance, monodispersed particles sinter
at a faster rate than powders with a broader
size distribution, but these particles are
neither practical to make nor optimum for all
consolidation methods; they may lead to
defects such as cracks or large grains in the
consolidated component (Chappell, Birchall
and Ring, 1986). The behavior of fine particu-
late systems is closely related to the nature
and extent of structures ('hard' or 'soft'
agglomerates) present. The obvious challenge
in process design and operation is to select
reactants and process conditions to avoid
fine particle sizes.
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LASER PROCESSES
Arne K. Knudsen
INTRODUCTION
The synthesis of powders in the gas phase
using hot wall thermal processes suffers
from a number of disadvantages. In thermally
driven processes, reactant gases must be
heated in a reactor under conditions that
often lead to particle agglomeration, powder
accumulation on reactor surfaces or impurity
incorporation from the reactor materials
themselves. These effects are a result of
reactors which involve relatively slow heating
associated with convection or radiation. As a
means of achieving cold wall reactions with
rapid heating and cooling rates, Haggerty
and co-workers (Cannon et al., 1982a,b;
Marra and Haggerty, 1982) first demonstrated
the use of infrared lasers in the synthesis of
non-oxide ceramic powders.
In laser-driven syntheses, a stream of
reactant gases is introduced into a vacuum
chamber. A focused laser beam intersects the
reactant jet and induces a rapid increase in
temperature in the gas stream. The result is
nucleation and growth of particles. The
products and unreacted raw materials exiting
the beam are rapidly cooled, thus limiting the
formation of agglomerates or coalescence of
large particles.
Powders produced via laser reactions tend to
be of high purity, controlled stoichiometry and
uniform particle size. Such powders may offer
advantages in the consolidation of ceramic
parts. In particular, the control of surface and
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
13
bulk chemistry in materials with very high
surface areas is desirable in the development
of improved ceramic processing (low tempera-
ture consolidation, high mechanical strength,
controlled chemistry etc.). A number of non-
oxide powders have been produced via this
process. These materials include SiC, Si3 N 4 ,
TiB2, B4 C and ZrB2' in addition to a number
of metals and oxide powders.
LASER SYNTHESIS OF POWDERS
LASER SOURCES
Lasers have been utilized in a number of
applications in materials processing including
machining, ablation, surface modification and
laser-assisted chemical vapor deposition.
Lasers (Light Amplification by the Stimulated
Emission of Radiation) are sources of coherent
optical radiation with intensities which are
generally much higher than those offered by
conventional radiation sources. Laser oscilla-
tion has been demonstrated in gases, liquids
and solids over a frequency regime which
extends from the microwave to the x-ray
regions of the optical spectrum. Lasers may
operate in either a pulsed or continuous
(CW) mode. In general, the peak intensity of
pulsed lasers is much higher than CW lasers,
e.g. 106 vs 104 W for CO2 lasers.
In the synthesis of non-oxide powders,
infrared lasers are commonly employed.
344 Laser processes
Nd-YAG and Nd-glass lasers operate in
pulsed or pseudo-CW mode with emission
wavelengths of 1.064 and 1.059 j.Lm, respec-
tively. The output power of these lasers can
be in excess of 5000 W. The CO2 gas laser has
been used in the majority of powder synthesis
studies. Carbon dioxide (C02) lasers are
tunable over the frequency range of 900-
1l00cm-1. This range can be extended some-
what through the substitution of isotopic 18 0
and/ or 13e. The highest gain transition for
12C1602 lasers is found at 944 cm-l which is
the frequency used in most powder synthesis
experiments. Pulsed or TEA (Transversely
Emitting Atmospheric) CO2 lasers with aver-
age powers as high as 1.5 kW are available.
The more commonly used CW CO2 lasers
with output powers as high as 8000 Ware
also marketed commercially.
Powder synthesis using lasers requires that
a portion of the optical radiation must be
absorbed by either the reactants or by a 'sensi-
tizer'. Absorption of CW laser radiation is
generally a single photon process which
results in excitation to higher energy levels.
Ultraviolet and visible lasers induce transi-
tions in electronic energy levels which can
lead to bond scission and radical formation.
Infrared lasers, on the other hand, promote
excitation of rotational-vibrational transitions.
The intensity of pulsed lasers is such that
absorption may involve many photons. This
can lead to excitation into higher electronic
energy levels or even in the case of highly
focused lasers, dielectric breakdown. At
atmospheric pressures, rotational-vibrational
excitation is rapidly randomized within the
absorbing molecule and, indeed, within the
gas stream itself via collisional energy redistri-
bution. Thus, the temperature of the reactants,
defined on the basis of the kinetic and
molecular energy distribution, is raised.
Sensitizers are species which are not
involved in the desired reaction but which,
nevertheless, are strongly absorbing. For CO2
laser radiation, Sif4 and SF6 which are quite
stable thermally and chemically, are commonly
employed. Incorporation of these compounds
will improve coupling between the laser and
reactant.
REACTOR DESIGN
The large majority of non-oxide powders
synthesized via the laser process utilize a
reactor similar in design to that displayed in
Figure 13.1. The gas stream is confined in a
narrow diameter tube. The laser beam enters
the reactor vessel through windows trans-
parent at the laser wavelength. The laser
may be focused using appropriate optics, e.g.
quartz (Nd-YAG) or KCl and ZnSe (C02), The
windows and the reactant jet are normally
blanketed with an inert gas which serves to
cool the windows and to confine the reactant
stream. Since the reactor walls are not subject
to high temperature, there is considerable
latitude in the choice of the materials of
construction (glass, steel etc.). The reactor is
normally evacuable and is maintained at a
constant pressure via a gas pumping system,
e.g. mechanical, aspiration. Powders are
collected on any of several types of filters,
including fiber-based and electrostatic preci-
pitation. Characterization of the reactor hot
zone may be facilitated by the use of an He-
Ne laser oriented orthogonally to the reactant
jet and the laser heat source. With some funda-
mental assumptions as to the scattering and
absorption efficiencies of product particles,
the formation of particles in the reactant
flame may be monitored (Haggerty, 1984).
CHEMISTRY
In the synthesis of non-oxide powders, the vast
majority of work has involved the preparation
of silicon-based products. Silane (SiH4 ) exhibits
a strong absorption at 944cm-t, is quite
reactive (.~Gf = 56.8 kJ / mol), is available in
high purity and contains only silicon and
hydrogen. In an effort to utilize less expensive
silicon sources, chlorinated silanes have been
substituted for SiH4 in the synthesis of SiC
 Laser synthesis of powders 345

tfilter
To

Reaction
flame

. Laser
beam

Water cooled
copper"becrn stopM

Figure 13.1 Schematic of typical laser powder synthesis cell. (Cannon, W.R., Danforth, S.c., Flint, J.H.,
Haggerty, J.s. and Marra, R.A., 'Sinterable ceramic powders from laser-driven reactions: I, Process
description and modeling,' J. Am. Ceram. Soc., 65(7), 324-30, 1982. Reproduced by permission of the
American Ceramic Society, Westerville, OH.)

and Si3N 4. The standard free energies of thermodynamically favorable route to B-

reaction associated with the synthesis of these containing powders:
powders from SiH4 are quite favorable, as
shown below: 4BCl3 + CH4 + 4H2 ---- B4C + 12HCl
~G(298K) =418.8kJ/mol (13.5)
!
SiH4 + C2H4 ---- SiC + 3H2
~G(1500 K) = -46.8 kJ Imol (13.6)
~G(298K) = -160.2kJ/mol (13.1)
2BCl3 + TiCl4 + 5H2 ---- TiB2 + lOHCl
~G(1500K) = -225.8kJ/mol (13.2)
~G(298K) = 367.6kJ/mol (13.7)
3SiH4 + 4NH3 ---- Si3N4 + 12H2
B2H6 + TiCl4 ---- TiB2 + 4HCl + H2
~G(298K) = -751.8kJ/mol (13.3) ~G(298K) = -71.9kJ/mol (13.8)
~G(1500 K) = -1245.4 kJ/mol (13.4)
Other reactants which have been utilized
Boron trichloride (BCI3) is also strongly in laser-driven reactions include Ti(CO)s,
absorbing to CO2 laser radiation (molar Zr(BH4)4 and WF6. A summary of non-oxide
extinction coefficient = 0.0004 Pa -1 cm -1 at powder syntheses is given in Table 13.1.
944cm- 1) (Richton and Farrow, 1982). The One of the more interesting applications of
formation of B4C and TiB2 from BCl3 can be the laser synthesis technique is in the prepara-
described by reactions which are endothermic tion of composite powders. Simply by adjust-
at room temperature. The use of diborane, ing the composition and concentration of
B2H 6 , as a source of boron, offers a more species within the reactant stream, a variety
346 Laser processes
Table 13.1 Laser-synthesized non-oxide powders

Product Chemistry Laser Reference

SiC SiH4 +C 2H 6 CWC02 Cannon et al. (1982a,b)

SiH4 +C 2H 2 CWC02 Gilissen et al. (1994); Vassen and Stoever (1993);
Tougne et al. (1993)
Si02 +C YAG Okutani et al. (1991)
SiH4 + C<4Hx CWC02 Cauchetier, Croix and Luce (1988)
Clx(CH3)~_xSi ArF O'Neil et al. (1989)
SiH2Cl 2 + C 2H 4 CWC02 Suzuki et al. (1992)
Si3N 4 SiH4 + NH3 CWC0 2 Cannon et al. (1982a,b); Li et al. (1994);
Van Weeren et al. (1994)
SiH2Cl2 + NH 3(SF6) Bauer et al. (1989)
(CH 3SiHNH)x Xiao, Strutt and Gonsalves (1990)
Si-C-N ( (CH 3hSihNH CWC02 Rice (1986)
((CH 3hSihNH + NH3 Li, Liang and Hu (1995)
SiH4 + CH3NH2 Cauchetier et al. (1991); Alexandrescu et al. (1991);
Borsella et al. (1995)
SiH4 + C 2H 4 + NH3 Suzuki et al. (1993)
BN BCl3 + NH3 CWC02 Willaime, Boulanger and Cauchetier (1995);
Baraton et al. (1994)
TiSi2 TiCl4 + SiH4 CWC02 Gupta, West and Yardley (1985)
WSi2 WF6 +SiH4 CWC02 Gupta, West and Yardley (1985)
Fe-Si Fe(CO)s + SiH4 CWC02 Frurip, Staszak and Blander (1984)
B4 C BCl3 + CH4 + H2 CWC0 2 Knudsen (unpublished results 1987, 1987a)
TiB2 B2H6 + TiCl4 CWC0 2 Casey and Haggerty (1987)
BCl3 + TiCl4 + H2 Knudsen (1987b)
B4 C-TiB2 BCl3 + TiCl4 + CH4 H 2 CWC02 Knudsen and Rafaniello (1990, 1991)
ZrB 2 Zr(BH4)4 TEA/CWC02 Cauchetier et al. (1987)

of composite powders have been produced.
The preparation of Si-C-N powders has
been demonstrated using mixtures of SiH4,
NH zCH3 and NH3 (Cauchetier et al., 1991).
The incorporation of N into the product
requires operation at lower laser powers,
whereas the product yield and SiC formation
were favored by higher power levels.
The synthesis of TiBz-B 4 C composite pow-
ders has been demonstrated using TiCl4,
B4C, CH4 and Hz (Knudsen, Haney and
Beaman, 1988; Knudsen and Rafaniello, 1990,
1991). The composition of these powders was
controlled by the concentration of TiCl4 in the
reactant stream. Thus, composites which vary
from 100% B4 C to 100% TiB2 could be pre-
pared. Mixtures of SiH4, BCl3, CH4 and Hz
(Knudsen, unpublished results 1987) have
been used to produce SiC-B4C powders.
The chemical purity and stoichiometry of
laser powder is largely determined by the
purity and stoichiometry of the reactant
gases. Thus, this process provides a con-
venient method of preparing materials with
well controlled chemistry. In the synthesis of
composite products, control over phase com-
position is also readily achieved.
FUNDAMENTALS
Reactions involving the synthesis of SiC
and Si3N4 from SiHc C 2H 4 and SiHcNH3'
respectively, have been thoroughly modeled.
Silane (SiH4) is strongly absorbing at the
high gain lOP(20) COz laser transition. Thus,
irradiation of an SiH4 reactant stream results
in the formation of a highly luminescent
flame with several distinct zones, as shown
 Laser synthesis of powders 347
(ITVTI) 50
,,
\ 2400

,,
45
,,
~i.~
::,, If
0.5
g 2000
J" I
4b\ l!!
\ True
0.4
,
:J

't/j \
w
I " ~emperature .;!o

'Vj
<I>
... 0.3 ._
35
Co
E 1600
\
... >
'iii
(/)
~ I I " Brightness 0.2 'f:
/! .... Temperature
....
UJ
Laser
'VEbnb'yof Beam
'a 0.1
pcrticulo1e pllme 1200
\
I
V I

, 0
\
\ 0 2 6 8 10 12 14
\ Distance from Nozzle (mm)

Figure 13.3 Calculated and measured temperatures

observed in the synthesis of SiC (60 kPa (~0.6 atm);
SiH 4 /C 2 H 2 1Ar=2.16 x 10- 3 /1.2 X 10-3 10m3 /h (36/
20/0cm3 /min) flow rate). The true temperature is
derived from an optical pyrometric measurement
of the brightness temperature corrected for the
emissivity of the viewed region. (Flint, J.H.,
Marra, R.A. and Haggerty, J.5., 'Powder tem-
perature, size, and number density in laser-driven
reactions,' Aerosol Sci. Technol., 5, 249-60, 1986
by the American Association for Aerosol Research.
Reprinted by permission of Elsevier Science,
Amsterdam.)

Figure 13.2 Schematic of powder synthesis reaction
zone. (Flint, J.H., Marra, R.A. and Haggerty, J.5.,
'Powder temperature, size, and number density in
laser-driven reactions,' Aerosol Sci. Technol., 5, 249-
60, 1986 by the American Associa tion for Aerosol
Research. Reprinted by permission of Elsevier
Science, Amsterdam.)
in Figure 13.2. Included in the figure is the
roughly Gaussian intensity profile of the infra-
red laser. The temperature distribution in the
reaction flame is dependent on the reaction
chemistry, laser power, reactant and annular
flow rates and reactor pressure (Fantoni et
al., 1990). For example, the temperature distri-
bution in an SiHc C2 H 4 flame is shown in
Figure 13.3.
It is apparent from the results presented
in Figure 13.3 that the temperature of the
reactant stream is greater than 1773 K
(1500 DC) as reactants enter the laser beam. In
the laser zone, the temperature may be as high
as 2273 K (2000 DC). At the gas velocities
typically utilized in these processes, this
represents a heating rate of roughly 106 K/s.
In the laser beam, heating is due to absorption
of infrared radiation followed by collisional or
radiative coupling to other species. This
mechanism is also responsible for preheating
of the reactant stream prior to its entrance into
the laser zone (Flint, Marra and Haggerty,
1986).
Reactions involving SiH4 are thought to be
initiated by the decomposition of SiH4 to
elemental Si. The concentration of Si in the
vapor is supersaturated. Thus, nucleation of
Si particles occurs (Haggerty, 1984). Other
radicals thought to be important in this
348 Laser processes
process include those derived from Si2H 6 and
Si3HS (Rice and Woodin, 1989). Collisions of
these nucleated particles result in the growth
of larger Si particles. Below the melting point
of Si (1683 K; 1410 C), colliding particles grow
as uniform spheres. As they exit the heated
zone and are rapidly cooled, additional colli-
sions are not effective in further particle
growth (Flint and Haggerty, 1988).
The addition of a hydrocarbon, e.g. C 2H 4,
results in the carburization of Si at tem-
peratures above about 1473 K (1200C).
Introduction of C2H 4 also leads to a rapid
increase in the gas stream temperature to
~1873K (1600C) or as is shown in Figure
13.3, 2273 K (2000C). This temperature
increase has been attributed to the exothermi-
city of the Si-C2H 4 reaction and to increased
coupling between the laser and the forming
SiC particles (Flint and Haggerty, 1988).
Introduction of NH3 in the synthesis of
Si3N4 proceeds via a similar mechanism.
Ammonia (NH3) begins to react with Si
as SiH4 decomposes. In general, the Si3N4
powders are significantly smaller in average
diameter since the coalescence of liquid Si
droplets is precluded by the formation of
refractory Si3N4 (Flint and Haggerty, 1988).
To facilitate the formation of larger Si3N4 par-
ticles, reactor modifications which inject NH3
into the reactant stream above the laser zone
have been adopted (Aoki, Flint and Haggerty,
1988).
The purity, crystallinity, particle size and
degree of agglomeration are strongly influ-
enced by a number of factors. In the synthesis
of B4C, TiB2 and B4C-TiB2 composites, the
stoichiometry of the products is directly
related to the stoichiometry of raw materials
(Knudsen, unpublished results 1987, 1987a,b;
Knudsen and Rafaniello, 1990, 1991). The
maximum hardness of B4C has been shown
to correspond to a B/C ratio of 4.1 (Niihara,
Nakahira and Hirai, 1984). The product B/C
ratio is roughly 50% of the BCl3/CH4 ratio
in the feed gas, as shown in Figure 13.4
(Knudsen, unpublished results 1987).
35
30
~
e.... 25
lii
-c
~
0
20
c..
.5 15
c:
0
-eas 10
U
5
0
0 2 4 6 8 10 12 14 16 18 20
Carbon in Feed (%)
Figure 13.4 Stoichiometry of recovered powder
(atomic B/C ratio) relative to the BCl3 /CH 4 ratio
in reactant gas stream. (Knudsen, A.K., 'Laser-
driven synthesis and densification of ultrafine
boron carbide powders,' Adv. Ceram., 21, 237-47,
1987. Reproduced by permission of the Ameri-
can Ceramic Society, Westerville, OH.)
Laser power can be varied over several orders
of magnitude by focusing/ defocusing the beam
and through the use of high power lasers. Inten-
sity strongly influences the synthesis flame tem-
perature. In the synthesis of Si3 N 4, increased
intensities favor improved stoichiometry and
reduced particle size (Cannon et al., 1982b). A
flame temperature above 1300 K (1027C) is
required for the production of fully crystalline
Si3N4 (Symons and Danforth, 1987). The content
of residual Si and C from S~-C2H2 and Si~
C2~ reactions decreases with increased laser
power as shown in Figure 13.5 (Cauchetier,
Croix and Luce, 1988).
The reactor pressure is related to the flame
temperature and, thus, to product yield and
chemistry. In the synthesis of SiC, the flame
temperature was found to exhibit a maximum
at a cell pressure of 0.065 MPa (488 torr)
(Fantoni et al., 1990). For Si3 N 4, higher pres-
sures result in increased particle diameters.
This is consistent with a constant density of
nucleation sites and a fixed depletion
volume. Thus, as the density of reactants
increases, the mass of each particle must also
increase (Cannon et al., 1982b).

5 (A) 5 presented in Table 13.2.
0 0 :;
(8) (u
(5
-S
()
10 10 Cl
.!:
c
'(ij
E
CD
a:
5 5
o 200 400 600
Laser Power (W)
Figure 13.5 Yield of SiC synthesis reactions for
(A) SiH4 -C 2 H 2 and (B) SiH 4 -C 2 H 4 mixtures.
(Cauchetier, M., Croix, O. and Luce, M., 'Laser syn-
thesis of silicon carbide powders from silane and
hydrocarbon mixtures: Adv. Ceram. Mater., 3(6),
548-52, 1988. Reproduced by permission of the
American Ceramic Society, Westerville, OH.)
Residence time in the laser beam can be
controlled by the reactant flow rates and the
size of the beam itself. Not surprisingly,
extension of the residence time results in
an increase in particle size. For example,
the Brunauer-Emmett-Teller (BET)-derived
average particle diameter of laser-synthesized
SiC increased as much as threefold as the
reactant residence time was increased from
0.5 to 9ms.
POWDER CHARACTERISTICS
Powder synthesized via laser-driven reactions
is, not surprisingly, similar in particle size and
morphology to non-oxides synthesized via
other gas phase synthesis methods. Represen-
tative micrographs of SiC, Si3N 4, B4C, TiB2
and composite TiB 2-B4C powders are shown
in Figure 13.6. A summary of the powder
Laser synthesis of powders 349
characteristics of these ceramic powders is
In general, the homogeneous nucleation of
particles in the laser flame results in powders
which are equiaxed and fine. As an example,
B4C powder (Figure 13.6(c)) exhibits a narrow
particle size distribution centered at about
35 nm. With modifications to the reactor and
reactant inlet geometry designed to increase
particle diameter, such as NH3 injected high
in the laser beam in the synthesis of Si3 N 4,
larger particles may be prepared. Commonly,
the particle size distribution of these powders
is polymodal, reflecting Si droplets which
have coalesced into large (200 nm) particles
as well as smaller (40 nm) 'primary' particles.
Titanium diboride (TiB 2) powders are rather
distinctive in their adoption of a characteristic
hexagonal morphology. Large TiB2 platelets
are clearly visible in the composite powder
displayed in Figure 13.6(e).
The high surface free energy of laser-
synthesized powders tends to favor the
formation of weak agglomerates. These
agglomerates may assume a chain-like struc-
ture. Destabilization of these agglomerates,
necessary for the fabrication of high density
ceramic greenware, has proven to be challen-
ging. The fine particle sizes and, consequently,
the high surface areas of laser powders also
render them susceptible to both hydrolysis
and oxidation. Thus, processing in an inert
atmosphere may be necessary in systems
where a non-oxidized surface chemistry is
critical, e.g. Si3N4 (Nilsen, Danforth and
Wautier, 1987).
ECONOMIC CONSIDERATIONS
The practical utilization of laser synthesis in
the production of commercial quantities of
ceramic powders has not been demonstrated.
Whereas the engineering and chemistry are
well within current capabilities, lack of
demand for ultra fine non-oxide powders and
raw material cost have limited interest in
commercial production. Haggerty estimated
350 Laser processes

(a)

Figure 13.6 Laser-synthesized powders: (a) SiC; (b) Si3 N 4 ; (c) B4 C; (d) TiB 2; (e) B4 C-C-TiB2 composite. a):
Lihrmann, J.-M. and Cauchetier, M., 'A model for the formation of nanosized SiC powders by laser-
induced gas-phase reaction,' J. Eur. Ceram. Soc., 13(1), 41-46, 1994. Reprinted with kind permission
from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK. (b): Symons, W.
and Danforth, S.c., 'Hot isostatic pressing of laser synthesized silicon nitride powder,' in Proceedings
for the Third International Symposium on Ceramic Materials and Components for Engines (ed. V.J. Tennery),
pp. 67-75, 27-30 November 1988, Las Vegas, NV, 1988. Reproduced by permission of the American
Ceramic Society, Westerville, OH. (c): Knudsen, A.K., 'Laser-driven synthesis and densification of ultra fine
boron carbide powders,' Adv. Ceram., 21, 237-47, 1987. Reproduced by permission of the American
Ceramic Society, Westerville, OH. (d): Knudsen, unpublished results, 1987. (e): Knudsen, Haney and
Beaman, 1988.)

the costs associated with scale-up of SiC and
Si3N4 from silane (Haggerty, 1984). Haggerty's
analysis incorporated resistance heating to
700 K (427C) with a CO2 laser used to heat
the reactants to 1273 K (1000C). With a 2 cm
(",0.8 in) reactant diameter, a gas velocity of
500 cm/ s (16.4 ft/ s) and a laser power of 1.3-
1.5 kW, Haggerty found that the production
rates of 5-7kg/h (11-15.4lb/h) could be
realized for SiC and Si3N4 powders. In general,
raw materials costs accounted for 30-90% of the
production costs of these products. Energy
costs were estimated to be 2.1 (Si3N 4) and
1.9 kW . h/kg (SiC), respectively. These results
have stimulated interest in the substitution of
less expensive chlorosilanes for silane.
The utilization of laser synthesis on a
commercial scale will require a significant
reduction in the cost of raw materials.
Energy and equipment costs do not appear
to represent a significant impediment to com-
mercial synthesis.

Figure 13.6(b)
APPLICATIONS
The processing of laser-synthesized ceramic
powders is similar to the processing of other
vapor-phase-synthesized materials. The high
surface area and fine particle sizes associated
with these powders result in high sintering
activity. In addition, densification of fine pow-
ders offers the potential for fabricating fine-
grained microstructures. Thus, parts with
high strength or unique phase distributions
may be prepared.
POWDER PROCESSING
The dispersion of high surface area powders
is challenging due to the tendency for the
particles to agglomerate. In addition, signifi-
cant particle-particle friction reduces the
Applications 351
packing efficiency in green compacts. Thus,
a number of research efforts have focused
on improved routes to dispersing laser-
synthesized powders.
Compaction of as-synthesized powders
results in greenware with densities ranging
from 35% to 50% of theoretical. For most
sintering or reaction-bonding applications,
such low densities are unacceptable. In the
case of reaction-bonded Si3 N 4 , an Si density
of 40-49% would be expected to yield a
nitrided density of only 50-60% of theoretical
(Danforth and Haggerty, 1983). These densi-
ties may, however, be increased through the
use of colloidal processing.
In a study involving the dispersion of
Si3 N 4 , powders maintained in an inert
atmosphere and those exposed to air were
compared. Samples were dispersed in
352 Laser processes
Figure 13.6(c)
hexane using an imidazoline dispersant. As
displayed in Figure 13.7, the exposed powders
exhibited significantly higher green densities
than those which were not exposed to atmo-
spheric moisture. Hydrolysis of the powder
surfaces results in the formation of silanol
and silazane surfaces, whereas the unexposed
surface tends to consist primarily of silazane
(Siz-NH) structures (Nilsen, Riman and
Danforth, 1988). This difference in surface
chemistry is reflected in a significant change
in powder processability. Solution-stabilized
Si3N4 has been dispersed in isopropanol and
pressed in a colloidal press to a density of
52% of theoretical (Aoki, Flint and Haggerty,
1988).
CONSOLIDATION
Sintering studies involving ultrafine laser pow-
ders have shown evidence of local densification
at relatively low temperatures. For example,
heat treatment of Si3N4 powders results in par-
ticle growth, although this growth is generally
associated with crystalline particles. Thus, as
the compact microstructure coarsens, the
larger particles are found to be crystalline,
whereas amorphous particles remain small in
size. This coarsening is generally not accompa-
nied by macroscopic shrinkage of the compact
(Sawhill and Haggerty, 1982).
Pressureless sintering of laser-synthesized
SiC has shown more promise. Laser SiC,

Figure 13.6(d)
doped with B as a sintering aid, has been sin-
tered to densities as high as 95% of theoretical.
These densities were consistently higher than
those obtained from a commercial SiC powder
(Croix et al., 1991).
Measurable consolidation of laser Si3N4
requires the application of pressure. Powders
that were either exposed to or protected
from atmospheric moisture were con-
solidated via hot isostatic pressing. As
shown in Figure 13.8, laser-synthesized
Si3N4 can be consolidated to high density.
The densities of hydrolyzed powder,
however, were significantly greater than
those observed in powders not exposed to
ambient atmosphere (Symons and Danforth,
1988).
Applications 353
1.0 .... m
Hot pressing offers the most effective
means of densifying ultrafine powders. Laser
B4C and B4C-TiB2 composites are readily hot
pressed to full density. The densification
of laser-synthesized and other B4 C powders is
compared in Figure 13.9 (Knudsen, 1987a). In
general, laser B4C is significantly more active
than commercially available B4 C powders.
As with many vapor phase syntheses, laser-
driven syntheses produce powders with
ultrafine particles and very high surface
areas. Unfortunately, ceramic processors have
not developed techniques to disperse and fab-
ricate these materials. Thus, the low densities
commonly observed with these products pre-
clude the consolidation to high density without
the assistance of pressure.
354 Laser processes

Figure 13.6(e)

Table 13.2 Typical properties of laser-synthesized powders

Powder Particle diameter Morphology Surface area Impurities Crystallinity Reference

(nm) (m 2 /g)
SiC 30 Equiaxed 60 0, C, Si {3, crystalline Cauchetier, Croix
and Luce (1988)
Si3N4 10-200 Polymodal, 40-160 0, Si Cl:, crystalline Aoki, Flint and
equiaxed Haggerty (1988);
Symons and
Danforth (1987)
B4C 34 Equiaxed 55 0, Cl Crystalline Knudsen (1987a)
BN 11-31 Graphite-like, 85-234 O,Cl Crystalline Baraton et al.
turbostratic (1994)
TiB2 25-330 Hexagonal 30-50 0, Cl Crystalline Knudsen (1987b;
unpublished
results 1987);
Casey and
Haggerty (1987)
 Applications 355
Pressing Pressure (MPa)
100 200 300 400
50

~
iii
c
CD
0
(ij
()
40
~0
CD
..c o Exposed Powder
I-
0~
Unexposed Powder

30
0 10 20 30 40 50 60
Pressing Pressure (KSI)

Figure 13.7 Packing density of Si3N4 powder as a function of uniaxial pressure for powders unexposed
and exposed to the ambient environment. (Nilsen, K., Riman, R.E. and Danforth, S.c., 'The effect of
moisture on the processing of silicon nitride in imidazoline-hexane solutions,' in Proceedings for the
Third International Symposium on Ceramic Materials and Components for Engines (ed. V.]. Tennery), pp. 155-
67,27-30 November 1988, Las Vegas, NV, 1988. Reproduced by permission of the American Ceramic
Society, Westerville, OH.)

PROPERTIES
Temperature (K) Reaction bonding of laser-synthesized silicon
1900 2100 2300 powder has been widely studied. Character-
100
.~
ization of reaction-bonded silicon nitride
90 Exposed
IJ)
c o Unexposed
(RBSN) parts indicates that strength is
CD
Cl 80 strongly dependent on porosity. Reaction-
(ij
0 70 bonded silicon nitride (RBSN) derived from
~0 60 laser Si is markedly stronger, e.g. 250-500%,
CD
.s::: at comparable porosities when compared to
I- 50
-;R.
0
parts prepared from conventionally prepared
40 silicon powders (Flint and Haggerty, 1988).
1600 1700 1800 1900 2000 2100
This improved strength is likely due to the
Temperature (0G)
fine grain sizes achievable with ultrafine
Figure 13.8 Density vs temperature for Si3N4 parts powders. Sintered laser SiC has also proven
prepared from hot isostatic pressing of powders to exhibit elevated strength and hardness
unexposed and exposed to the ambient environ- over parts prepared from commercial SiC
ment. (Symons, W. and Danforth, S.c., 'Hot powders. In fact, the measured strength,
isostatic pressing of laser synthesized silicon crt = 645 60 MPa, and microhardness, Hv =
nitride powder,' in Proceedings for the Third Inter-
national Symposium on Ceramic Materials and Com-
23.8 CPa, are considerably higher than are
ponents for Engines (ed. V.]. Tennery), pp. 67-75, normally observed in sintered SiC and are
27-30 November 1988, Las Vegas, NV, 1988. comparable to hot-pressed SiC (Haggerty et
Reproduced by permission of the American al., 1988). The fine microstructure of laser-
Ceramic Society, Westerville, OH.) derived parts, however, also results in a
356 Laser processes
Temperature (K) decrease in the oxidation resistance (Croix
100
1800 2000 2200 2400
. et al., 1991).
Hot-pressed laser B4C represents a system
95 where the advantages in using an ultrafine
i!"-
'iii
cQ) 90
powder are apparent. The average grain size
0 of B4 C is strongly dependent on the consolida-
iii 85
.!.1 tion temperature. The use of a powder which
~ 80 densifies at a low temperature, relative to
0
Q)

f= 75 lower surface area materials, facilitates the

<fl.
70
65L-~--~--~--~--L-~ __~__~
1500 1600 1700 1800 1900 2000 2100 2200 2300
Temperature (' C)
Figure 13.9 Density (% theoretical) vs hot pressing
temperature for B4 C powders with average particle
diameters of 0.3--0.4 /-lm (1), 2.9 /-lm (2) and 0.034 /-lm
(3, laser powder). (Knudsen, A.K., 'Laser-driven
synthesis and densification of ultrafine boron
carbide powders,' Adv. Ceram., 21, 237-47,
preparation of a fine-grained microstructure
in systems sensitive to high temperature
(Knudsen, 1987a).
The consolidation of B4C-TiB2 composite
powders results in a unique microstructure,
as displayed in Figure 13.10. The distribution
of fine (I-211,m) TiB2 (bright phase) grains in
a similarly fine-grained matrix is apparent
in the figure. This microstructure results in a
significant improvement in the fracture tough-
ness (Krc = 5.6 vs 3.4Mpa m 1/ 2) and hardness
(Hv = 35 vs 32 GPa) over the B4C matrix phase
or when compared to composite parts pre-

. - . . ... .. ---.-,
1987. Reproduced by permission of the American pared from physical mixtures of B4 C and TiB2
Ceramic Society, Westerville, OH.) powders (Knudsen, Haney and Beaman, 1988).

-- -- .-.,.
....
~
":-i
'4{- " ~., ...... ,,~,.
,. *'.... '..L.,.-.tI t ,-."
~ - '

" ...
-

- - .

,', .,. '..-!..-."

.,'". ,....
.. ' .... ~.. .
,\1"" -

..
I
J. .. ", '6.,
.. - ,.'. ... ami ....,.-" ~

........
..,

,-.-
-

, .......,
.

..-,..... .. ...
.. .......
,.. -. . a~, __ : .~.....

.... .........mil.'
~
'.~
" ~
.' t. e ..-

.... ...
I \- ..... , _." "... .., . . . . . .'
-

~~. .

.\..... -=--. .. .
,.
. ta . . . . . . . . ,.. . . . . ".

'... . ,. .
~ \- ~

. ..-.-, ,... .
"

" It a.&.-. . ..
. ..a_~.. ,4 . ,..
_ "
~. .. -
~ ,. '.~I- ~
Figure 13.10 Scanning electron micrograph of 80 wt% B4 C/20 wt% TiB2 composite hot pressed from laser-
synthesized composite powder (Knudsen, Haney and Beaman, 1988).

Demand for laser-synthesized powders will
only follow the development of technology for
the practical handling and processing of these
powders into ceramic parts.
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Bauer, R.A, Smulders, R, Becht, J.G.M., van der
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Casey, J.D. and Haggerty, J.S. (1987) Laser-induced
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PLASMA PROCESSES 14
Peter C. Kong and Emil Pfender

INTRODUCTION collision dominated. Under such conditions,

local thermodynamic equilibrium (LTE) may
This chapter presents an overview of recent
prevail, which includes kinetic equilibrium
research efforts in plasma synthesis of non-
(Te :::::: T h, where Te is the electron temperature
oxide ceramic powders. There has been a
and This the heavy particle or sensible
strong interest in nitrides, followed by
temperature) as well as chemical equilibrium,
carbides and finally borides. Electric arc and
i.e. particle concentrations in an LTE plasma
electrodeless plasma reactors have been
are only a function of the temperature.
developed for producing ultrafine and pure
Examples of thermal plasmas are those
powders of such ceramic materials. Novel
produced in high intensity arcs, plasma
plasma reactors, using multiple torches or
torches, or in high intensity, high frequency
combinations of direct current (DC) and
discharges.
radio frequency (RF) plasma generation, and
In contrast, in low pressure plasmas, the
innovative process designs have contributed
mean free paths are much longer and, there-
to the advancement of plasma powder
fore, the collisions between particles are
synthesis.
much less frequent. Under these conditions,
the electron temperature, Te, may be much
DEFINITION OF PLASMA STATE: THERMAL higher than the sensible temperatures, T h, of
PLASMAS AND COLD PLASMAS the heavy particles, i.e. Te Th (Figure 14.1).
Plasmas produced in various types of glow
A plasma is a gas of sufficient energy content
discharges, in low intensity high frequency
such that a significant fraction of the species
discharges and in corona discharges, are
present is ionized and, hence, is a conductor
typical examples of cold plasmas. Thermal
of electricity. Although there are free charges
and cold plasmas cover a wide range of pres-
in a plasma, overall negative and positive
sures, temperatures and electron densities.
charges compensate each other. Therefore,
They are classified as shown in Figure 14.2.
plasmas are electrically neutral, a property
which is known as quasi-neutrality.
There are two types of plasmas, namely,
PLASMA SUITABILITY FOR SYNTHESIS
high pressure thermal plasmas and low pres-
OF CERAMICS
sure non-equilibrium cold plasmas. For high
pressure plasmas, the mean free paths The process used for synthesizing particles
between electrons and heavy particles are determines the degree of their sintering
extremely short and, therefore, the plasma is ability since the process controls the chemical

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
360 Plasma processes
105~-------------------------,
102L---~--~--~--~--~--~~
10-4 10-3 10-2 10- 1 100 101 102 103
Pressure (kPa)
Figure 14.1 Variation of electron and heavy particle
temperatures with pressure.
homogeneity of the powders, the particle
morphologies, the product purity and its size
distribution. The interest of thermal plasma
synthesis of ultrafine and ultrapure powders
has been increasing, especially in the area of
ceramic materials (Taylor and Pirzada, 1994).
Since the temperatures in a thermal plasma
are extremely high (>10 000 K), chemical
reactions are much more energetic than in
conventional processes. Furthermore, the
quench rates (",10 6 K/s) of the reactions are
extremely fast, resulting in preservation of
the products, especially for metastable
compounds. Fast reaction and quench rates
result in very short overall processing times
which may be as short as milliseconds.
Thermal plasmas which provide high tem-
peratures and steep temperature gradients
offer an attractive and chemically non-specific
route for synthesizing fine refractory pow-
ders. Furthermore, in a plasma, the super-
saturation of vapor species which provides
the driving force for particle condensation
can be very large, leading to the production
of ultrafine particles by homogeneous nuclea-
tion. Non-oxide boride, carbide and nitride
ceramic powders and solid solutions have
been successfully synthesized in thermal
plasma reactors. Today, this technology is
known as 'thermal plasma synthesis'. In
thermal plasma synthesis, the reactants may
be gases, liquids or solids before injection into
the plasma. However, gas phase precursors
for metals are uncommon. Therefore, the

5r---------------~--------------~------_,
Controlled
1 ev =7736 K Thermonuclear
4 Fu ion

~ 3
Fusion Plasmas
~
~

rn
1!!
(J) 2
Solar
Corona
a.
E
~ Shock "C
Ole
c:
e Waves .~ ~
00
"0 ~"C
.JJ!e -;;~
(J)
al~
bJ:
on
iii 0 High Pressure
C)
0 Arcs
...J

-1

-2~--~~~~--~--~--~--~--~--~--~
o 5 10 15 20 25
--Vacuum Log Number Density (cm- 3) Solid--

Figure 14.2 Classification of plasmas.


most commonly used reactants for plasma
synthesis have been solids. Recently, a liquid
injection method (Kong and Pfender, 1990)
has been developed to overcome the problems
associated with solid injection and to capitalize
on the benefits of gaseous reactants.
Thermal plasmas suitable for powder
synthesis are primarily produced by means
of high intensity arcs (AC or DC) and high
frequency discharges (RF and microwave
(MW. Recent advances in novel reactor and
process designs have enhanced the quality of
powder produced in thermal plasmas. These
novel designs aim at maximizing the heating,
mixing and residence time of reactants in the
plasma. Either the discharge itself or the
plasma flame downstream of the discharge
may be used for the synthesis.
PLASMA GENERATION
Plasmas may be generated by the passage of
an electric current through a gas. Since gases
at ambient temperatures are excellent insula-
tors, a sufficient number of charge carriers
have to be generated to make the gas
electrically conducting. The passage of an
electrical current through an ionized gas
leads to an array of phenomena known as gas-
eous discharges. Such gaseous discharges are
the most common, but not the only means for
producing plasmas. Plasmas are also pro-
duced by electrodeless RF discharges, micro-
waves, shock waves, lasers and high energy
particle beams. Finally, plasmas may also be
produced by heating of gases (vapors) in a
high temperature furnace. Because of inherent
temperature limitations, this method is
restricted to metal vapors with low ionization
potentials.
ARC PLASMAS
Although both AC and DC arcs are in use,
only DC arcs will be considered. Both trans-
ferred and non-transferred arcs have been
used to promote chemical reactions. The
Plasma generation 361
non-transferred arcs may be operated in the
low voltage (20-200 V) mode and are charac-
terized by their ability to be sustainable at
relatively low flows and high exit gas
enthalpies. Typically, the flow through the
device is mildly turbulent, and the gas may
or may not have a swirl component. The low
flow condition in the low voltage mode is well
suited for materials synthesis. But there is one
disadvantage with the low voltage mode for
high power operation. The device must be
operated at high currents, thus leading to
significant electrode erosion. The high voltage
mode uses longer anode nozzles and usually
has a significant swirl component super-
imposed. The more intense the swirl, the
longer the arc and the higher the voltage.
Typical voltages for this type of device range
between 200 and more than 1000 V. The
advantage is operation at lower currents,
minimizing electrode erosion at high power
levels.
In the transferred arc operation mode, the
arc is terminated on a secondary anode and
the pilot anode remains on floating potential.
This principle may be extended by adding
graphite or metallic segments, electrically
insulated from each other, between the pilot
and the secondary anode. This is known as a
wall stabilized 'cascaded arc' which produces
high enthalpy plasma flows (Pfender, 1984).
But, because of heat losses to the segments,
the overall efficiency of such devices is
rather low. For this reason, such devices are
rarely used for plasma synthesis. An uncon-
fined transferred arc may be stabilized by con-
vection, whereas a 'free burning arc' may
establish its own stabilizing mechanism by a
strong cathode jet (Pfender, 1984). These
types of arcs have been used extensively in
powder synthesis.
HIGH FREQUENCY DISCHARGES
There are two types of plasmas which can
be sustained by high frequency discharges.
The first one is the radio frequency (RF)
362 Plasma processes
inductively coupled plasma (ICP) and the
second is the microwave coupled plasma
(MWP). Usually the frequency ranges from
kHz to MHz for RF ICPs to GHz for MWPs.
These types of plasmas are referred to as
electrodeless discharges. Radio frequency
inductively coupled discharges are capable
of producing ultraclean, high temperature,
relatively large diameter and low velocity
plasmas which are particularly suitable for
chemical reactions. Since ICP is an electrode-
less plasma, the reactor is insensitive to the
type of gas used. Therefore, this type of
reactor is ideal for using reactive gases for
specific chemical reactions. However, MWPs
differ significantly from DC arc plasmas and
ICPs by higher electron densities and higher
reactivities at much lower input powers.
Unfortunately, the operating pressure range
for MWP is limited and the plasma volume
is very small compared to ICPs and DC arcs
at high pressures. This difficulty arises from
the dimensional restriction of MWP genera-
tion at high pressures in a resonant cavity.
This problem was resolved by coupling a rec-
tangular waveguide to a tapered coaxial
waveguide which also acts as an electrode
for igniting a high reactivity, high enthalpy,
low input power and large volume H2 MWP
jet at 100 kPa (1 atrn) pressure (Mitsuda,
Yoshida and Akashi, 1988). Under their oper-
ating conditions for the MWP it would be
impossible to sustain either a DC arc plasma
or an ICP for H 2.
PLASMA REACTORS
CONVENTIONAL REACTORS
Conventional plasma reactors usually consist
of either a DC or an RF plasma torch con-
nected to a reaction chamber. The reaction
chamber can be metallic, quartz or graphite.
A powder collector and a filter, followed by a
gas scrubbing system, are downstream of the
reaction chamber. Particle synthesis can be
performed in the discharge itself or in the
tail jet region. In practice, most of the
reactions are carried out in the field-free
region of the plasma to avoid stability prob-
lems. Microwave plasmas have not been used
to any considerable extent in powder synth-
esis due to the difficulties of sustaining a
large plasma volume at high pressures.
Novel reactor designs attempt to address
these problems.
NOVEL REACTORS
Hybrid plasmas
It is possible to operate an ICP in tandem with
a DC or another ICP. In contrast to DC arc
discharges, which exhibit maximum tempera-
tures in the core of the plasma, the ICP shows
an off-axis temperature maximum. In general,
the maximum temperature is substantially
lower than that of a DC plasma. The super-
imposed DC plasma or ICP may act as a pre-
ionization source, and the second ICP adds
auxiliary heat downstream to maintain high
temperature levels. Hybrid plasmas increase
the volume of the combined plasmas and
alter the temperature profiles. It is also
possible to superimpose successive ICPs
beyond the first tandem set to produce a
longer hot reaction zone with relatively
uniform temperature. Yoshida et al. (1983)
performed modeling and experimental work
on an RF-DC hybrid plasma reactor for the
synthesis of Si3N 4 . They noted that the arc jet
flow produced a high temperature and high
velocity channel which eliminated the usual
recirculation eddy found in an ordinary RF
plasma. This hybrid plasma generated a
rather large and uniform high temperature
region for materials synthesis.
Multiple plasma torch reactor
The majority of plasma synthesis processes
use solid particulates as reactants. The
residence time for injected particles in a
plasma is extremely brief, which may result

in incomplete evaporation of particles. There-
fore, small particle sizes are desirable to
ensure complete evaporation. However, feed-
ing small particles into a thermal plasma is a
formidable problem, because of the high
viscosity of a plasma. Two novel plasma
reactor designs attempted to address the prob-
lem of particle injection, entrainment, mixing
and heating in the plasma. The first design
employs three plasma torches to create a co-
planar radially impinging plasma flow
(Bolotov et al., 1983). This system produces a
large stagnation area in the center of the
reactor where solids are introduced. Recircu-
lation was observed above and below the
plane of the colliding plasmas. Temperature
maxima were observed off-axis in the reactor.
The second design also uses three plasma
torches to create a strong converging axial
plasma flow (Lu and Pfender, 1989). The con-
verging flow creates a long plasma flame with
a lower temperature valley in the center. Solids
injected through this valley are totally engulfed
1/ -"~-
DCJet-----;------~~
Window
Quartz
Reaction
Tube
Figure 14.3 Schematic of the triple torch plasma reactor (only two torches are shown).
Plasma reactors 363
by the plasma. A converging flow triple DC
plasma torch reactor is depicted in Figure 14.3.
Multiple DC torches - RF combined
plasma reactor
A DC-RF combined plasma torch device was
described in a European patent application
(Saiki et al., 1988). The apparatus consists of
three DC plasma torches (similar to the one
described by Lu and Pfender (1989 and an
RF coil arranged in tandem (Figure 14.4).
The three plasma jets form a converging
plasma flow, and an RF field is superimposed
downstream onto the DC plasma flame. The
applied RF field directly couples to the
converging DC plasma flow and superheats
the DC plasma by generating an RF plasma
which surrounds the main gas flow. This
triple DC-RF combined plasma differs from
the DC-RF or the RF-RF hybrid plasmas by
not requiring the use of the usual sheath gas
to generate the downstream RF plasmas.
Translation Linkage
Chamber
364 Plasma processes

RF-DC Combined Plasma

.~--~I4--I-- High Temperature

DC Jet Channel

Figure 1.4.~ Schematic of a hybrid plasma reactor (combination of DC triple torch and RF torch) (Adapted
from Saiki et al., 1988.) .

Counter-flow liquid injection tion zone which rotates counter-clockwise

plasma reactor is induced by the strong plasma flow.
2. The temperature distribution shows a large
Rece~tly, a counter-flow liquid injection
plateau of approximately 5500 K (5227C)
techmque for the synthesis of various ceramic
in the mixing region.
powders in thermal plasmas has been
3. Slow quench rates prevail downstream of
developed (Kong and Pfender, 1990). This
the recirculation and the mixing region.
technique has been designated as Counter-
4. Particle trajectory calculations indicate that
Flow Liquid Injection Plasma Synthesis (CF-
a 50 J-Lm liquid particle, assuming no
LIPS). Organometallic liquids have been
evaporation, has a minimum residence time
used for the synthesis of non-oxides. With
of 120 ms in the high temperature region.
this. method, atomized liquids are injected
This residence time is at least two orders of
agamst a DC plasma jet for vaporization and
magnitude higher than in the case of conven-
reaction to form powders (Figure 14.5). CF-
tional parallel-flow injection into a plasma.
LIPS has a number of advantages when
5. Smaller particles will experience an even
compared to solid injection (Kong and
longer residence time in the high tempera-
Pfender, 1990). Modeling results (Paik et al.,
ture zone.
1991) show the following key features of the
6. Considering evaporation, particles less
reactor.
than 100 J-Lm in diameter will evaporate
1. Three recirculation zones are indicated completely in the plasma within a few
inside of the reactor. The largest recircula- milliseconds.

Cathode - - - I:tet.
Anode---II
Atomized
Liquid Reactants
Chamber
Figure 14.5 Schematic of the counter-flow liquid injection plasma system.
POWDER SYNTHESIS
The most common reactants for thermal
plasma synthesis of non-oxide ceramics are
solids and metal halides. Some of the most
relevant processes for plasma synthesis of
nitrides, carbides and borides are listed in
Tables 14.1, 14.5 and 14.10, respectively. In
the following sections, specific examples of
plasma processes for the synthesis of non-
oxide powders will be discussed in more
detail.
NITRIDES
A survey of recent plasma synthesis routes for
nitride powders is shown in Table 14.1.
Powder synthesis 365
_ ...-- Plasma Torch
Quartz Reaction Tube
Counter-flow
Liquid Injection
Probe
Gas Exhaust
Aluminum nitride (AIN)
Aluminum nitride (AIN) is a non-oxide ceramic
material with a high thermal and very low elec-
trical conductivity and an expansion coefficient
close to that of silicon. Because of these proper-
ties, this is a material of choice for the electronic
packaging industry (Chapters 1 and 2). Con-
ventional methods for producing AlN rely on
carbothermal reduction of alumina.
Thermal plasma synthesis of AIN has been
explored by a number of investigators over
the past decades. This is because the high
enthalpy content and the controlled atmo-
sphere in plasmas provide the proper pre-
requisites for producing high purity material.
Both RF and DC arc plasma reactors have
been used for this purpose.
366 Plasma processes
Table 14.1 Plasma-produced nitride powders

Compound Reactants Phast Plasma b Reference

AIN AI-N2 s/g TTP Lu and Pfender (1989)

AIN AI-NH r N 2 s/g TTP-RF Saiki et al. (1988)
AIN AI-N2 s/g DC Matsumoto (1968a)
AIN AI20 3-C-N2 s/g DC Matsumoto, Shirato and Miyazaki (1968)
AIN AI-N2-NH3 s/g RF Zyatkevich et al. (1977)
AIN AI-N2 s/g DC Vissokov and Brakalov (1983)
AlN AI-N2-NH3 s/g RF Baba, Shohata and Yonezawa (1984, 1989)
AIN AI-N2 s/g DC Watanabe and Yazaki (1986)
AIN AI-N2-NH3 s/g RF Zyatkevich et al. (1970)
AIN AI-N2 s/g TTP Lu and Pfender (1990)
AIN AI-N2 s/g RF Wehling, Heitz and Hausner (1991)
AIN AI-N2 or NH3 s/g DC Godin et al. (1991); Cao et al. (1994)
AIN AI-NH3 s/g DC Ageorges et al. (1993)
AIN AI-N2 s/g DC Shah and Etemadi (1988)
BN B-N2 s/g DC Zhdanovskii and Lakomskii (1970)
NbN NbFs-N 2 gig MW Troitskii et al. (1994)
Si3N 4 Si-NH3 s/g DC Chang, Kong and Pfender (1989); Chang (1986)
Si3N 4 SiClc NH 3 l/g RF Zhu and Yan (1985)
Si3N 4 Si-N2 s/g RF Humbert, Morvan and Amouroux (1989)
Si3N 4 Si-N2 s/g DC Harvey and Bratton (1980)
Si3N 4 Si02-H2-N 2 s/g DC Harvey and Bratton (1980)
Si3N 4 SiHcNH3 gig RF Schulz, Kandziora and Hausner (1989); Wehling,
Heitz and Hausner (1991)
Si3N 4 Si-Nz-NH3 s/g DC Pavlovic et al. (1993)
Si3N 4 SiClc NH3 l/g RF Schulz, Kandziora and Hausner (1989); Wehling,
Heitz and Hausner (1991)
Si3N 4 Si-N2 s/g RF Schulz, Kandziora and Hausner (1989); Wehling,
Heitz and Hausner (1991)
Si3N 4 SiClc NH3 l/g DC Kubo, Futaki and Shiraishi (1989)
Si3N 4 SiClc NH 3 l/g CCP Schulz et al. (1991)
Si3N 4 SiClc NH 3 l/g RF Szepyolgyi and Toth (1991); Doerfl et al. (1993);
Szepyolgyi et al. (1994)
Si3N 4 SiHcNH3 gig RF Vogt et al. (1984, 1985); Vogt, Phillips and Taylor
(1987); Schulz and Hausner (1992)
Si3N 4 SiCl4 -NH3-N 2 gig DC Jennett, Harmsworth and Jones (1994)
Si3N 4 Various gig RF Mach et al. (1994)
Si3N 4 SiC4-NHrAr-H2 gig RF Soucy, Jurewicz and Boulos (1995)
TaN TaN-N2 s/g DC Matsumoto, Konuma and Kanzaki (1979)
TiN Ti-N2 s/g RF Humbert, Morvan and Amouroux (1989)
TiN Ti-N2 s/g DC Zhdanovskii and Lakomskii (1970)
TiN TiCI4-H2-N 2 l/g MW Troitskii et al. (1983)
TiN Ti-N2 s/g RF Yoshida et al. (1979)
TiBxN y TiClc BClr H 2-N2 l/g MW Troitskii, Grebtsov and Aivzov (1974)
TiCxNy TiClc H 2-N2-CH4 l/g MW Troitskii et al. (1983)
TiCxN 1 _ x TiCl4 -CHc N 2-H 2 l/g DC Zeng et al. (1989)
TixVyN TiClc VClc H 2-N2 l/g MW Troitskii et al. (1983)
VN VClc H 2-N 2 l/g MW Troitskii et al. (1983)
ZrN Zr-N 2 s/g DC Matsumoto (1968b)
Nitrides Various-Ar, N2 s/g DC Umemoto et al. (1994)
as = solid; I = liquid; g = gas.
hTTP = triple torch plasma; RF = radio frequency; DC = direct current; MW = microwave; CCP = capacitively coupled
plasma.

Saiki et al. (1988) synthesized AlN by using
aluminum powder in combination with NH3
and/ or H2 as reactants in a combined triple
torch RF plasma reactor (Figure 14.4). Particle
size distributions of the product ranged from
100 to 300 nm. Smaller particle sizes (30 nm)
have also been produced in an RF plasma
reactor as reported by Wehling, Heitz and
Hausner (1991). They used Al powder and
N2 as reactants.
A somewhat different approach for produ-
cing ultrafine AlN powders has been reported
by Baba, Shohata and Yonezawa (1984). They
used an Ar-N2 RF plasma tail flame for
vaporizing Al from an Al block and injected
NH3 in the vicinity of the metal blocks to
assist nitridation of the vaporizing Al atoms.
They were able to achieve high production
rates of up to 0.1-D.2 kg/h (0.22-D.44Ib /h) of
AlN. Nitridation of the Al vapor was complete
and the product was free from any Al metal
contamination. The specific surface of the
powder was 30-80 m 2/ g and the equivalent
particle size was estimated between 23 and
60 nm. The powder contained 2-5 wt% 0 which
was contained in the starting Al powders. In
subsequent work, Baba, Shohata and Yonezawa
(1989) demonstrated that the plasma produced
an ultrafine AlN powder that was highly
sinterable. Powder compacts could be sintered
to full density at 1873 K (1600 C).
In the previously discussed examples, RF
plasmas served as the processing tool for
producing AlN. In this case, the product is
completely free from electrode contamination,
because no electrodes are in contact with the
plasma. This is an important consideration if
extreme purity of the product is a require-
ment. If some contamination from the elec-
trodes can be tolerated, electric arcs in the
transferred or non-transferred mode and/ or
plasma jets produced by arcs can be employed
for AlN synthesis.
Vissokov and Brakalov (1983), for example,
synthesized ultrafine AlN powders by vapor-
izing Al powders in an Ar-N 2 DC arc. An AlN
powder of 50 nm average size and specific
Powder synthesis 367
surface area of 100 m 2/ g resulted. The prod-
uct, however, contained some unreacted AI.
An AlN powder compact could be sintered
to full density at 1600 K (1327C). Similar
experiments using a high velocity plasma
spray gun have been reported by Watanabe
and Yazaki (1986). They noted that the
product particles were either spherical or
polyhedral.
Transferred arcs with Al as the anode pro-
vide efficient heating and evaporation of AI.
Godin et al. (1991) as well as Shah and Etemadi
(1988) produced a molten bath of Al with
N2 or NH3 as the plasma gas and reactant.
Godin et al. (1991) demonstrated that only
excess NH3 produced stoichiometric AIN
powders with a bimodal size distribution.
The majority of the powder is in a size range
around 0.7/-tm and a minor peak of the distri-
bution around 4/-tm. The powder contained
up to 1.5 wt% O.
An example for AlN synthesis in thermal
plasmas produced by non-transferred arcs is
a triple torch plasma reactor (TTPR) (Lu and
Pfender, 1989, 1990). Plasma jets emanating
from three similar torches form a converging
plasma volume (Figure 14.3) into which
reactants were fed. Aluminum nitride (AIN)
was synthesized with this reactor using 1-
2/-tm Al powder and N2 as a plasma gas.
Powders collected inside a quartz reaction
tube downstream of the plasma plume
revealed a pure white AlN. Powders con-
densed on the reactor chamber wall contained
unreacted ultrafine Al and AlN. Particle size
analysis showed a bimodal distribution with
the mean located at 0.5 and 2/-tm. A significant
portion of the powders was within the larger
size range. The larger particles represent
partially sintered hard aggregates while the
smaller particles revealed dispersible single
crystallites. These results point to the highly
heterogeneous environment of a plasma jet.
The crystallites show predominantly hexago-
nal habits. A scanning electron photomicro-
graph (SEM) of AlN particles synthesized in
this TTP reactor is shown in Figure 14.6.
368 Plasma processes

O.lOOJim
I I

(a) (b)

(e)
Figure 14.6 SEM photomicrographs of AlN powder produced by plasma synthesis: (a) single AlN crystal;
(b) assembly of AlN crystals; (c) partially sintered AlN powder.

Besides hexagonal AlN, a significant temperatures or is stabilized by its nanosize.

amount of cubic AlN was also formed. Cubic Under the high plasma temperature environ-
AlN is a high temperature phase and is ment, it is probable that cubic AlN may
stabilized by fast quenching from high form as the major phase, but subsequently

transform into the hexagonal phase under
prolonged high heat treatment in the quartz
reaction tube. The growth in particle size for
the hexagonal phase is significant since the
temperature in this portion of the quartz
reaction tube is much higher than that 0.15 m
(5.9 in) downstream of the plasma plume.
Scanning electron photomicrographs (SEMs)
of the particles show a size range from 0.1 to
0.4 Jim. The particle size distribution deter-
mined by centrifugal sedimentation of AlN
by mass and by number indicates that the
number distribution is single modal while
the mass distribution is bimodal.
High purity ultra fine powders (UFP) of AlN
have been prepared by the reaction of a
nitrogen plasma with metallic Al in a DC
plasma reactor. The particle size can be con-
trolled by the partial pressure of the reactants,
temperature and reaction rate (Cao et al.,
1994).
Silicon nitride (Si 3 N 4 )
Similar to AIN, Si3N4 is another important
non-oxide ceramic material with great poten-
tial for structural applications. A number of
attempts have been made to synthesize high
purity Si3N4 powders. Electrode contamina-
tion problems can be avoided by using RF
plasmas. Schulz and Hausner (1992) designed
a novel coil arrangement for generating a
rather long and stable RF plasma for the
synthesis of high purity Si3N4 powder. A
schematic of this RF plasma reactor is shown
in Figure 14.7.
Reactive gases NH3 and SiH4 have been
used in combination with N2 as the quench
gas. The chemical reaction proceeds according
to
(14.1 )
The gases and gas flow rates used in this RF
plasma synthesis experiment are shown in
Table 14.2. The reaction chamber (Figure
14.7), consisting of a water-cooled conver-
ging-diverging nozzle, enhances the quench
Powder synthesis 369
A: Sheath Gas
B: Carrier Gas
C: Plasma Gas
D: Cooling Gas
E: Silane
F: Ammonia
G: Quench Gas
F .............
Figure 14.7 Schematic of RF plasma reactor with
extended coil. (Schulz, O. and Hausner, H.,
'Plasma synthesis of silicon nitride powders. 1. RF-
plasma system for the synthesis of ceramic powder:
Ceram. Int., 18, 177, 1992. Reprinted with kind per-
mission from Elsevier Science Ltd, The Boulevard,
Langford Lane, Kidlington OX5 1GB, UK.)
rates. The reactants are injected into the
throat region of the nozzle with velocities
between 10 and 30 ml s (32.8-98.4 ftl s) and
the maximum pressure in the reaction
chamber is approximately 200kPa (rv2atm).
Gas temperatures were measured by focusing
an optical pyrometer on the end of an alu-
mina tube which was placed in the center of
the flow immediately below the exit of the
reactor. Temperature varied in the range
773-1773K (500-1500C). Temperatures in
the throat of the nozzle were estimated to
be around 2273 K (2000C). A comparison
of characteristics of the Si3N4 powders
produced in this reactor with commercially
available powders (Starck) are shown in
Table 14.3.
Silicon nitride (Si3 N 4) powders produced
by the plasma route are typically ultrafine
370 Plasma processes
Table 14.2 Gas flow rates used in RF plasma syn- As indicated in Table 14.1, the RF plasma
thesis of Si3N4 synthesis route to Si3N4 has attracted con-
siderable interest. This is believed to be
Gas Function Flow rate
mainly due to the potential of producing
(l/min (m 3 /h
high purity powders with this approach.
Ar Sheath gas 10-50 (0.6-3) However, experiments using arcs or plasma
Ar Carrier gas 1-3 (0.06-0.18) jets produced by arcs have also been reported
Ar Plasma gas 3-15 (0.18-0.9) in the literature. Only one example will be
Air Cooling gas 1 (0.06) discussed in the following.
N2 Quench gas 15-150 (0.9-9) Chang, Kong and Pfender (1989) produced
NH3 Ammonia reactant 3-30 (0.18-1.8)
SiH4 Silane reactant 3-30 (0.18-1.8) Si3N4 in a convection-stabilized free-burning
arc (FBA) reactor using Si and NH3 as
Source: Schulz, O. and Hausner, H., 'Plasma synthesis of reactants. Ammonia (NH3) was injected
silicon nitride powders. 1. RF-plasma system for the both upstream into the arc and also down-
synthesis of ceramic powders: Ceram. Int., 18, 177,
1992. Reprinted with kind permission from Elsevier stream into the tail flame to assist the con-
Science Ltd, The Boulevard, Langford Lane, Kidlington version of Si to the nitride. The nitride yield
OX51GB, UK.) was low when only the upstream or the
downstream NH3 source was used for nitri-
and amorphous, and contain small amounts of dation. The yield was considerably higher
the (3 crystalline phase. The nitrogen content is when both NH3 sources were used in the
substantially below the theoretical value of reaction. The powders consisted of a variety
40%. This is probably due to the presence of of morphologies which included whiskers,
unreacted silicon (SO. The other impurities nodular fibers, prisms, matte, dendrites,
are strongly related to the purity of the platelets and needles. These particles were
starting materials. The relatively high oxygen found in different parts of the reactor. Their
contamination stems from the oxygen content sizes varied between 20 nm and 2 {Lm. A
in the sheath, carrier and plasma gas (argon) summary diagram (Chang, Kong and Pfen-
or from the quench gas (nitrogen). The der, 1989) of the Si3N4 particle morphology
powder size increases significantly by heat found in the FBA reactor is shown in
treating it for 2 h in nitrogen at 1573 K Figure 14.8. In general, most of the particles
(1300C) (Table 14.4). synthesized were aggregates with particle
Increases in the nitrogen content in the heat- sizes ranging from 50 to 150 nm. The statisti-
treated powder could be due to the conversion cal mean of the particle size was around
of Si particles to the nitride. 80nm.

Table 14.3 Characteristics of Si3N4 powders

Powder Particle Surface Crystallinity (3-phase Nitrogen Oxygen Carbon Metallic Tap
size area (%) content content content content impurities density
(t-t m) (m 2 /g) (%) (%) (%) (%) (ppm) (% th.dJ

Plasma Si3N4 0.1-0.4 40-80 0-30 10-60 30-36 0.5-5.0 0.05-0.2 50-500 2-6
Starck Si3N4 0.8 20 100 5 38 2.0 0.15 750 21
(LC12)
% th.d.: percent of theoretical density.
Source: Schulz, O. and Hausner, H., 'Plasma synthesis of silicon nitride powders. 1. RF-plasma system for the synthesis
of ceramic powders: Ceram. Int., 18, 177, 1992. Reprinted with kind permission from Elsevier Science Ltd, The
Boulevard, Langford Lane, Kidlington OX51GB, UK.
 Powder synthesis 371
Table 14.4 Heat treatment of Si3N4 powders

Powder Particle Specific fJ-phase Nitrogen Oxygen Carbon Metallic Tap

sIze surface content content content content impurities density
(p,m) (m 2 /g) (%) (%) (%) (%) (ppm) (% th.dJ

As prepared 0.22 64 30 35 2.10 0.11 106 4.2

N2 (2h, 1573K 0.60 32 13 37 3.60 0.02 78 6.6
(1300C))

% th.d.: percent of theoretical density.

Source: Schulz, O. and Hausner, H., 'Plasma synthesis of silicon nitride powders. 1. RF-plasma system for the synthesis
of ceramic powders: Ceram. Int., 18, 177, 1992. Reprinted with kind permission from Elsevier Science Ltd, The
Boulevard, Langford Lane, Kidlington OX51GB, UK.

Other nitrides thermal plasma reactors (Table 14.1). Among

these nitrides, TiN has been of particular
Besides AlN and Si3 N 4 , there are other interest. Yoshida et al. (1979), for example, pro-
nitrides which have been synthesized in duced ultrafine TiN powders with a statistical

ex Dendrite ex+~ Whisker

ex+~ Platelet
@=2" \ /
/~

/f ex+~ Needle Bundle
@)=500A-,~k
,,
<X+~ Needle
"
\~~~~

\
\
<;/
~ Prism

Figure 14.8 Summary diagram of Si3N4 particle morphologies produced in a free-burning arc plasma
reactor.
372 Plasma processes

Table 14.5 Plasma-produced carbide powders

Compound Reactants Phast!' Plasmi Reference

SiC Si-CH 4 slg TTP-RF Saiki et al. (1988); Guo, Gitzhofer and Boulos (1995)
SiC SiH4-CH 4 gig RF Vogt et al. (1984, 1985); Vogt, Phillips and Taylor
(1987)
SiC SiC14-C 2 H 4 gig RF Kijima (1993)
SiC SiCl4-H 2 -organic gig DC Baumgartner and Rossing (1987); Becker et al.
(1987); Edd (1987)
SiC Si-CHc H 2 slg DC Inoue, Nariki and Tanaka (1989)
SiC SiC bulk-H2 -He slg DC Nariki, Inoue and Tanaka (1990)
SiC Si02 -CHc H 2 slg RF Asakami, Hokazono and Kato (1988)
SiC SiCl4- CH c H 2 l/g DC Chase (1974)
SiC SiClc CH4 gig RF-DC Eguchi and Yoshida (1993)
SiC CH3 SiCl3-H 2 l/g DC Chase (1974)
SiC SiH4-B2 H 6-CH 4 gig DC Kondo and Saiki (1987); Saiki and Kondo (1989)
SiC SiH4-C 2H 4 gig RF Kijima, Noguchi and Konishi (1989)
SiC SiH4-CH 4 gig RF-RF Kameyama et al. (1990)
SiC Si02-C sis DC Naden and Bagha (1990)
SiC CH 3SiCl3-H2 l/g RF Goldfarb and Woodroffe (1989)
SiC SiCl4- CH c H2 l/g DC-RF Yoshida et al. (1983); Murakami, Yoshida and
Akashi (1988); Murakami and Yoshida (1989)
SiC Si03-CH 4 slg DC Kong, Huang and Pfender (1983); Kong (1985);
Kong et al. (1985)
SiC SiO-CH4-H2 slg DC Kong, Huang and Pfender (1983); Kong (1985);
Kong et al. (1985); Kong, Huang and Pfender
(1986); Kong and Pfender (1987a, b)
SiC SiCl4-CH3 SiCI3 -CH 4 gig DC Zhu et al. (1993)
SiC-Si3 N4 CH 3 SiCl3 -NH r H 2 gig RF Seon and Rhee (1993)
SiC Rice hull slg RF Singh et al. (1993); Stachowicz et al. (1993)
TiC Iimenite-CH 4 slg Taylor et al. (1995)
W 2c, WC, W03 -C-H 2 sla DC Mosieev et al. (1982)
WC 1 _ x
WC 1 _ x W03 -CH 4 slg DC Kong et al. (1983)
WC CH c WCI6-H2 gig DC Chase (1974)
wc, W 2C, W-C, W-CH4, slg DC Ronsheim et al. (1981)
WC 1 _ x WCI6-CH 4
wc, w 2c, W-C H C H 2' slg RF-RF Sakanaka et al. (1989)
WC 1 _ x W03 -CH 4-H 2
WxHfyC z WOr Hf02-C sis DC Matsumoto et al. (1977)
WxTiyCz WO r Ti0 2-C sis DC Matsumoto et al. (1977)
WxZryC z W03 - Zr02-C sis DC Matsumoto et al. (1977)
ZrC O.7 Zr(OR)4-C 2 l/g TIP Lu et al. (1990)
ZrC x ZrSi04 -C-H2 slg DC Matsumoto and Miyazaki (1973)
B4C BCl3 -CH4-H2 gig RF MacKinnon and Reuben (1975); MacKinnon,
Hamblyn and Reuben (1977)
B4C B2 O r CH4 slg DC Taylor et al. (1994)
B4C CH4-BCl 3 gig DC Chase (1974)
MoC 1 _ x MoOrC sis DC Matsumoto and Yaguchi (1977)
MoxHfyC z MoOrHf-C sis DC Matsumoto and Yaguchi (1977)
NbC 1 _ x Nb2 Os-C sis DC Matsumoto and Saito (1975)
NbC Nb 2Os-C sis DC Matsumoto and Saito (1974)
TaC1 _ x Ta20s-C sis DC Matsumoto and Saito (1975)
TiC TiClc CH4-H 2 l/g RF Chase (1974)
TiC Ti02-CH 4 slg DC Taylor, Pirzada and McColm (1993)
 Powder synthesis 373
Table 14.5 Continued

Compound Reactants Phasr! Plasmab Reference

TiC Ti-C 2 H c -CH4 s/g RF McFeaters et al. (1994)

UC-UC 2 C-U0 2 sis DC Druzhinin et al. (1977)
TiC, SiC, B4 C Various s/g DC Taylor, Bhaduri and Pirzada (1993)
Ti02 , Si02 , B2 0 3 -CH4 s/g DC Taylor and Pirzada (1993a,b)
Wc, SiC, TiC, TaC Various s/g MW Salsman (1993)

as = solid; I = liquid; g = gas. . .

bTIP = triple torch plasma; RF = radio frequency; DC = dIrect current; MW = mIcrowave.

mean particle size of around 10 nm by passing Silicon carbide (SiC)

Ti powders 25 jLm) through an Ar-N 2 RF
Silicon carbide is a hard material with high
plasma. The conversion of Ti to TiN was
thermal shock resistance, high mechanical
close to 100%. The color of the powder was
strength and high resistance to wear and
black, which was attributed to particle sizes
chemical attack. It is used in powder form
ranging from 5 to 150 nm. Most of the crystal-
or as a coating. Plasma reactors based on
lites were single crystals and clearly showed
DC, RF or combinations of DC with RF
cubic habits. The chemical compositions and
(hybrid reactors) have been successfully
lattice parameters of the powder cha~ged
employed for such processes (Table 14.5). A
with Nz-Ti ratios. The powder contamed
few examples of such synthesis processes
small amounts of oxygen which probably
will be discussed in the following.
originated from the Ti powders.
A DC plasma reactor with hydrogen as
Studies about the formation of metal and
plasma gas and reductant was used in the
metal-nitride composite ultrafine powder,
production of SiC (Becker et al., 1987; Edd,
including AI, Fe, Cr, Cu, Ni, Si, Ti and premixed
1987). In this reaction, SiCl4 was the feed
elemental powders of AI-Cu, AI-Ni, Ni-Ti, AI-
stock for Si, and pure hydrocarbons or halo-
Ti and Si-Ti using a plasma jet of Ar-N2 as
genated hydrocarbons provided ca:bon for
working gas indicate that with some o.f ~he
the reaction. The reaction was delIberately
pure metal powders as precursors, no mtnde
controlled to incorporate a small amount of
powders formed (Umemoto et al., 1994).
free carbon to be used as a sintering aid. A
Superconducting niobium nitride has been
small amount of BCl3 was also added to the
produced by reduction or nitr~dat~.on of
reaction to provide the necessary boron (B)
NbFs in a microwave plasma (TrOltskll et al.,
as an additional sintering aid. These powders
1994).
have an average f)-SiC particle size of 0.5 jLm
A few attempts have been reported using
(Figure 14.9) and are highly sinterable
plasma reactors to synthesize BN, TaN, VN
(Baumgartner and Rossing, 1987). Powders
and ZrN and some more complex nitrides
with <0.3 wt% B can be pressureless sintered
such as TiBxNy . The cubic phase of !~N is of
to 98% of the theoretical density at 2373 K
interest as a superconductor (a transItIon tem-
(2100C).
perature of Tc = 8.3K (-264.7C.
In a similar experiment, boron-doped f)-SiC
was synthesized using a two-reaction-zone
CARBIDES
DC plasma reactor (Saiki and Kondo, 1989).
Recent efforts in the plasma synthesis of car- Silane (SiH4 ) and diborane were pyrolyzed
bide powders are summarized in Table 14.5. in an upper reaction chamber to produce
374 Plasma processes

Figure 14.9 TEM photomicrograph of plasma-produced SiC powder. {Baumgartner, H.R. and Rossing,
B.R., 'Pressureless sintering and properties of plasma synthesized SiC powders,' in Ceramic Transactions,
2, Silicon Carbide '87 (eds J.D. Cawley and c.E. Semler), 1987. Reproduced by permission of the American
Ceramic Society, Westerville, OH.)

fused silicon particles. The silicon particles
were carbonized by CH4 in a second reaction
zone. The temperature differential in the
two reaction zones varied from 473 to 773 K
(200-500C). The particles had a size dis-
tribution from 0.1 to 0.7/-Lm with a surface
area of 9.6m2/g. The product contained
0.8 wt% Band 0.6 wt% free carbon as the
in-situ-generated sintering aids for the
carbide.
A different approach using an Si bulk
anode and CH4 -H2 reactive gases in an Ar
arc (Inoue, Nariki and Tanaka, 1989) has
been proposed for the synthesis of SiC. The
cathode was directed at an angle of 45 to
the surface of the Si bulk anode. A strong Si
vapor jet emanated from the surface of the
molten anode and was carbonized by the
CH 4 to SiC. The ultrafine powders consisted
of a- and jJ-SiC with Si and C impurities.
The ultrafine powders produced were nearly
spherical with a particle size of 20-40 nm.
Hexagon-shaped particles with sizes from
100-200/-Lm were also found.
In a related experiment, ultrafine jJ-SiC was
formed under different plasma gas composi-
tions (Nariki, Inoue and Tanaka, 1990) by arc
evaporation of a-SiC containing 10 wt% Si.
The powder production rate was 3-5 mg/
s . kW when pure Ar was the plasma gas. It
decreased to about half of that value when
50vol% of H2 or He was added to the Ar

plasma gas. However, the mean particle size
of 12 nm was narrower with either Ar-H2 or
Ar-He as plasma gas. When pure Ar was
used, the mean particle size was about 25 nm
and the size distribution was much wider.
The smaller particles produced with the
mixed plasmas revealed much higher thermal
conductivities. This seems to indicate that
faster cooling suppressed the growth of SiC
particles.
Using a DC plasma jet, Kong, Huang and
Pfender (1983, 1986), Kong (1985), Kong et al.
(1985) and Kong and Pfender (1987a,b)
synthesized jJ-SiC according to the reactions
Si02 + 3CH4 ---+ SiC + 2CO + 6H2 (14.2)
SiO + 2CH4 ---+ SiC + CO + 4H2 (14.3)
Figure 14.10 Silicon carbide single crystals synthesized in a plasma jet reactor. (Scale bars in
angstroms, 1 A= 0.1 nm.)
Powder synthesis 375
The reactions involving Si02 (-44 Mm) and
CH4 showed a very poor carbide yield
20%). In contrast, the reaction between
SiO and CH4 produced a very high yield of
carbide. The SiO powder, <1 Mm, was
prepared by hydrogen reduction of Si02 in a
graphite tube confined DC plasma jet. Syn-
thesis of SiC revealed spherical and faceted
particles throughout the experiments. The par-
ticle size showed a bimodal distribution with
the spherical particles in the 15-40 nm range
being the major component. Well faceted
platelets in the 0.1-0.2 Mm range were the
minor component (Figure 14.10). Several con-
clusions were drawn from the results. High
temperature gas phase reactions occurred
between 2300 and 4000 K (2027 and 3727 C).
376 Plasma processes
Two important gas phase intermediates, SiC2
and Si2C, were involved in SiC(s) formation
by a chemical vapor deposition process. The
experimental yield, 97.3%, of SiC at a C~
SiO mole ratio of 2.32 was in good agreement
with thermodynamic equilibrium calcula-
tions. Hydrogen (H2) was essential to control
the free carbon precipitation. Homogeneous
nucleation was the predominant process for
the formation of ultrafine powders, while het-
erogeneous processes were involved in the for-
mation of larger single crystal platelets. A
convective stabilized transferred arc was also
used for the synthesis of j3-SiC through the
same SiO and CH4 reaction.
The feasibility of generating ultrafine, pure
ceramic carbides (TiC, SiC, B4C) has been
demonstrated using a non-transferred arc
thermal plasma tubular reactor (Taylor,
Bhaduri and Pirzada, 1993; Taylor and
Pirzada, 1993a,b).
The synthesis of SiC powders has also been
carried out in RF plasma reactors (Vogt et al.,
1984, 1985; Vogt, Philips and Taylor, 1987;
Asakami, Hokagano and Kato, 1988; Goldfarb
and Woodroffe, 1989; Kijima, 1993) using
SiH4 and CH4 as reactants. Goldfarb and
Woodroffe (989) pyrolyzed organometallic
silicon (CH3SiCl3) in an Ar-H2 RF plasma jet
and deposited a j3-SiC coating on a substrate
at atmospheric pressure. A rapid deposition
rate up to 10 p,m/min has been observed.
The high rate resulted from efficient material
transport and was limited by surface reaction
rates. Submicron particle deposition and
heterogeneous nucleation on the surface
were two probable mechanisms for the
coating formation.
Silicon carbide-silicon nitride (SiC-Si3N 4)
composite powders have been synthesized
by introducing trichloromethylsilane, ammo-
nia and hydrogen into a high temperature RF
thermal argon plasma. When the mole ratio of
ammonia to trichloromethylsilane was
between 1 and 2, SiC-Si3N 4 composite pow-
ders were formed, and when it exceeded 4
only Si3N4 was formed (Seon and Rhee, 1993).
A combination of DC with RF (hybrid)
thermal plasma reactors has been utilized for
powder synthesis as well as for deposition of
SiC coatings. Murakami, Yoshida and Akashi
(988) and Murakami and Yoshida (989)
deposited thick j3-SiC layers at a rate of
500 p,m/h on a graphite substrate from SiCl4
and CH4 in an Ar-H2 plasma under soft
vacuum (2.7 x 104 Pa; 203 torr). The process
was carried out with a flow rate of 1.5 g/min
(0.2lb/h) SiCl4 and 0.31/min (0.64scfh) CH4
and deposition temperatures of 1273-1373 K
0000-1100C). The density of the deposited
coating was measured at 3200 kg/m3 (3.2 g/
cm3) which was nearly equal to the theoretical
density. The coating was polycrystalline
for short deposition time, but showed a (200)
epitaxy for long deposition time.
A ring-slit arrangement has been used for
the preparation of SiC powders in a hybrid
plasma system. This ring-slit arrangement
enables the control of the SiC composition as
well as the particle size distribution (Eguchi
and Yoshida, 1993).
A somewhat unusual DC triple torch-RF
combined plasma reactor (Saiki et al., 1988)
shown in Figure 14.4 was used for the syn-
thesis of SiC. In this synthesis, Si powders
(44-100 p,m) doped with 1.43% B were injected
into the converging part of the DC plasma jets.
Silicon was vaporized in the combined plasma
and nucleated into fine liquid droplets at the
lower temperature region of the combined
plasma. Methane (CH4) was injected into the
tail flame beneath the RF coil and carbonized
the Si droplets to spherical j3-SiC. The product
revealed a size range from 0.3 to 0.5 p,m.
Vapor phase reactions using volatile Si
reactants for the synthesis of ultrafine SiC
powder had been assessed by Zhu et al.
(993). For production of SiC powder by
vapor phase reactions, the volatile compounds
assessed included SiH4, (CH3)4Si, CH3SiCl3
and SiC4.
SiH4 + CH4 --t SiC + 4H2
1573-1673K (1300-1400C) (14.4)
 Powder synthesis 377
(CH3)4Si --+ SiC + 3CH4 15r---------------------------,
1173-1673 K (900-1400C) (14.5)
CH3SiCl3 --+ SiC + 3HCl
>2273 K (>2000C) (14.6)
SiC4 + CH4 --+ SiC + 4HCl
>2273 K (>2000 0c) (14.7)
The reaction temperature indicates that
the first two reactions can be performed in a
resistive furnace to form the SiC. However,
2.5 '--__...J...._ _---<.......__..L...-_ _---L..._ _ _ _
the last two are high temperature reactions
~~.....J

0.5 0.7 0.9 1.1

which are ideal candidates for plasma pro-
cesses. A plot of the equilibrium constants,
log Kp, for the above reactions as a function
of reaction temperature is shown in Figure
14.11. The first two reactions have large
log Kp at low temperatures and the log Kp
values decrease as the temperature increases.
At high temperatures, the forward rate for
these reactions becomes less likely. In contrast,
the last two reactions, with CH3SiCl3 and SiC4
as reactants, require high temperatures
>2273 K (>2000C) to form SiC. It is obvious
from the plot of log Kp that these two reactions
are favored at high temperatures.
A DC plasma reactor was used to synthesize
SiC following the last two gas phase reactions.
A mixture of Ar and H2 was used as the
plasma gas. The results of plasma synthesis
experiments using CH3SiCl3 and SiC4 as
reactants are shown in Tables 14.6 and 14.7,
respectively.
103 fT, (Kl)
Figure 14.11 Temperature dependence of the equi-
librium constants Kp for ,a-SiC formation. (Zhu,
C.W., Zhao, G.Y., Revankar, V. and Hlavacek, V.,
'Synthesis of ultrafine SiC powders in a dc plasma
reactor,' J. Mat. Sei., 28, 659, 1993. Reproduced by
permission of Chapman & Hall, London, UK.)
In run number 1 (Table 14.6), the reaction
should reach stoichiometry for SiC without
requiring excess carbon from CH4. However,
the powder revealed a yellow-gray color
which indicates the presence of free silicon
in the product. This phenomenon is very
common in plasmas because hydrocarbons
will be formed in the reaction, thus depleting
the carbon source for SiC formation. The
carbon source is further depleted when hydro-
gen (H2) is used to control the precipitation of
free carbon in a plasma reaction. For higher

Table 14.6 SiC synthesis using CH3 SiCl3

Run Ar H2 kW CH4 /CH3 SiCI3 Color of

(i/min (m 3 /h (i/min (m 3 /h powder

1 1.42 (23.7) 0.031 (0.52) 9 0.00 Yellow-gray

2 1.42 (23.7) 0.031 (0.52) 9 0.05 Gray
3 1.42 (23.7) 0.031 (0.52) 9 0.11 Dark gray
4 1.42 (23.7) 0.031 (0.52) 9 0.17 Light black
5 1.42 (23.7) 0.031 (0.52) 9 0.21 Black
6 1.42 (23.7) 0.031 (0.52) 9 0.32 Dark black
7 1.42 (23.7) 0.034 (0.57) 11 0.05 Black

Source: Zhu, C.W., Zhao, G.Y., Revankar, V. and Hlavacek, V., 'Synthesis of ultrafine SiC powders in a dc plasma
reactor,' J. Mat. Sci., 28, 659, 1993. Reproduced by permission of Chapman & Hall, London, UK.
378 Plasma processes
Table 14.7 SiC synthesis using SiCl4

Run Ar H2 kW CH4 /SiCI 4 Color of

(lfmin (m 3 /h)) (l/min (m 3 /h)) powder

8 1.42 (23.7) 0.031 (0.52) 9 0.69 Yellow

9 1.42 (23.7) 0.031 (0.52) 9 0.93 Yellow-gray
10 1.42 (23.7) 0.031 (0.52) 9 1.08 Gray
11 1.42 (23.7) 0.031 (0.52) 9 1.15 Light black
12 1.42 (23.7) 0.031 (0.52) 9 1.39 Black
13 1.42 (23.7) 0.031 (0.52) 9 1.60 Dark black
14 1.42 (23.7) 0.034 (0.57) 11 1.15 Black
Source: Zhu, C.W., Zhao, G.Y., Revankar, V. and Hlavacek, V., 'Synthesis of ultrafine SiC powders in a dc plasma
reactor: J. Mat. Sci., 28, 659, 1993. Reproduced by permission of Chapman & Hall, London, UK.

CHc CH3 SiCl3 ratios (runs 2-7 in Table 14.6),
the color of the powder changed from gray to
black. Gray powder (runs 2 and 3) represents a
relatively pure SiC with little free carbon con-
tamination. Black powders indicate excess
amounts of free carbon formed in the reaction.
The same trend was observed with the CHc
SiCl4 reaction (Table 14.7). When the reactants
are sub-stoichiometric, the color of the powder
appears yellow to yellow-gray (runs 8 and 9).
The color of the powder changes from gray
to black when different levels of excess CH4
are used. X-ray diffraction of the powders
obtained from these two reactions showed
predominantly diamond cubic jJ-SiC forma-
tion with a trace amount of hexagonal a-SiC.
The results of powder characterization are
shown in Table 14.8.
Rice hulls, an agricultural waste product,
have been investigated as a starting material
for SiC synthesis by Singh et al. (1993) and
by Stachowicz et al. (1993). Rice hulls consist
of silica in hydrated amorphous form and
cellulose, which yield carbon when thermally
decomposed. The relative abundance of very
high surface area silica in close proximity to
active carbon makes rice hulls amenable for
SiC formation during pyrolysis processes.
The overall reaction for SiC formation from
rice hulls can be described by carbothermal
reduction of silica:
Si02 (amorphous) + 3C (amorphous)
----'> SiC+2CO (14.8)
Raw rice hull was ground to about 105 J-Lm and
heated at 820 K (547C) for 2 h in ambient
nitrogen. The resultant product was in the
form of a fine powder. The chemical composi-
tion of the starting powder was quantitatively
determined by ICP emission spectroscopy
(Table 14.9).

Table 14.8 Characterization of the ,B-SiC

Reaction Average particle diameter (nm)" Specific surface Excess Excess

no. area, BET silicon carbon
TEM BET X-ray (m 2 /g) content content

3 (Run 2) 48 35 32 42.0 Very small Very small

4 (Run 10) 38 30 28 45.8 Very small Very small
a TEM = transmission electron microscopy; BET = Brunauer-Emmett-Teller analysis.
Source: Zhu, C.W., Zhao, G.Y., Revankar, V. and Hlavacek, V., 'Synthesis of ultrafine SiC powders in a dc plasma
reactor: J. Mat. Sci., 28, 659, 1993. Reproduced by permission of Chapman & Hall, London, UK.
 Powder synthesis 379
Table 14.9 Chemical composition of the the major planes {lll}, {220} and {3ll}
starting rice hulls also show signs of shifting in the 2(}
positions. The broadening and shifting of x-
Oxide Weight % Mole % ray diffraction peaks indicate the presence
Si02 49.0 0.817 of lattice strain. Induced lattice strain in
C 47.0 3.917 particles exposed to high quench rates is
K 20 0.95 0.010 frequently observed. Formation of a small
Al20 3 0.93 0.009 amount of hexagonal a-SiC was also evident
MgO 0.62 0.015 in the diffraction pattern. The x-ray diffrac-
Na20 0.16 0.003
tion traces of the plasma produced powder
CaO 0.96 0.017
MnO 0.10 0.001 heat treated at 973 K (700C) in air to
FeO 0.36 0.005 remove excess carbon are shown in Figure
14.12(b). The peaks show considerable sharp-
ening which means there is substantial grain
Silicon carbide synthesis was carried out in growth and lattice strain relaxation during
a 20kW, 3MHz RF plasma reactor. Argon heating of the powder. Scanning (SEM) and
was used as both the plasma generating transmission (TEM) electron photomicro-
and the powder carrier gas. The mole ratio graphs (Figures 14.13(a) and (b (Stachowicz
of C/Si02 = 4.8 for the calcined rice hulls is et al., 1993), show particles in the size range
above the stoichiometric amount of C needed from 10 to 20 nm. Selected area electron
for reaction. This ratio indicates that there diffraction showed broad diffused rings, indi-
would be excess free C remaining from the cating the ultrafine nature of the particles.
reaction and all the Si02 should be converted The results of infrared Fourier transform
to SiC. X-ray diffraction traces (Figure (FTIR) analysis of the starting rice hulls, of
14.12(a clearly show the formation of cubic treated and untreated SiC and reference SiC
{3-SiC in the product. The x-ray diffraction are shown in Figure 14.14. The starting rice
peaks show considerable broadening, indi- hulls show a strong silica absorption peak at
cating ultrafine particles. Besides broadening, rv 11 00 cm -1. All other traces showed the

(j)
a-SiC
~
c:
=> b
~
I!! !3-SiC !3-SiC !3-SiC
:e
~
~

-
II) !3-SiC
c:
CD a

20 40 60 80 100 120 140

28
Figure 14.12 X-ray diffraction diagrams of SiC produced from rice hulls: (a) before heat treating; (b) after
heat treating. (Stachowicz, L., Singh, S.K., Pfender, E. and Girshick, S.L., 'Synthesis of ultrafine SiC
powders from rice hulls (husks): a plasma process,' Plasma Chern. Plasma Process., 13(3), 447, 1993.
Reproduced by permission of Plenum Publishing Corporation, New York, NY.)
380 Plasma processes

Figure 14.13 (a) SEM and (b) TEM photomicrographs of SiC produced from rice hulls. The arrows indicate
single-crystal platelets. (Stachowicz, L., Singh, S.K., Pfender, E. and Girshick, S.L., 'Synthesis of ultrafine
SiC powders from rice hulls (husks); a plasma process,' Plasma Chern. Plasma Process., 13(3),447, 1993.
Reproduced by permission of Plenum Publishing Corporation, New York, NY.)
 Powder synthesis 381

Rice hull treated in N2

(J)
o
C
<tS
:::
E SiC after plasma treatment,
~ oxidation, etching
~
f-

SiC - standard

4000 3000 2000 1000

Wavenumber (cm- 1)

Figure 14.14 FTIR analysis of rice hulls after various treatments compared to the SiC-standard.

strong Si-C vibration at ",850 em -1. In the as-
produced SiC, there is a distinct strong
absorption peak at ",1000cm- I and a weak
shoulder at 1100 em-I. While the latter is asso-
ciated with unreacted Si02 the former is asso-
ciated with silicon sub oxides, SiO x . It is well
known that SiO and other SiO x phases can
be formed during plasma reduction and
rapid quenching.
Tungsten carbide (WC)
As indicated in Table 14.5, plasma synthesis of
various tungsten carbides, including tungsten
carbide solid solutions, attracted some inter-
est, but by far less than SiC. Only a few
examples of such processes will be discussed.
Kong et al. (1983) synthesized (J-WC I - x in a
graphite-tube-confined plasma jet by injecting
a-WC or W03 with CH4 The maximum
conversion of a-WC into (J-WC I - x reached
52%, whereas conversion in excess of 98%
was observed with W0 3 . X-ray lattice
parameter measurements indicated that the
carbon content for this (J-WC I - x phase was
less than 61 %. The usual carbon composition
for the (J-WC 1 - x solid solution ranges from
61 % to 68%. The temperature of transition of
(J-WC 1 - x to (J-W 2C and a-WC began around
743 K (470C) and accelerated substantially
at 973 K (700C). This new phase had a sharp
lattice parameter change between 973 and
1073 K (700 and 800C) upon annealing in
Ar.
382 Plasma processes
Ultrafine tungsten carbide powder has been
prepared with an RF-RF hybrid plasma torch
system which consisted of an upper lOMHz
torch and a lower 3 MHz torch (Sakanaka
et al., 1989). Tungsten oxide powder was
injected with CH4 in an Ar-H2 plasma at
100kPa (1 atm) and WC, W 2C and f3-WC l - x
were formed. In the CHrW reaction (C/W
ratio: 4-11) W 2 C was the major product, 13-
WC l - x was the secondary phase product,
and about 10% of unreacted W remained.
In the W03-CH4 reaction (W IC = 0.06),
ultrafine cubic f3-WC l - x powder of 5-20nm
diameter was produced with 95% purity.
Cubic ternary tungsten carbide solid solu-
tions (Matsumoto et al., 1977) of the W-Ti x -
C, W-Zrx-C and W-Hfx-C systems were syn-
thesized by graphite reduction of the respec-
tive oxides in an Ar plasma arc reactor.
These cubic ternary carbide solid solutions
were stabilized by substituting Ti, Zr or Hf
atoms for W in the W-C lattice. These carbide
solid solutions are low temperature ceramic
superconductors with the magnitude of Tc
decreasing in the sequence Ti > Zr > Hf.
Other carbides
A non-transferred arc thermal plasma method
has been used for the synthesis of very fine
(0.2-0.4 j.Lm) TiC powders from Ti02 and
CH4 (Taylor, Pirzada and McColm, 1993).
Numerical modeling results of TiC synthesis
Table 14.10 Plasma-produced boride powders
Compound Reactants Phast
TiB2 TiC4-BCl3-H2-CxHy gig
TiB2 TiC4-BCl3-H2-CxHy l/g
TiB2 TiCl4-BCl3-H2-CxHy l/g
Ti~ TiC4-BClrH2-CxHy l/g
MoB2 Mo-B sis
NbB2 Nb 20s-B, Nb-B sis
ZrB2 ZrC4-BCl3-H2 slg
a s = solid; 1= liquid; g = gas.
b DC = direct current.
indicate that the synthesis is governed by
interactions between several parallel pro-
cesses and that there is a delicate balance
between reactant stoichiometry, system pres-
sure, cooling rate, product formation and
soot formation. This balance may be a limiting
feature of ceramic carbide production in ther-
mal plasma reactors (McFeaters et al., 1994).
The feasibility of synthesizing other car-
bides such as zrC, B4 C, MoC l _ XI NbC l - x ,
TaC l _ x , TiC, UC and UC2 in thermal plasmas
has been demonstrated by using DC as well as
RF plasma reactors (Taylor et al., 1994).
Research, however, has not focused on any
one of those carbides and there is no evidence
for a continuing interest in pursuing such
investigations or the development of com-
mercial plasma processes for producing such
carbides at the present time. Finally, it should
be mentioned that a microwave plasma
process has also been proposed for carbide
synthesis. Major advantages of this process
are reduced processing time and reduced
energy requirement compared to conven-
tional processing methods (Salsman, 1993).
BORIDES
A survey of recent plasma synthesis methods
for boride powders is shown in Table 14.10.
Unlike nitrides and carbides, few reports
have been made on the plasma synthesis of
borides.
Plasmd' Reference
DC Becker et al. (1987); Edd (1987)
DC Carson and Holden (1977)
DC Steiger (1981)
DC Baumgartner and Steiger (1984)
DC Matsumoto et al. (1978);
Matsumoto, Konuma and Kanzaki (1979)
DC Matsumoto, Shioiri and Kanzaki (1982)
DC Steiger (1981)

Titanium diboride (TiB 2 )
Among the borides listed in Table 14.10, TiB2
attracted the strongest interest due to its out-
standing properties as an armor material. A
DC plasma reactor was used for the pilot-
plant production of TiB2 (Becker et al., 1987;
Edd, 1987). Hydrogen was used as the
plasma gas and also served as the reductant.
Titanium tetrachloride (TiC4), BCl3 and a
small amount of a chlorinated organic to add
carbon to the product were co-reduced in the
hydrogen plasma to form TiB2. The powder
was easily dispersible and had a mean particle
size of 0.5 11m. An anti-swirl gas was used to
cancel the helical flow of the hot H2 plasma
gas. The resulting gas was a well collimated
gas stream. It could be used to produce
finely divided TiB2 powders without the
product growth on the reactant inlet or the
reactor wall.
Steiger (1981) disclosed the method for pro-
ducing TiB2 using a pure DC H2 plasma
according to the following reaction:
TiCl4 + 2BCl3 + 5H2 -+ TiB2 + 10HCl (14.9)
Titanium tetrachloride (TiC4) and BCh
were used as reactants with an H2-Ar carrier
gas for injection into the plasma. Trichloro-
ethane was co-injected with TiC4 and BCl3
to provide a controlled amount of carbon in
the powder. This carbon serves as a sintering
additive for the product to inhibit grain
growth during densification. The TiB2 had a
specific surface area of 7 m 2/ g and the crystal-
lites were equiaxed hexagonal thin platelets
with diameter-to-thickness ratios of about
1.5:1 to 10:1. Subsequent sintering studies
(Baumgartner and Steiger, 1984) showed
that the TiB2 powder could be pressureless
sintered to >99% of theoretical density at
2273-2473 K (2000-2200 C) within 1 h.
Other borides
Other borides, such as MoB2, NbB 2 and ZrB2
have been synthesized using DC plasma
References 383
reactors in laboratory experiments. No larger
scale studies have been reported.
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synthesis and properties of ultradispersal nio-
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Umemoto, M., Kubosaka, M., Udaka, M., Kawasaki,
K and Okane, I. (1994) Formation of metal nitride
composite ultrafine powders by plasma jet. J. Jpn
Soc. Powder Metal., 41(8), 1006.
Vissokov, G.P. and Brakalov, L.B. (1983) Chemical
preparation of ultrafine AIN by electric arc
plasma. J. Mat. Sci., 18, 2011.
Vogt, G.J., Phillips, D.S. and Taylor, TN. (1987)
Plasma synthesis and characterization of ultra-
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Powder Science (eds G.L. Messing, J.W. McCauley,
KS. Mazdiyasni and RA. Haber), published by
The American Ceramic Society, Inc., Vol. 21,
p.203.
Vogt, G.J., Hollabaugh, CM., Hull, D.E., Newkirk,
L.R and Petrovic, J.J. (1984) Novel RF plasma
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Vogt, G.J., Vigil, RS., Newkirk, L.R and Trkula, M.
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References 387
Wehling, C, Heitz, F. and Hausner, H. (1991)
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Vol. 1, paper 1.4-5.
Yoshida, T., Kawasaki, A., Nakagawa, K. and Akashi,
K. (1979) The synthesis of ultrafine titanium nitride
in an rf plasma. J. Mat. Sci., 14, 1624.
Yoshida, T., Toshiko, T., Hirobumi, N. and Akashi,
K (1983) Characterization of a hybrid plasma
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App. Phys., 54, 640.
Zeng, D., Hu, S., Luo, Q., Zhou, G., Lei, Z. and
Zhang, S. (1989) Preparation of ultrafine
powder of titanium carbonitride using an arc
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national Symposium on Plasma Chemistry (ed. R
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Zhdanovskii, A.A. and Lakomskii, V.1. (1970)
Feasibility of preparation of refractory metal
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Zhu, C.W. and Yan, V.P. (1985) Synthesis of ultra-
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Eindhoven, The Netherlands, Vol. 2, p. 657.
Zhu, CW., Zhao, G.Y., Revankar, V. and Hlavacek,
V. (1993) Synthesis of ultrafine SiC powders in a
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GN., Oleinik, G.5., Pilyankevich, A.N. and
Pokrovskii, D.o. (1970) Product of the reaction
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Zyatkevich, D.P., Grabis, Ya.P., Makarenko, G.N.,
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PART FIVE
LIQUID PHASE SYNTHESIS PROCESSES
The high quality standard a-silicon nitride
(Si3N 4) powder currently in the marketplace
is manufactured by a non-aqueous liquid
phase silicon diimide (Si(NH)2) intermediate
process. Although the synthesis of Si3N4 by a
diimide intermediate process is the primary
focus of Part Five, other processes discussed
include the synthesis of Si3N4 from silazane
and the synthesis of other nitrides, carbides
and borides by liquid phase processes.
OVERALL PROCESS
This process consists of two steps: (1) the
formation of an (Si(NHh) intermediate from
silicon tetrachloride (SiCl4) and ammonia
(NH3) and (2) calcination of the intermediate
to drive off NH3 and form crystalline a-Si3N 4.
There are several variations of this process
which include the use of either gaseous or
liquid NH3 and either gaseous or liquid
SiCl4 (gaseous ammonia-liquid silicon tetra-
chloride route, liquid ammonia-liquid silicon
tetrachloride route, liquid ammonia-organic-
diluted silicon tetrachloride route, and vapor
silicon tetrachloride-liquid ammonia route).
The reaction phases are dictated by the pro-
cess temperature and pressure.
In the commercial process, reaction occurs
at the interface between SiC14, dissolved in a
solvent mixture, and liquid NH 3. Dilution of
the SiCl4 in the solvent mixture moderates
the exothermicity of the reaction and allows
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
better control of the process. Ammonium
chloride (NH4Cl) is typically produced as a
by-product of the reaction. In addition to
liquid phase reaction, other unit operations
involved in the process include washing,
filtration, drying and calcination. Probable
process steps include the recycle of unreacted
SiC14 and NH 3.
SAFETY ISSUES
Safe practices in the scale-up development of
new processes always require special insight
into the chemistry and engineering (AIChE,
1972). Nowhere is this concern more critical
than when one is working with air sensitive,
liquid phase reactants under pressure. For a
given heat of reaction, reactions which have
a liquid phase present will have a likelihood
for a faster heat evolution rate than for the
same reaction with a solid because of the
greater interdiffusivities (at nearly equal con-
centration of components per unit volume as
solids).
Certainly, the intrinsic factors which affect
the ease of process control (discussed in com-
paring diimide processes) also tend to affect
the robustness of the process to fault condi-
tions. A process choice that is not strongly
exothermic is favored for safety. To prevent
reversed flows of liquids, one can sometimes
use check valves. Because the potential
products are solids rather than gases, the
390 Liquid phase synthesis processes
risk of explosions with reversed fluid flows
are lower than, say, for manufacture of nitro-
gen-containing explosives. Reactor rupture
disks are necessary, and, if polymeric, may
require separate gas shrouding to prevent
oxygen contamination into the product.
During thermal decomposition, gases are
evolved inside a refractory ceramic vessel.
Since the downstream line might become
blocked with solids, good practice suggests
use of a cover gas flow for decomposition
with an upstream pressure relief mechanism.
Special concerns are associated with the use
of SiC4. In the case of a leak, water reacts
to form hydrogen chloride (HCn gas, which
dissolves in water to form hydrochloric acid.
Hydrochloric acid, in tum, will diminish (i.e.
dissolve) the structural integrity of stainless
steel piping. Avoidance of moisture condensa-
tion on the vessels containing SiC4 is desired
to restrict the water concentration. Due to its
low viscosity, SiC4 can leak through small
gaps (in fittings) in cases where water would
not. The source of any tarnished areas should
be addressed promptly and leak-checked
using internal pressurization with helium (in
'sniffing detection mode').
Active nitrogen sources are associated with
breathing and blinding hazards. Also, there is
a narrow range of NH 3-air mixtures which
will bum. Even under a pressure gradient,
water and water vapor in air can be drawn
into an NH3 liquid- or vapor-filled volume,
unless a separator (such as a toluene-filled
trap) is present. Hydrazine is a well-estab-
lished propulsion fuel. The manufacturers'
Materials Safety Data Sheet (MSDS) informa-
tion is a starting point which supersedes any
comments here.
Although NH3 is less hazardous than some
room temperature gases (because a freshly
increased concentration from a sudden,
small leak can be sensed and identified at a
fairly low level by most people), good ventila-
tion of the site is needed. The air exchange rate
should be great enough to bring the ambient
level down quickly from vaporization of the
volume of liquid NH3 in use. There is also a
critical level of gaseous NH3 concentration
for which bronchial arrest is immediate.
Even at low concentrations, long term expo-
sure to low levels can give rise to various
sensitizations. With the non-oxide product
demands for low oxide content, the preven-
tion of such small leaks will go hand-in-hand
with routine practices, such as helium leak
testing of the special enclosed O-ring fittings
of the equipment and (gloved-hand) checking
with moist pH paper.
The hazard from blinding from liquid NH3
is perhaps less widely recognized. In opera-
tion under varying temperatures, fittings
which had passed helium leak checks at
uniform temperature can open up. (Helium
leak checking can also be run on equipment
filled with NH3.) Liquid NH3 can jet out of
small openings and travel meters before
vaporizing. Since the NH3 diffuSivity is
greater than that of water, water flushing is
an ineffective first aid (although the only one
available to reduce continuing damage), since
the NH3 outdistances the flushing water. Strict
adherence to chemical goggle use is necessary
for work around the equipment. This practice
must extend to times when no NH3 is
expected to be present, as liquid NH3 can be
entrapped in some ball valves and within
solid residues.
With experience with gas-flow purging and
reliable leak testing, handling NH3 can
become almost water-like. Therefore, continu-
ing caution is especially required, because - in
spite of similarities - the hazards of liquid
NH3 are not 'water-like'.
REFERENCE
AIChE (1972) AIChE Pilot Plant Safety Manual (pre-
pared by the editors of Chern. Eng. Prog.), Amer-
ican Institute of Chemical Engineers, New York.
LIQUID PHASE REACTION PROCESSES
Gary M. Crosbie
INTRODUCTION
Liquid phase processing routes hold consider-
able promise to meet the growing demands for
more reliable advanced non-oxide ceramics.
These routes to new products bring the advan-
tages that are the norm for the present, large
scale chemical process industry (CPl). Indeed,
most of the examples given in a well-known
survey of industrial processes (Lowenheim
and Moran, 1975) describe reactions with a
liquid phase present at the reaction site. Only
a few of these are examples with solids as the
product, rather than another liquid.
In contrast, the presence of liquids in
the bond-forming reactions for non-oxide
materials is comparatively rare in commercial
production. The historical roots for this bias
extend back to the metallurgical roots of the
non-oxide ceramics field and to the traditional
oxide ceramic powder routes such as calcina-
tion of a precursor solid, such as a hydroxide,
carbonate or sulfate. Analogs of such reactions
for non-oxides are described in other chapters
of this book and include solid-solid, gas-solid
and gas-gas pairs as the reactant phases.
Certain liquid phase routes hold the promise
of providing to non-oxide ceramics the histori-
cal advantages of liquid phase processing to
meet the demands of the growing markets for
non-oxide ceramic powders. With adaptations,
the large scale unit operations common to CPI
can be applied to the manufacture of the non-
oxide materials by such routes.
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
15
SCOPE: BOND FORMA nON WITH
LIQUID PRESENT
In this chapter, we limit the discussion to
reactions with a liquid phase present in large
quantity during the formation of the non-
oxide bond. The liquid can be a reactant or
a solvent carrier. Such liquid reactants
include NH3(l), hydrazine, CCl4, HCN, N 2 (l),
supercritical NH3, SiC~, SiBr4, SnCl4, TiC~,
dichloromethylsilane, silazanes and borazines.
Some common solvents or carriers include
benzene, pentane and cyclohexane. To retain
the liquid as a liquid, pressure may be
needed, as in the case of ammonia (NH3) near
room temperature. For the non-oxides, the
demands for anaerobic handling are often
extreme, as the driving force to form oxides
or hydroxides is large.
There are strong materials and chemical
engineering rationales for categorization of
processes by phases present during reaction.
It is understood that, in addition to the
chemical constitution, the microstructure of
materials can strongly affect the mechanical
and other properties of materials. With
ceramic materials there usually is no option
available to melt or dissolve as with metals,
so evidence of the powder microstructure
(and flaws) can be detected in the final
sintered product. With the liquid routes,
there is some definite point at which there is
no prior precursor microstructure. This point
of freedom-from-microstructure is the basis
392 Liquid phase reaction processes
for an expectation that liquid phase process
consistency and robustness can be indepen-
dent of much of the variability of the process
inputs.
RATIONALE FOR SILICON NITRIDE
EMPHASIS
Among liquid phase processes, the emphasis
on Si3N4 is due to its relatively large scale
commercial production (of non-oxide pow-
ders) from liquids. One version, the 'organic-
liquid-diluted silicon tetrachloride-liquid
NH3' route, has an established commercial
capacity over 100 t/yr.
This commercial demand is due to the
desired combination of properties in the
silicon nitride (Si3N 4) ceramics: strength,
toughness and elevated temperature oxi-
dation resistance.
Diimide processes yield powders which are
desired for pressureless sintering to high
densities with minimums of additives and
shrinkage (Cambier et al., 1990). The sub-
micron (but not less than 0.2/-Lm) equiaxed
particles from decomposition of an amor-
phous precursor pack and flow well for high
green density. For sintering, the high a-Si3N4
content provides more stored energy to drive
pressureless sintering (than surface area
alone) and can lead to a high degree of
interlocking of grains (for composite-like
toughness). As the diimide route is a low
temperature synthesis route (rather than a
high temperature one or a refining process),
high purities can be achieved which allow
elevated temperature mechanical properties
(Woetting and Ziegler, 1986) through higher
viscosity grain boundaries.
SILICON NITRIDE POWDER PROCESSES:
IMIDE INTERMEDIATE ROUTES
The reactions to form silicon nitride (Si3 N 4)
via an imide intermediate have two principal
stages, with rinsing in between. First, silicon
tetrachloride (SiCl4) is reacted with NH3
(usually with an NH3 excess) to form the
silicon diimide (Si(NH}z) (Chemical Abstracts
indexes it as silanediimine). The molecular
scale analogy is the substitution of (NH)
groups for bridging oxygens in Si02. After
removal of the by-product ammonium chlor-
ide ammoniate (4NH 4Cl 3NH3) by rinsing,
the diimide is heated under nitrogen (N 2) to
remove hydrogen (H 2) and then crystallize
the Si3N 4.
According to Billy (1959), the reactions are
SiCl4 + 18NH3 ----> ~x +Si(NHh-h
+ 4NH4Cl 3NH3 (15.1)
where the products are the polymeric silicon
diimide and ammonium chloride triammo-
niate. The nitride is formed by decomposition:
Si(NHh ----> + ~ NH3
~ Si3N4
(or + ~N2 + H 2, at higher
temperatures) (15.2)
Related process variants use bromide or
iodide analogs of SiCl4 to gain enhanced
solubility to aid in rinsing, but at the cost of
a more expensive precursor. With large scale
and recycling to remake the precursor, the
alternatives may become more attractive.
PROCESS DESCRIPTIONS
Gaseous ammonia-liquid silicon
tetrachloride routes
At ambient temperature and pressure, SiCl4 is
a liquid and NH3 is a gas. It follows that
probably the earliest synthesis of silicon di-
imide was obtained by bubbling NH3 into
SiCI4. Segal (1989) cites one case with benzene
as the organic diluent as far back as 1830. More
recent development efforts have been pursued
(Mitomo, Tanaka and Tanaka, 1974; Marosi,
1988), but any commercial use is not widely
known.
Reasons for this apparent non-use probably
include the initial by-product (HCl), inability
 Silicon nitride processes: imide intermediate routes
to react to completeness and competition from
gas-gas routes: Because the gaseous NHr
liquid SiCl4 approach does not preserve an
excess of NH 3, corrosive HCl is expected to
form first as a by-product rather than the
NH4Cl-ammoniate. Then, as the reaction pro-
ceeds with the continued formation of solids, a
slurry in SiCl4 thickens, so that the silicon con-
tent likely cannot be reacted to completion.
However, with dilution of the chloride liquid
in an organic solvent (Mazdiyasni and Cooke,
1973), completion is achievable, but carbon
contamination is expected to be tied up with
the imide and chloride solids. Furthermore,
by comparison, the gas-gas processes which
also lack a means to rinse out the by-product
chloride solids leave only the ammonium
chloride (NH 4Cl) with the diimide, rather
than both NH4Cl and an organic. Further-
more, loss of gaseous silicon imidochlorides,
on decomposition with chlorine present, is
expected to lower yield.
Liquid ammonia-liquid silicon
tetrachloride route
By cooling the reaction system below 240 K
(-33 DC) (or operation under pressure), NH3
can be used as a liquid. When maintained in
excess, NH3 prevents formation of the corro-
sive HCl. Also, it keeps a flowable system as
the silicon precursor is reacted to completion
and provides a means to remove the NH4 Cl
by-product.
A schematic liquid ammonia-liquid chlor-
ide reactor design is shown in Figure 15. I.
Following the description given by Morgan
(973), NH3 is loaded and SiCl4 is injected
from above, with N2 gas purging immediately
before and after each injection (to reduce
solids formation at the inlet, which may lead
to clogging). Similar liquid-liquid operation,
but under pressure, was carried out by
Crosbie, Predmesky and Nicholson (990).
Concerns are for uniformity of product due
to 0) the strongly exothermic reaction which
produces strong local heating and (2) the
393
SiCI 4 (liq)
---.J Vent
N2 purge
Figure 15.1 Liquid chlorid~1iquid ammonia
reactor.
apparent difficulty in achieving chloride
removal, once entrapped inside previously
formed SiCl4 droplets. The exotherm itself is
a concern for scale-up of this reactor design.
Liquid ammonia-organic-diluted silicon
tetrachloride route
In the liquid ammonia-organic-diluted silicon
tetrachloride route, the SiC14 is diluted in an
organic liquid to achieve control over the
liquid-liquid exotherm. This process is prac-
ticed commercially with Si3N4 production of
greater than 100 t/yr. The method of Ube
Industries' 'two-liquid layer' patent to Iwai,
Kawahito and Yamada (980) is shown
schematically in Figure 15.2. As before, liquid
NH3 is loaded into the reactor. Then, a denser
stream with SiCl4 diluted in a 4: 1 mixture of
cyclohexane and benzene is added. The solid
silicon diimide polymer forms at the interface
between SiCl4 , dissolved in the cyclohexane-
benzene mixture, and liquid NH3. By-product
chloride solids immediately begin to dissolve
into the upper NH3 layer. The diimide is
collected by filtration, washed with liquid
NH 3, dried of residual NH3 and decomposed
to amorphous Si3N4 powder via a 1273 K
(1000 DC) calcination in N 2. The amorphous
394 Liquid phase reaction processes
Vent
4:1 cyclohexane 4:1 cyclohexane
+ benzene
Figure 15.2 Organic diluted chloride-liquid am-
monia reactor.
product is finally crystallized at ",1773 K
(",1500C) to a high purity a-Si3N 4 powder.
The NH3 and solvent can be recycled while
the by-product NH4Cl can be recovered and
sold. The overall process is shown schemati-
cally in a flow diagram (Figure 15.3). This
diagram and process description have been
constructed from information contained in
the process patent (Iwai, Kawahito and
Yamada, 1980) and several informative
publications (Yamada, 1993, 1994).
With slurry transfers and rinsing, the
chloride can be removed. Concerns are for
the retention of carbon from the organics pre-
sent at the imide formation. While this may
mask oxygen contamination, it is a concern
for powders to prevent later CO gas formation
in sintered solids and to maintain dielectric
properties.
Vapor silicon tetrachloride-liquid
ammonia route
To address the concern for carbon contami-
nation while maintaining reaction control,
another development uses a gaseous diluent
for the SiCl4. In the case (Crosbie and
Predmesky, 1988) that the process is operated
under pressure (not at the low temperatures
needed to maintain liquid NH3 at usual ambi-
ent pressure), a special advantage is realized: a
nearly heat neutral reaction zone.
A schematic of the vapor chloride-liquid
ammonia reactor design is shown in Figure
15.4. The vapor is introduced below the
liquid NH3 surface, and the reaction takes
place at the bubble surfaces. As the SiC4 is
consumed by the reaction, the excess NH3
seeks to re-establish its own vapor pressure
equilibrium with the carrier gas (such as N 2 ).
As NH3 evaporates, the heat of vaporization is
extracted from the location where the heat of
SiCl4 reaction is produced, to produce a nearly
heat neutral reaction zone.
Other liquid phase reactions forming imides
Pugar and Morgan (1988) pursued a low
temperature analog of nitridation of silicon.
Detectable quantities of imide are formed
by grinding a silicon powder in an active
nitrogen source, such as hydrazine or liquid
NH 3
THERMOCHEMISTRY AND KINETICS
Free energy of reaction
Estimates of reaction free energy were calcu-
lated (Crosbie et al., 1989). An estimate was
made of the standard heat of reaction of a
related, but hypothetical reaction, for which
thermochemical data were available or could
be estimated:
LViR(298) = -676 kJ Imol (15.3)
~GR(298) = -384kJ/mol
For the special case of the vapor chloride-
liquid NH3 reaction (Figure 15.4), an addi-
tional term enters the reactor heat balance.
Because the liquid NH3 vaporizes to establish
its partial pressure (often 50% of the total
pressure), the latent heat of vaporization
 Silicon nitride processes: imide intermediate routes 395

SiCI4 Solvent NH3

~ ~ I
l 244K

*
Interfacial SiC14+18N H3
0.23 kPa
Reaction
(Si(NH)A

t
NH3
t
Filtration

*
r-- and NH3> NH4CI
Wash
I Recovery
(Si(NH)2)X
I Decant

Calcination
* (Si(NH)2)x
-1273 K
I
S'13 N4(A)+ 2NH 3
Solvent
Recycle
~

Calcination -1823 K
Si 3N4(A) ~ Si3 N4

Mild Milling

~
Figure 15.3 Organic diluted silicon tetrachloride-liquid ammonia flow diagram.

must be included. Estimates of this heat
balance for the 50% condition were prepared
(Crosbie, 1986) and are shown in Figure 15.5.
From the vapor pressure curves of NH3 and
SiCl4 , lower amounts of N2 are needed in the
pressurized domain. This tends to minimize
the added cost of the N2 stream in the vapor
chloride-liquid NH3 route.
The kinetics of the NH3 + SiCl4 reaction are
fast. For the liquid SiCl4 reaction (but not the
organic-diluted SiC14 reaction), the release of
heat is typically described as 'violent'. In pres-
surized operation of the liquid-liquid reaction
(Crosbie, Predmesky and Nicholson, 1990),
sharp temperature rises were recorded after
each injection of SiC14 . For the controlled-rate
designs of Figures 15.2 and 15.4, the reaction
rate is mass-limited by the dilution with either
the organic liquid or with the carrier gas,
respectively. For the vapor-liquid design, a
396 Liquid phase reaction processes

To Condenser has various features. These are attributed to

volatile imido chlorides. In the treatments of
gas-gas imide intermediates, NH3 gas during
the <1273 K (1000C) imide decomposition
helps remove Cl. However, volatile imido-
chlorides carry away silicon, thereby reducing
NH3
(liq) yield based on an Si balance.

SiCI 4 (g)
+ N2 (g) ENGINEERING PRACTICE

Practices common to routes with

Figure 15.4 Vapor chloride-liquid ammonia
reactor.
taller reactor and down-draft agitation help to
increase bubble-liquid contact time, as in
other gas-liquid reactions.
In the absence of chloride residue, the ther-
mal decomposition in the presence of an N2
cover gas parallels the decomposition of NH3
to N2 and H 2. As Si(NH)2 decomposes to
Si3N 4 , a featureless decomposition is observed
(Billy, 1959) by thermogravimetry.
If the chloride by-product is retained, the
weight-temperature curve on decomposition
liquid ammonia
As processes move from lab to commercial
settings, the use of pressurized equipment for
NH3 is economically driven. By use of pres-
sure, the need for external refrigeration can
be reduced or eliminated. The feed, NH3, can
itself be vaporized to provide any initial cool-
ing. A vapor pressure curve for NH3 is given in
Figure 15.6, which directs the temperature-
pressure relationship. Ammonia is quite
compressible, and the pressures involved to
remove the need for refrigeration are moder-
ate. There are special safety issues for NH3,
which need to be addressed.

150r-------------------------------------~

~ 100
~
m
i
::r:
50
II:
a; Endothermic
z O~r-------------------------~~~__;
Exothermic
(Saturated SiCI4 Vapour Feed)
-50~----~----~----~------~----~----~
253 273 293 313
Reactor Temperature (K)

Figure 15.5 Heat balance estimates for vapor-liquid process.

 Silicon nitride processes: imide intermediate routes 397
333
323
313
303
293
283

-
2' 273
.... 263
253
243
233
223
213
203

a 500 1000 1500

9'NH :s (kPa absolute)

Figure 15.6 Vapor pressure of liquid ammonia: b.p. = boiling point; m.p. = melting point.

Pressure alone is not enough to keep However, in liquid-liquid cases, the chloride
moisture from entering the system and may be encased or entrapped, leading to
contributing oxygen contamination. There- its retention. In other cases, above 278 K
fore, the apparatus must be sealed vacuum- (5C), a viscous ammoniate impedes attaining
tight. One approach (Crosbie, Predmesky
and Nicholson, 1990) to reduce oxygen Helium Leal<
contamination is to use enclosed O-ring Test Port
fittings, shown in Figure 15.7. These allow
'\.
both vacuum for purging of the system and
pressure for operation near room tempera-
~
,
ture. Furthermore, the fittings enclose a
volume which allows access for helium .--- r-
leak testing, even during powder-making
operations.
Chloride by-product removal seems critical
to maintain the microstructural and purity
advantages of imide-liquid ammonia routes.
- '--

In the liquid-liquid route at low temperature,

Morgan (1973) reported that week-long
Soxhlet extraction was needed. In principle,
pressurized operation at temperatures near
ambient should help, as solubility increases.
~ j
Figure 15.7 Enclosed O-ring fittings. (Copyright
1987, 1990 Swagelok Co., Solon, OH. All rights
reserved.)
398 Liquid phase reaction processes
equilibrium (Jander, 1966) even in the imide-
free NH r NH4Cl system. In tests by Crosbie,
Predmesky and Nicholson (1990), three
50 min rinses at 288 K (15C) extracted much
more chloride than three 15 min rinses at 273 K
(OC).
Liquid silicon tetrachloride-liquid
ammonia route
Injection of the liquid chloride, even at lab
scale, apparently must be pulsed to allow for
heat extraction to the cooled reactor walls. To
avoid inlet clogs which have Si-N bonds (and
are difficult to clear), the liquid chloride path
should be purged with N2 or other non-
reactive gas. Extra agitation and recycling of
the rinsing NH3 (Beckwith and Williams,
1987) help to remove the by-product and to
provide opportunities for addition of sintering
aids.
Organic-diluted silicon tetrachloride-liquid
ammonia route
Beyond the common aspect of pressurized
operation, the liquid ammonia-organic
diluted SiCl4 commercial method undoubt-
edly incorporates many engineering aspects
which are not widely discussed. It can be
speculated that design points are related to:
1. maintaining the two-layer density differ-
ences as solids are formed and NH4CI is
dissolved into the upper NH 3;
2. maximizing utilization of the reactor
volume by selecting a sufficiently high
SiCl4 concentration in the organic carrier;
3. agitating the liquids to help transfer heat
away from the reaction interface to the
reactor cooling means.
Vapor chloride-liquid ammonia route
In contrast to the organic carrier route, this
method uses a non-reactive gas carrier. The
amount of N2 carrier gas is markedly reduced
by operation under pressure near ambient. It
could be reduced further at yet higher tem-
peratures, if the NH3 can be kept liquid at its
correspondingly higher pressures. There may
well be site-dependent trade-offs based on
reactor ambient temperature among conden-
ser cooling (or compression) costs, reactor
wall thickness for pressure and transportation
costs from natural-gas-dependent NH3 gener-
ating sources. A taller reactor design is favored
to be compatible with higher pressures and at
the same time provides a longer bubble-liquid
contact time.
In the work of Crosbie, Predmesky and
Nicholson (1990), the saturator was kept
above the reactor temperature to keep conden-
sation away from the SiCl4 vessels. This choice
led to a need for a stable, flowing gas mixer
which was achieved with a symmetrical flow
design: volumes upstream of the flow control
valves were proportioned to the flow rates, so
pressure changes in the reactor vessel from a
downstream cause affect each stream in the
same proportion.
Thermal decomposition to produce
crystalline Si3N4
As shown in the process flow diagram of
Figure 15.3, the silicon diimide must be
decomposed (to drive off NH 3) to first
produce an amorphous Si3N4 powder. The
amorphous Si3N4 is then crystallized in a
second higher temperature calcination. The
few materials tolerant of the non-oxidizing,
1723 K (1450C) decomposition temperature,
such as alumina, are limited in strength
and thermal shock resistance. Thus, it is
important to release the pressure before trans-
fer to the refractory vessel. All steps here
continue to require anaerobic handling. By
venting some excess NH3 to a scrubber-
recovery system, the slurry temperature can
be dropped to give a lower pressure, before
a slurry transfer.
During heating, a low flow of an N2 cover gas
is used. Below, say, 773 K (500C), off-gases are
 Silicon nitride processes: imide intermediate routes
mostly NH3 which can be recovered as such.
The cross-linking polymerization of the imide
and subsequent crystallization are treatable
with radiation, such as gamma-ray radiation
(Ube Industries, 1986). At higher temperatures,
the NH3 content decomposes to N2 and H 2,
which must be swept away. If the chloride
has not been removed, it will deposit in cooler
regions along with imidochloride residues, pos-
sibly causing an overpressure in the reactor.
Yamada, Kawahito and Iwai (1983) find for
the final crystallization that there are two
Arrhenius slopes and two microstructures.
Crystallization is exothermic, but less so than
nitridation of silicon powder (Arrol, 1974;
Mangels, 1981). From the dependence of
crystallization rate on temperature, an appar-
ent activation energy of 890 kJ / mol can be
calculated from Figure 15.8 below 1703 K
(1430C).
399
POWDER PROPERTIES
Liquid silicon tetrachloride-liquid
ammonia
A typical liquid-liquid reaction produced
nitride (Crosbie, Predmesky and Nicholson,
1990), which followed the Morgan (1973) sug-
gestion for pressurized operation, is shown in
Figure 15.9. The needles are abundant in the
structure, and are likely due to chloride resi-
due from entrapments in the non-uniformities
from the exothermic reaction. In other treat-
ments with more effective Cl removal, other
microstructures could result. In work by
Morgan (1973), hot pressing reached 85%
density. This is not a commercial product,
and can only be construed as an indication.
(Some gas-gas reactions produce equiaxed
powders, in spite of chloride presence at
early stages.)

100 aD~ ___ Kl~OO~oe-

80 ( /0/_
-
l -/'
~
~
>.
60
."t::!

L /
c 1713 K
-
.:
(ij
en 40 1703 K
&
1/,1
~
~ 0 1693 K
1673
()

~/~
K
~1658 K
20
1633 K
,.
A

/
0
0 2 4 6 8 10 12
Heating duration (h)
Figure 15.8 Effects of temperature and duration on the crystallinity of diimide intermediate Si3 N 4 .
(Yamada, T., 'Preparation and evaluation of sinterable silicon nitride powder by imide decomposition
method,' Am. Ceram. Soc. Bull., 72(5),99-106, 119, 1993. Reproduced by permission of the American
Ceramic Society, Westerville, OH.)
400 Liquid phase reaction processes

Figure 15.9 Liquid chloride-liquid ammonia powder.

Figure 15.10 Organic diluted chloride-liquid ammonia powder.

 Silicon nitride processes: silazane intermediate routes
Organic-diluted silicon tetrachloride-liquid
ammonia
This is the leading high purity nitride powder
route. It has been the subject of extensive
characterizations. It is pressureless sinterable
(Crosbie, Nicholson and Stiles, 1989) with
only dry mixing to greater than 98% of
theoretical density. An image from Ube
Industries is shown in Figure 15.10. The
equiaxed powder 'E-10' has about 10 m 2 / g
BET surface area. The typical purity character-
istics are listed in Table 15.1 and the particle
size distributions are shown in Figure 15.11.
Except for carbon at 0.17wt%, cations and
chloride are below 100 ppm. Oxygen content
is largely located on the surface, at 1.1 wt%.
The powder has been analyzed by MAS-
NMR (Carduner et al., 1987) and for distri-
bution of oxygen (Peuckert and Greil, 1987).
Additional characterization is given by
Kohtoku (1989).
Vapor silicon tetrachloride-liquid
ammonia route
Characterization (Crosbie, Predmesky and
Nicholson, 1990) demonstrated an inter-
mediate imide similar to that of Billy (1959),
with low oxygen content. In the course of
decomposition, oxygen pick-up compromised
401
the sintering properties, so Si2 N 2 0 was
present. Densities of only ",87% were achieved
with this powder for conditions that produced
greater than 98% for the two-liquid layer
nitride powder. The equiaxed microstructure
of the (oxygen-contaminated) powder is
shown in Figure 15.12.
SILICON NITRIDE POWDER PROCESSES:
SILAZANE INTERMEDIATE ROUTES
Among the large group of organosilicon com-
pounds, the silazanes (Kruger and Rochow,
1964) share the direct Si-N bonding with
the silicon diimide of the previous section.
This family is the closest analog for the
nitride of the polymethylsilane (PMS) for
the carbide, which has achieved commercial
success for (mainly) SiC fibers (Chapter 17).
In terms of strategies for choosing pre-
ceramic polymers (Paine and Narula, 1990),
the pre-existence of the desired bond tends
to enhance the ceramic yield. Just as PMS is
not a precursor of choice for SiC powder
because of its cost, the laboratory demonstra-
tions with the silazanes have usually been
pointed toward a goal of fibers, membranes,
coatings, or of use as a binder for Si3N4
powder from some other process. In Chapter
17, the use of silazanes for nitride-containing
fibers is discussed.

Table 15.1 Typical characteristics of Si3N4 powders from organic-diluted chloride-liquid ammonia
reaction

Chemical composition Property

N 0 C CI Fe Al Ca a- Si3 N 4 Specific Mean particle

(wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (wt%) surface area size, d so
(m 2 /g) (jLm)

SN-ElO 38.6 1.3 0.1 50 50 20 10 97 11 0.55

SN-E05 38.7 1.2 0.1 50 50 20 10 100 5 0.7
SN-EPS 38.7 1.2 0.1 50 50 20 10 98 7 0.7

Source: Yamada, T., 'Preparation and evaluation of sinterable silicon nitride powder by imide decomposition method:
Am. Ceram. Soc. Bull., 72(5), 99-106, 119, 1993. Reproduced by permission of the American Ceramic Society,
Westerville,OH.
402 Liquid phase reaction processes
100r---~--~--~~rT~~----~~~~TT~

SN-ESP
SN-E1O
SN-EOS
c
o SN-E03
~
o
Q.
E
8
~
"'5
E
:::I
()

o~~~~~~--~~
0.1 0.2 0.4 0 .6
..~------~~--~.w
4 6 2
10
Particle diameter (J,lm)

Figure 15.11 Particle size distributions of Ube Si3N4 powders. (Yamada, T., 'Preparation and evaluation of
sinterable silicon nitride powder by imide decomposition method,' Am. Ceram. Soc. Bull., 72(5), 99-106, 119,
1993. Reproduced by permission of the American Ceramic Society, Westerville, OH.)

Figure 15.12 Vapor chloride-liquid ammonia powder.


Along with the silicon-nitrogen (Si-N)
bonds (the majority of which can be retained
in certain thermal decomposition schemes),
there are also SiC/carbon residues. For the
PMS case, where the goal is to decompose to
a silicon carbide material, the carbon is
desired. However, such carbon residues in
Si3N4 are not desired, except for some cases
for fine composites of Si3N4 with SiC. Depend-
ing on the phase the carbon is in, the carbon
can gasify (to CO) inside a sintered part, to
the detriment of the mechanical and oxidation
resistance of the part.
PROCESS DESCRIPTIONS
Polymeric precursors with nitrogen content
are described by Wynne and Rice (1984),
with an emphasis on their use for fibers for
composite reinforcement. The large shrinkage
and high cost are tolerated in the fiber
product, but are less likely to be tolerated for
a powder.
Many variants of silazane syntheses have
been described by Seyferth et al. (1988) with
many interesting complexities. Of the poten-
tial silazane routes to powders, it is likely
that the lowest cost ones are those formed by
basic (e.g. potassium hydride, KH) catalysis
cross-linking of reaction products of dichloro-
methylsilane (CH3(H)SiClz) with NH 3.
The silazane which results often is in the
form of a high viscosity liquid, which is
desired for making fibers. When decomposed
in bulk, however, the product is more of a
solid than a powder. Any milling or other
comminution may add back the contamina-
tion from the mill and media. Certainly,
there is interest in use of such precursors to
make ceramics directly (without using a
powder). However, these routes tend to be
limited to making small parts or porous ones
as a result of the low spatial concentration of Si
in a unit volume of a silazane when compared
to the spatial concentration for an Si3N4
compact, for example. In a recent volume
(Laine, 1992), several silazane variants have
Boron nitride and aluminum nitride processes 403
been examined for use as fiber or coating
precursors.
Although initial reports with supercritical
fluid extraction (SFE) processing of Si3N4
from Si3N4 feeds (Petersen, Matson and
Smith, 1986) were unsuccessful, there is
evidence of Si3N4 solid formation via SFE
routes from dimethyldichlorosilane precursors
(Sullivan, 1990). The solids could conceivably
be ground to form powders, but the direct
formation of Si3N4 might bypass entirely the
need for powders for some porous shapes.
THERMOCHEMISTRY
Working with catalyzed polymerization at
low temperatures, the conversion of a chloride
bond in a dichlorodimethylsilane to an Si-N
bond is analogous to that in the SiCl4 case.
The reported synthesis routes indicate which
reactions do proceed, from which the free
energies can be estimated.
For the thermal decomposition of the sila-
zanes, Riedel and Seher (1991) have measured
in detail the decomposition and crystallization
kinetics for the formation of Si3N4 powders.
BORON NITRIDE AND ALUMINUM
NITRIDE PROCESSES
Liquid phase processes for compounds other
than silicon nitrides and carbides have been
examined in the laboratory, but not in large
production. Inorganic and organic variants
of the silicon diimide and silazane have been
demonstrated to produce fine powders of
other cations with low oxygen contents and
ultrafine particle sizes.
PROCESS DESCRIPTIONS
Liquid ammonia-liquid boron
trichloride route
In an organic-free route to boron nitride,
Kalyoncu (1986) describes the intermediate
reaction product of NH3 with boron trichloride
404 Liquid phase reaction processes
(BCI3) as a B(NH2h:
6NH3(1) + BCI3(1) ---+ B(NH2h
+ 3NH4CI (15.4)
Upon heating to ",1273 K (1000C), x-ray dif-
fraction shows crystalline BN is formed with
an 80-100 m 2/ g specific surface area and
0.7 wt% oxygen. Boron trichloride (BCI3) is
the starting material for a 'two-liquid layer'
reaction in an example which appears in the
original Ube patent (Iwai, Kawahito and
Yamada, 1980t but this example is deleted
from the reissue (Iwai, Kawahito and
Yamada, 1985), although the VC4 + NH3 ---+
VN case is retained. Niederhauser (1962)
demonstrated liquid NH3 reactions separately
with VC4 (to form VN), with a suspension of
ZrCl4 (to form ZrN), and with TiC4 dissolved
in CCl4 (to form TiN powder for use as a
pigment).
Aminoborane and related routes
Organometallic/ metal-organic routes for boron
nitride (BN) have been reviewed (Narula, 1987;
Paine and Narula, 1990). Therein, the strategies
for forming bonds between Band N at low tem-
perature and obtaining medium molecular
weight polymers are described as a means to
enhance yield on thermal decomposition.
Among others, one case to form the amino-
borane as an intermediate on the way to
hexagonal BN, which is cited by Narula,
Paine and Schaeffer (1988), is
R2BCl + R~NSiMe3 ---+ R2BNR~ (15.5)
This reaction has been used to prepare
several poly(borazinyl) amines. In related
compounds (Narula et al., 1989), the result of
thermal decomposition is hexagonal BN with
good crystallinity and yields.
Aluminum chloride routes to AIN
The aluminum chloride analog of the liquid
ammonia-organic-diluted silicon tetrachlor-
ide was attempted by Iwai, Kawahito and
Yamada (1980) without success. Schleich
(1988) dissolved AICl3 in hexamethyldisilane
(HMOS) and heated the solution to 363-
393 K (90-120 C) to form an AI-N-containing
complex as an intermediate claimed to be:
HMOS + AICl3 ---+ (AI-N) complex
+ TMSCI (15.6)
Upon thermal decomposition, the complex
formed AlN with a surface area of 150-200 m2/ g.
Organoaluminum compound routes
An early example of laboratory organometal-
lic routes to AlN is that of Interrante, Carpen-
ter II and Whitmarsh (1986). They reacted
trialkylaluminum compounds with NH3 to
form a Lewis acid-base adduct, which forms
AlN on thermal decomposition:
R3AI + NH3 ---+ R3AI : NH3 (15.7)
where R = CH3, CH2H s , ... (Hurley et al.,
1990) used a diisobutyl aluminum amide, [(i-
butylhAlNH2h, dissolved in toluene, as a
source of aluminum additive for a polysilazane
route. As found for the polysilazanes, a l.3wt%
carbon residue remained after decomposition.
THERMOCHEMISTRY
Glasson and Jayweera (1968) describe the
thermochemistry of reactions forming nitrides
(including transition metal nitrides) from
metals and chlorides with NH3 gas present.
Likewise, for deposition of films from gas,
there is much work reported. For the low
temperature liquid phase reactions, there is a
scarcity of data for the intermediate products,
so the best guide to the thermochemistry is the
report of the product itself being produced for
a given set of conditions.
POWDER PROPERTIES
These routes, operated in laboratory, give fine
powders (100-200m2/g) with less than 1 wt%
oxygen.

CARBIDES AND BORIDES
The oxidizing atmosphere temperature resis-
tance (and high hardness) of particular car-
bides (e.g. SiC) and borides (e.g. ZrB2) can
exceed that of the nitrides and most other
non-oxide compounds. The traditional routes
practiced commercially are ones with solid
state reactants and high temperature reactions,
which are not available for Si3N4 due to its
decomposition.
PROCESSES
Rapid expansion of solution route
To generate SiC precursor powders (instead
of fibers) from liquid phases with organo-
metallics, Matson and Smith (1986) have
used a rapid expansion method with the
same polycarbosilane (PCS) as used for
the Yajima process fibers, in a pentane solu-
tion, to produce fine powders. The poly-
carbosilane with its solubility is formed
by a reaction to convert the (insoluble) Si-Si
backbone to a (soluble) Si-(CH2)-Si-(CH2)-
one:
(15.8)
It is likely that in similar ways, the many new
fiber precursors reviewed by Laine (1992) (and
earlier ones reviewed in Gmelin et al. (1989
could be used to make powders by routes
developed for fibers. These routes may
include ones which do not necessitate the
conversion to PCS, such as ones based
on polysilastyrene copolymers, [PhMeSi]n-
[Me2Si]m, which can be cross-linked with
ultraviolet light and converted to SiC by heat-
ing in vacuum. Commercialization of any of
the organometallic routes for powders is not
widely known.
References 405
Molten salts
In the practice of surface treatment of metals,
(liquid) salt baths are used to precipitate fine
carbide and nitride particles for hardening
near the surface. Dissolving the metal may
leave a fine powder, but this is unlikely to be
a practical approach. As an indication of a
more practical approach, Kushkov et al.
(1991) have reported plating Mo 2C from a
molten salt bath. Although this is more
properly a coating method than a powder
method, it is representative of use of a liquid
for synthesis of a carbide at lower tempera-
tures than used in reactions with solid state
feeds.
Amorphous transition metal borides
O'Handley, Chou and DeCristofaro (1979)
have used melting and rapid solidification
routes to form amorphous transition metal-
boron compounds.
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Ube Industries (1986) Manufacture of crystalline
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Koho, Patent Application 84: 141407. (Cited
from Chem. Abstracts, 101(26), abst. no. 234596e.)
Woetting, C. and Ziegler, C. (1986) Powder charac-
teristics and sintering behavior of Si3 N 4. Powder
Metall. Int., 18(1), 25-32.
Wynne, KJ. and Rice, RW. (1984) Ceramics via
polymer pyrolysis. Ann. Rev. Mater. Sci., 14,
297-334.
Yamada, T. (1993) Preparation and evaluation of
sinterable silicon nitride powder by imide
decomposition method. Am. Ceram. Soc. Bull.,
72(5),99-106, 119.
Yamada, T. (1994) Synthesis and characterization of
sinterable silicon nitride powder. Ceram. Trans.,
42,15-27.
Yamada, T., Kawahito, T. and Iwai, T. (1983) Crys-
tallization of amorphous Si3N4 by the thermal
decomposition of Si(NH)2. J. Mater. Sci. Lett.,
2(6),275-78.
PART SIX
SYNTHESIS OF WHISKERS,
PLATELETS AND FIBERS
Non-oxide whiskers, platelets and fibers are
incorporated into ceramic matrix composites
(CMC) to improve the mechanical properties
(toughness) of the composites relative to the
monolithic materials. Part Six begins with a
review of the processes for synthesizing
whiskers and platelets (Chapter 16). This is
followed by a review of the synthesis of
fibers from polymers (Chapter 17).
Whiskers are short, discontinuous, rod- or
needle-shaped single crystals in the size
range 0.1-5 JLm in diameter and >5 JLm in
length. Because whiskers are nearly single
crystals with very ordered structures, they
typically have very high tensile strengths
which makes them excellent reinforcement
materials for composites. Desirable fibers typi-
cally have a diameter <30 JLm which is suit-
able for weaving and knitting. Controlled
interfacial weak bonding between fiber and
matrix permits non-brittle fracture of CMCs
with fiber pullout, resembling a woody frac-
ture. Platelets have some advantages com-
pared to whiskers and fibers in utilization in
composite materials. The platelets are free
flowing and consequently can be easily
mixed with other powders. They offer the
optimum disk shape for crack deflection.
The commercial-scale production of whis-
kers and platelets typically uses carbothermal
reduction (Chapter 3) and reactions of halo-
gen-based or sulfur-based precursors. In this
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
process, whiskers grow by a vapor phase
chemical reaction method with deposition on
a substrate. Other non-oxide ceramic whisker
growth methods include vapor phase forma-
tion and condensation, vapor-liquid-solid
(VLS) methods, and growth from melt solu-
tions. Gas or liquid phase transport of the
reactants and porosity (free volume) are
necessary for whisker growth. Platelets are
normally formed by a two-step reaction pro-
cess. The first step requires an extended
reaction time at a lower temperature. Product
from the first step is cooled, remixed and then
fired at a higher temperature to produce the
platelets. Platelet formation is facilitated by
the addition of certain catalysts. The synthesis
of silicon carbide (SiC) whiskers and platelets,
which dominate the commercial market, are
the focus of Chapter 16.
Most ceramic fibers are prepared commer-
cially from organometallic polymers. A poly-
mer is synthesized, melt-spun to fiber, and
cross-linked (cured) to prevent melting on
subsequent pyrolysis to ceramic fiber. The
spinning process generally consists of melt
spinning at elevated temperature followed
by drawing under tension to finer diameter.
The cross-linking (or cure) process can be
accomplished by chemical, thermal or radia-
tion methods. The cured polymer is then
pyrolyzed to a ceramic product using an inert
or potentially reactive atmosphere (such as N2
410 Synthesis of whiskers, platelets and fibers
to produce nitrides). The simultaneous shrink-
age and loss of pyrolysis gases leads to a
ceramic fiber which has a density below
theoretical for its composition. The synthesis
processes, composition and structure, and
properties of non-oxide ceramic fibers derived
from polymers are described in Chapter 17.
SAFETY ISSUES
Because their sizes and shapes are similar to
those of asbestos, SiC whiskers should be con-
sidered hazardous (Gross, 1970). In the United
States, Material Safety Data Sheets (MSDS) are
packaged with all products containing loose
whiskers and the directions in the data
sheets should be followed. In addition, the
American Society for Testing of Materials
(ASTM) has developed standards for hand-
ling SiC whiskers, AI2 0 3-SiC whisker compo-
sites and Si3 N c SiC whisker composites.
Health studies have established that inhala-
tion exposure to certain materials like asbestos
can lead to the formation of malignant tumors
in the linings of the lungs. The cellular
response to SiC whiskers during in-vitro and
in-vivo rodent tests is of the same order as
asbestos (Birchall et al., 1988). Results of
rodent implantation and cell culture studies
of SiC whiskers indicated a potential inhala-
tion hazard and carcinogenic risk from whis-
kers in the submicron range (Bogoroch and
Luck, 1988). Experimental animal studies
have shown that the ability to cause cancerous
growth is more related to the physical dimen-
sions of the material. In addition, it is rela-
tively independent of the chemical nature of
the material, provided the fibers are durable
in the body. SiC whiskers are in the proper
size range (",0.5 JLm) and are durable. Thus,
in the absence of any validated chronic low
level inhalation studies, SiC whiskers should
be considered as carcinogenic.
While inhalation of airborne SiC whiskers is
the most serious threat, a secondary threat
exists from skin exposure. This may cause
various levels of dermatitis or skin irritation
and is especially true if any cuts, bums or
abrasions are present.
As discussed, airborne dispersion and sub-
sequent inhalation of SiC whiskers is the most
serious health hazard. However, with proper
workplace handling requirements and proce-
dures, large quantities of SiC whiskers can be
safely processed (Bogoroch and Luck, 1988).
To date, no release of whiskers has been
observed from dense ceramic matrix compo-
sites during fracture or wear processes.
Safety issues related to carbothermal reduc-
tion processes, such as those used to produce
some whiskers and platelets, are discussed in
Part Two. The handling of halogen-based pre-
cursors and reaction products, including SiC4
and other liquid metal halides, are discussed
in Parts Four and Five.
REFERENCES
Birchall, J.D., Stanley, D.R, Mockford, M.J., Pigott,
G.H. and Pinto, P.J. (1988) Toxicity of silicon
carbide whiskers. J. Mater. Sci. Lett., 7, 350-52.
Bogoroch, R and Luck, S.R (1988) Workplace
handling requirements and procedures for
ACMC silicon carbide whiskers based on a sub-
chronic inhalation study in rats, in Whisker and
Fiber Toughened Ceramics (eds RA. Bradley, D.E.
Clark, D.C. Larsen and J.O. Stiegler) ASM Inter-
national, Metals Park, OH, pp. 81-89.
Gross, P. (1970) The pulmonary response to fibrous
dusts of diverse compositions. Am. Indust. Hyg.
Assoc. J., 125-32.
WHISKER AND PLATELET SYNTHESIS
PROCESSES
Terry N. Tiegs and Sam C. Weaver
INTRODUCTION
Recent emphasis has been placed on the incor-
poration of SiC whiskers into both metal and
ceramic matrix composites to improve the
mechanical properties of the composites
relative to the monolithic materials. In the
1960s, the whiskers were originally applied
to the reinforcement of metal matrices, such
as aluminum (Mortensen, 1990; Nair, Tien
and Bates, 1985). Since then, whiskers have
also been used to reinforce ceramics, such as
alumina (AI2 0 3 ), mullite and silicon nitride
(Si3 N 4 ) (Becher et ai., 1988, 1994; Wei and
Becher, 1985).
In this chapter, whiskers will be defined as
short, discontinuous, rod- or needle-shaped
single crystals in the size range 0.1-5 p,ID in
diameter and greater than 511m in length.
This differentiates them from other fibrous
materials that are polycrystalline, amorphous
or consist of multiple coatings.
Whiskers have been reported as early as
the 16th century, but it was not until the
1950s that they became the subject of intense
study when it was discovered they were
nearly single crystals and could have extremely
high strengths. Silicon carbide (SiC) whiskers,
introduced in the early 1960s, were the first
commercially available materials (Milewski,
1987). Since that time, the demand for whiskers
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
16
has increased due to composite materials
development and the commercial success of
some products. The current status of the
industry is one of constant change. In recent
years, numerous companies world-wide have
offered for sale or tested SiC whisker products
(Frevel, Saha and Petersen, 1995).
Several methods and numerous starting
raw materials have been used to grow SiC
whiskers. Most of the early research and pub-
lished data in the field employed the vapor-
liquid-solid (VLS) mechanism to produce
laboratory quantities of whiskers (Berman
and Ryan, 1971; Bootsma, Kippenberg and
Verspui, 1971a,b). Later large scale production
methods, discussed mainly in the patent
literature (Hayashi, Mochizuki and Ozawa,
1985; Horne and Ramsey, 1981; Nadkarni
and Jain, 1988; Schramm and Birtell, 1988;
Shalek, 1987; Shyne and Milewski, 1968;
Tanaka, Kawabe and Kobune, 1985), used
carbothermal reduction reactions of low
cost silica and carbon precursors, such as
rice hulls. Large quantities of whiskers
(>10 000 kg/yr; >22 000 lb/yr) were produced
with these methods at reasonable costs. This
allowed SiC whiskers to become economically
viable as reinforcing phases in components for
large scale, high volume applications.
This chapter will initially introduce a
variety of whisker growth methods for many
412 Whisker and platelet synthesis processes
types of non-oxide whiskers. However, the
major portion of the discussion will be con-
cerned with SiC whiskers, since these are the
ones of most interest currently and have the
largest database in the literature. Discussion
topics will include growth mechanisms,
growth processes (including precursor types
and reaction conditions), the types of SiC
whiskers available and characterization of
properties. Also included is a section on SiC
platelet synthesis.
NON-OXIDE WHISKER GROWTH
MECHANISMS
Whisker growth occurs by two main mechan-
isms: basal or tip growth (Milewski, 1991). For
basal growth, the whisker is extruded from a
substrate that continually provides more
atoms to the growing whisker. This type of
growth has been observed for tin-plated struc-
tures under stress (Milewski, 1991) and TiB2
whiskers (Kyriacou, Sepulveda and Watson,
1992; Motojima, 1975). In tip growth, atoms
migrate to the growing end of the whisker
either in the gas or liquid phase and attach
themselves by a variety of mechanisms. The
vast majority of whisker growth phenomenon
occurs by this mechanism as described below.
Four different methods of tip growth have
been described in the literature for producing
non-oxide whiskers of various types and
morphologies (Bracke, Schurmans and Ver-
hoest, 1986). The different methods are
described as follows.
1. Vapor phase formation and condensation.
This method involves either sublimation or
evaporation of the source material, mass
transport through the vapor phase and con-
densation at the growth site. Non-oxide
whiskers that have been made by this
method include CdSe, ZnS, CdS and SiC.
2. Vapor-liquid-solid (VLS) method. This
method involves vapor transport of the
constituents (or precursors) to a liquid
catalyst located at the tip of the whisker,
incorporation of the constituents into the
liquid and precipitation of the solid crystal
at the liquid-solid interface. Examples of
whiskers that have been grown in this
manner include carbon, SiC, Si, LaB6 and
Ge (Givargizov and Sheftal, 1971; Tairov,
Tsvetkov and Khlebnikov, 1981; Wagner
and Ellis, 1964; Yang and Chen, 1989).
3. Vapor phase chemical reaction. This
method involves a chemical reaction to
synthesize the components for whisker
growth. This is normally done in the
vapor phase with deposition on a substrate.
SiC, Si3N 4 , TiN, TiC, ZrN, ZrC and B4C
whiskers have been grown by this
method. This is the primary method for
large scale production of SiC whiskers on
a commercial basis. It includes carbo-
thermal reduction of silica and carbon
and reactions of halogen-based or sulfur-
based precursors.
4. Growth from melt solutions. In this
method, whisker growth is done from
saturated or supersaturated melt solutions
containing other fluxes or solvents. Silicon
nitride (Si3N 4 ) is the only reported non-
oxide material grown in this manner. The
best example is the acicular growth of (3-
Si3N4 grains during liquid phase sintering
of silicon nitride-based materials (Lange,
1983).
Three additional methods have been
reported for fabrication of oxide whiskers
and will not be discussed in this chapter.
Two of the methods, growth from solution
and growth from gels, are low temperature
processes and are probably not amenable to
carbide and nitride materials. The third
method, growth directly from melts, involves
whiskers grown directly from the component
melt solutions containing no fluxes and
should be amenable for non-oxide whisker
growth. However, while oxide-based
materials have reportedly been fabricated, no
non-oxides have supposedly been grown by
this method.

Few requirements are necessary for whisker
growth in any of these methods. All processes
that have been described in the literature
require gas or liquid phase transport of the
reactants. Thus, the most important factor gov-
erning whisker growth is that a free volume or
space is present. In this respect, rice hulls,
which have been extensively used in commer-
cial SiC whisker growth, are an extremely
fortuitous structure in that they supply not
only the reactants, but also the necessary free
volume for whisker growth. Even for the (3-
Si3N4 needle growth observed in liquid
phase sintered silicon nitride materials, room
for growth is required. For instance, when
second phases are present in those materials,
such as SiC whiskers, acicular grain growth
is inhibited. In other words, whiskers do not
grow if space is not provided. While catalysts
are used extensively and they improve quality
and yields substantially, they are not a pre-
requisite for all growth mechanisms.
SILICON CARBIDE WHISKER GROWTH
PROCESSES
The methods involved during SiC whisker
growth fall into three major categories:
1. vapor phase formation and condensation;
2. vapor-liquid-solid (VLS);
3. vapor phase chemical reaction, sometimes
referred to as vapor-solid (VS).
In all cases, vapor species are involved.
VAPOR PHASE FORMATION AND
CONDENSATION
Most of the work done on evaporation or
sublimation processes to make small quan-
tities of whiskers (Kippenberg and Verspui,
1969) occurred before the 1970s, although
some recent work has also been done (Lilov,
1994). Since SiC was the precursor, very high
temperatures were employed, usually T >
2473 K (>2200C). In this process, SiC is
heated in a closed container to create a high
Silicon carbide whisker growth processes 413
vapor pressure of the constituents and, upon
cooling, the SiC would condense out as
whiskers. The method was mainly a labora-
tory curiosity and consequently is not widely
used at the present time.
VAPOR-LIQUID-SOLID GROWTH
The VLS process has been studied and
reported in the literature for nearly 30 years.
The fundamentals of the growth mechanisms
were initially described by Bootsma and co-
workers at the Philips Company in a
number of seminal papers published in
the early 1970s (Bootsma, Kippenberg and
Verspui, 1971a,b). They showed that growth,
whisker morphology and crystal structure
were dependent on temperature, reactant
concentrations, catalyst nucleation behavior
and relationships between catalyst wetting
behavior and whisker diameter.
In recent times, the VLS process has been
investigated by Milewski and co-workers at
Los Alamos National Laboratory (LANL).
They worked on the optimization of catalyst
nucleation, gas composition, reactor geometry,
gas dynamics and reactant supply.
Obviously, in the VLS mechanism, a liquid
is present and is usually referred to as the
catalyst. The requirement for the catalyst is
that it can incorporate sufficient amounts of
both silicon and carbon for sustained SiC
growth. The most widely employed materials
have been metals, such as Fe, Co (Krishnarao,
1995), Cr and Mn. Boric acid, H 3B03, addition
contributes to the formation of an Si02-B2 0 3
liquid phase which has a dramatic effect on
whisker morphology (Cerovic, Milonjic and
Bibic, 1995). A typical VLS grown whisker is
shown in Figure 16.1. The growth sequence
occurs in four basic steps:
1. vapor transport of Si and C species;
2. solution of the Si and C into the liquid
catalyst;
3. diffusion of the Si and C through or on the
surface of the liquid phase;
414 Whisker and platelet synthesis processes
Figure 16.1 Typical VLS growth of SiC whiskers.
4. precipitation of SiC at the liquid-solid
interface.
Initially, the catalyst is in contact with a
substrate material (usually carbon) as the
temperature is raised to where melting
occurs. The liquid droplet absorbs Si and C
from the gas phase until it becomes super-
saturated. Nucleation of SiC occurs at the
interface with the substrate and continued
solution of gas species into the liquid catalyst
ball allows the whisker to grow as additional
SiC precipitates. Whisker growth occurs in the
(0001) or (111) crystallographic directions and

which direction affects the diametrical shape.
Hexagonal or trigonal cross-sections are
produced with growth in the (0001) or (111)
crystallographic directions, respectively.
Axial growth rates for VLS whiskers are
deceptively fast. Bootsma, Kippenberg and
Verspui (1971a,b, 1984) and Verspui, Kippen-
berg and Bootsma (1972) reported the growth
rate to be on the order of 1 mm/h or ",0.3 p,m/
s. Even higher growth rates of 2 mm/h
or 0.5 p,m/ s have been reported at LANL
(Milewski et al., 1985). As one can imagine,
the process is very dynamic and, con-
sequently, control of the reactant supply is
critical to uniform whisker growth.
Both the Philips and LANL processes are
based on the SiOz-C-H2 system. However,
other precursors have also been used. Chloro-
silanes were reported to have been used to
grow SiC whiskers by the VLS mechanism
(Berman and Ryan, 1971; Merz, 1960;
Wagner and Ellis, 1965). In the literature, it is
difficult to discern whether the processes
using chlorosilanes were totally VLS-type
mechanisms or included some vapor phase
chemical reaction mechanisms as well. Thus,
the reader should also consult the following
section on vapor phase chemical reactions
using halogen-based precursors.
Numerous silicon sources are available,
including SiCH3 Cl3 (MTS), Si(CH3 hCI2 and
SiCI4 . Carbon sources are even more varied,
such as MTS, CH3 Cl, carbon black, coke and
all hydrocarbon gases (methane, ethane,
butane etc.). Temperatures needed are 1573-
1773K (1300-1500C) and always T < 1873K
(1600C). Chlorine can also be found in other
processes such as those using NaCI and HC!,
but in all these cases generation of SiCl4 is
believed to occur.
Numerous catalysts are reported for use
with the chlorine-based processes. In these
systems, the catalyst ball stability is limited
to angles of 40-60. A comparison of Al and
Fe reported larger diameter whiskers with
the Fe due to higher solubility of carbon and
a slower reaction rate. Nickel as a catalyst
Silicon carbide whisker growth processes 415
resulted in SiC whisker yields of 46% vs 3%
for other catalysts (Pt, Pd, Fe, Cu and W).
During VLS type growth, at high MTS
concentrations, the catalyst ball wetting
angle becomes >180 and the ball falls off
(Wagner, 1970).
Although the VLS process has a significant
database of growth characteristics, it has
always been a laboratory-scale type process.
Initial work in scaling up the process to a
commercial level was performed in the mid-
1980s, which was based on the LANL
approach to the process. Further scale-up
was pursued by the Carborundum Company
(Hollar and Kim, 1991). Growth of long VLS
whiskers by a moving zone technique has
been described (Conrad, 1971).
VAPOR PHASE CHEMICAL REACTION
Silicon carbide (SiC) whisker growth pro-
cesses with vapor phase chemical reactions
can be classified into several different
methods according to the precursors and
volatile species involved. The common
thread in all the processes is that silicon and
carbon are allowed to form gaseous species
that can be transported in the vapor phase.
The processes are:
1. Halogen-based precursors;
2. Sulfur-based precursors;
3. Carbothermal reduction of oxide-based
precursors.
Vapor phase chemical reaction using
halogen-based precursors
The halogen-based precursors are based on
the formation of volatile silicon fluorides or
chlorides for vapor phase transport. The
basic reaction is
Chloro-(or fluoro-)silane
+ Carbon source + H2
---> SiC + HCl (or HF) (16.1 )
416 Whisker and platelet synthesis processes
Chlorine-based whisker growth processes
are the most widely used methods to fabricate
SiC whiskers (Postnikov, 1984). This is
because chlorosilanes are readily available
and form vapor species readily at moderate
temperatures.
The same silicon and carbon sources used in
the VLS whisker growth method are used for
the chemical reaction vapor phase growth.
These are namely MTS, Si(CH3 hCl2, SiCl4 ,
CH3 Cl, carbon black, coke and all hydro-
carbon gases (methane, ethane, butane etc.).
In the chlorosilane-based processes, the gas
ratios, concentrations and carrier gas are
critical to proper growth of SiC whiskers.
Typically, Si/C ratios are 1: 1.1-1.3. At
SijC < 1.1, polycrystalline ,8-SiC is produced.
At SijC > 1.5, ,8-SiC with rough surfaces is
produced. When hydrogen is used as the
carrier gas, ,8-SiC is formed, but when nitro-
gen is used, a-SiC is formed instead. The
gas concentrations depend on reactor size,
but are normally low. Reported values are
6-10 x 1O- 3 l/min or 5 X 1O(-3or-4) mol/h.
At high concentrations (>10- 2 mol/h), one
gets polycrystalline SiC. Best growth with
MTS and H2 is reported at 1823 K (1550C),
16kPa (rv 120torr) of MTS and a flow of 0.1-
0.15l/min.
Temperatures employed during chlorine
processes fall within certain ranges for
optimum whisker growth. At temperatures
T> 1923 K (>1650 C), polycrystalline SiC is
formed. When T > 1673 K (> 1400 C), whisker
growth was described as 'curved green-white'
while at temperatures T> 1673K (>1400C)
the whisker growth was described as 'straight
gray-green' .
Fluorine-based processes used Si (or SiC
particulate) reacted with HF to form SiF4 in a
reaction zone at temperatures T::::J 1973 K
(1700C), transport of the gaseous SiF4 into a
second condensation zone, at T::::J 1673 K
(1400C), where it was reacted with CO.
Whiskers 75-150 /Lm in diameter were claimed
by this process. In a similar process, a mixture
of H 2, N2 and Cl2 (or F) was passed over Si and
C at 1373-1753 K (1100-1480 0c). In this case,
whiskers 3-5/Lm in diameter were claimed.
Fluorine-based additives, such as NaF, AlF3,
MgF2' F(g) and HF, have also been used
in other processes. In all these, there is SiF4
generated.
Vapor phase chemical reaction using
sulfur-based precursors
Workers at Nagasaki University used
Si(CH3 )4 and H 2S at temperatures of 1373-
1623 K (1100-1350C) (Egashira, 1985). They
claimed that no catalyst balls were observed,
and the whiskers had tapered ends. Inter-
mediate vapor phase species were either SiS
or SiS2. A related process used H 2S, CO and
H 2, passed through a quartz tube at 1373-
1673 K (1100-1400 0c) (Lee et al., 1973).
Carbothermal reduction reactions using
oxide-based precursors
Carbo thermal reduction reactions using oxide-
based precursors form the basis for nearly all
of the commercial and high volume produc-
tion of SiC whiskers in the world. As such,
the range of materials used for precursors
and the reaction conditions used are virtually
unlimited. While some open literature exists
on these processes, most of the information
is derived from patents. The basic reactions
involved for the carbothermal reduction of
silica are
Si02(s) + C(s) ----> SiO(g) + CO(g) (16.2)
SiO(g) + 2C(s) ----> SiC(s) + CO(g) (16.3)
Si02(s) + 3C(s) ----> SiC(s) + 2CO(g) (16.4)
(Overall reaction)
Silica sources include a wide variety of
materials such as rice hulls (Cutler, 1973),
wheat husks (Motojima et al., 1995), colloidal
silica, silica gel, sea sand and hydrothermal
water. Carbon sources include carbon black,
charcoal and gaseous hydrocarbons. All of

the reported Si/C ratios used excess carbon in
the reaction with the ratios ranging from 0.6 to
3 (by weight). The reactions have been
reported to occur in several atmospheres
including nitrogen, argon, carbon monoxide,
hydrogen and combinations of these. The
reaction temperatures ranged from 1623
to 2073K (13S0-1800C), but were more
typically in the range 1673-1873 K (1400-
1600C). Catalysts used in these processes
include just about every metal and its com-
pounds: Fe, Co, Ni, Nb, Ta, Y, La and Mn to
name a few. Some processes claim that no
catalyst was used, but the impurities in the
raw materials may have acted as a catalyst to
promote growth.
Rice hulls were first used by Cutler (1973)
and Lee and Cutler (197S) to fabricate SiC
whiskers. This technology is the basis for the
largest number of commercial processes. It
was recognized that the rice hulls contain
significant quantities of silica and carbon
which could undergo carbothermal reduction.
As mentioned before, open space is required
for whisker growth to occur and rice hulls
are a very fortuitous structure in that open
space is part of the cellulose structure
(Sharma, Williams and Zangvil, 1984). Thus,
all of the proper conditions are present for
the growth of SiC whiskers to occur.
Other carbothermal reduction processes
do not employ rice hulls, but do require that
the bulk densities of the precursor mixtures
are less than about O.S g/ cm3 . To do this,
materials such as high surface area carbon
black (1S0-S00 m 2 / g) are used to lower the
bulk density. Other additives used to inten-
tionally create pores have also been used,
including sawdust, permeable cellulose and
NaCl. Tokai Carbon claims the NaCl used
in their process not only created pores, but
also increased whisker yield and aided
elongation (Kida, Motohiro and Yamamoto,
1987; Yamamoto, 1985).
Since the carbothermal reduction processes
are the only ones done on a commercial basis
involving large quantities of materials, a great
Silicon carbide whisker growth processes 417
deal of work has been done on reactor design
and configurations for these systems. In the
process, both SiO and CO gases are produced.
While the SiO is an intermediate, the CO is a
by-product that must be removed from the
system. At high concentrations of CO, the
production of SiO is inhibited. Another
consideration in the processes is that SiO gas
is 'heavy' and tends to segregate in systems
using low molecular weight gases (like
hydrogen and nitrogen) or in closed con-
tainers. High SiO concentrations have been
observed to result in irregular growth mor-
phology of the SiC whiskers as shown in
Figure 16.2. A similar growth phenomenon
has been observed with high SiO concentra-
tions during VLS whisker growth (Shalek et
al., 1988). Thus, reactor design to maintain
the proper conditions during whisker
growth is a major component in the produc-
tion process.
Several methods have been employed to
insure proper mixing of the reactant gases
and removal of CO. Purging of the gases by
strategically located gas inlets and outlets
was used by Advanced Composite Materials
Corporation (ACMC) in their reactor (Beatty
and Wyman, 1987). Others used trays with
holes in the bottom and gas flow through the
reactant bed (Schramm and Birtell, 1988;
Tanaka, Kawabe and Kobune, 1986). Another
design used gas flow through a two-zone
process of alternating layers of SiOrC and
fibrous carbon (Nadkarni and Jain, 1987).
In addition to whisker growth, considerable
quantities of SiC particulates are also pro-
duced during carbothermal reduction. Excess
carbon is typically added to the silica to ensure
complete reaction. Any unreacted portion
remains in the product material that comes
directly from the reactor. In fact, reported
contents from a large scale whisker growth
reaction list the products as lS% SiC whiskers,
60% SiC particulates and 2S% residual carbon
(Beatty and Wyman, 1987). Methods to
separate the whiskers from the other con-
stituents include immiscible hydrophobic
418 Whisker and platelet synthesis processes

Figure 16.2 Degradation of whisker growth due to high concentrations of SiO reactant gases.

liquid-liquid separation and froth flotation
(Parekh and Goldberger, 1981; Somasundaran
and Ananthapadmanabhan, 1981). After this
step, the product is oxidized between 823
and 973 K (550 and 700C) to remove any
remaining free carbon (see Chapter 19).
Carbothermal reduction has also been used
to manufacture Si3N4 whiskers (Tanaka and
Kawabe, 1985). The conditions are similar
to those for SiC whisker production except
that nitrogen gas has to be used and the reac-
tion temperatures maintained at T < 1723K

1450 0c). At higher temperatures, SiC is the
stable phase even in the presence of nitrogen.
SILICON CARBIDE WHISKER
CHARACTERIZAnON
PHYSICAL PROPERTIES
The SiC whiskers available at the present time
vary in their physical and chemical charac-
teristics between the different manufacturers.
In many cases, a batch-to-batch variation is
also observed. While the differences may
appear to be minor, such differences can
have a significant influence on the fabricability
of a dense composite and on the toughening
behavior of the whiskers in a composite
material. The differences arise due to different
process methods used by the manufacturers,
such as types of raw materials, catalysts,
reaction atmosphere, furnace configuration
(including off-gas systems) and fabrication
temperatures.
The physical characteristics of selected
currently available SiC whiskers are given in
Table 16.1. The diameter and aspect ratio, in
large part, determines the performance of the
whiskers in a number of applications. For
example, it is known that in alumina matrix
composites the toughening behavior is depen-
dent on the ability of the whiskers to debond
at the whisker-matrix interface and inhibit
crack propagation by crack bridging, crack
Table 16.1 Physical characteristics of various SiC whiskers
Manufacturer and grade
Advanced Composite Materials Corp., SC-9
Advanced Refractory Technology, M
Tokai Carbon, TWS-100
Tokai Carbon, TWS-200
Tokai Carbon, TWS-400
Shin-Etsu, KSC-42
Benchmark Structural Ceramics, 002
Silicon carbide whisker characterization 419
deflection and whisker pullout. The ability of
the whiskers to contribute to these toughening
mechanisms, in turn, is dependent on the
whisker diameter and debond length.
MORPHOLOGY
Visual examination by scanning electron
microscopy (SEM) reveals a wide variety of
morphologies from the different SiC whisker
manufacturers. The diversity of morphologies
is a direct result of the differences in
fabrication parameters used by the various
manufacturers. Several different types of
whisker morphologies are shown in Figures
16.3 to 16.6.
BULK AND SURFACE CHEMISTRY
PROPERTIES
The bulk chemistry of SiC whiskers is mainly
dependent on the starting raw materials and
the catalysts used in the whisker growth
processes. However, other variables, such as
reaction temperature, furnace atmosphere
and oxidizing treatments, also affect the final
bulk chemistry. A comparison of bulk chemis-
tries is shown in Table 16.2. An example of
how the differences in impurity contents are
dependent on the precursors, catalysts and
fabrication techniques used in the manu-
facture of the SiC whiskers can be seen with
the American Matrix Inc. (AMI) whiskers.
Diameter Approximate
range average aspect
(jLm) ratio (l:d)
0.5-0.8 30:1
0.7-1.2 10-25:1
0.3-0.6 10-40:1
0.3-0.6 10-40:1
1.0-1.4 10-30: 1
1.0 34: 1
0.5-1.5 20-200:1
COOOS X = )IS ~OOOZX = )IZ) "6-:::>S apBl~ 'Sla>[S!l{M :::>!S :::>W:::>V 91 aJn~H
Figure 16.4 Tateho SiC whiskers, Grade SCW-IS.
Figure 16.5 Tokai carbon SiC whiskers, Grade Tokamax.
Figure 16.6 AMI SiC whiskers, Grade #1.
424 Whisker and platelet synthesis processes
Table 16.2 Bulk chemistry of selected SiC whiskers
Manufacturer and grade
Al B Ca
(ppm) (ppm) (ppm)
ACMC, SC-9 100-200 <1 100-150
Shin-Etsu, KSC-42 2200 9 <3
Tokai Carbon, TWS-100 <800 50
Tokai Carbon, TWS-400 <800 <10
American Matrix 200 >1000 600
The process used boric acid as a catalyst and,
consequently, large amounts of associated
boron remain in the final product (Nixdorf
and Weaver, 1989a,b). Another example is illu-
strated by the ACMC whiskers. In that process,
rice hulls are used as the starting raw material
and the calcium observed in the final product
is directly related to the calcium content found
in the rice hull precursors. The distribution
of the impurities within a whisker occurs
both on external surfaces and within internal
inclusions (Nutt, 1985, 1988). The oxygen con-
tents are predominantly attributable to silica
and depend mainly on post-growth oxidation
treatments given the whiskers to remove any
residual carbon. These are usually done at
temperatures of 550-700C. Post-oxidation
treatments, such as HF acid leaching, can be
used to reduce the oxygen content (see Chap-
ter 19), but can also leave traces of fluorine
associated with the whisker surfaces.
As mentioned previously, control of the
whisker-matrix interface is necessary for
optimum properties in both ceramic and
metal matrix composites. Consequently, the
SiC whisker surface chemistry is important
because it determines the nature of the
interfacial bond between the matrix and the
whisker (Homeny, Vaughn and Ferber, 1990;
Tiegs, Harris and Geer, 1987). Since the
whisker fabrication methods vary from
different sources, a wide range of surface
chemistries have been observed (Karasek,
1989a,b, 1991). Surface chemistries of SiC
Element
Co Cr Fe Mg 0
(ppm) (ppm) (ppm) (ppm) (wt%)
<10 10-50 50-100 100-300 1-1.3
6 680 9
190 20 90 <200 <0.5
1500 50 210 <500 <0.5
15 25 200
whiskers are commonly characterized by
x-ray photon spectroscopy (XPS) which
analyzes the elements and bonding energies
within about 10nm (100A) of the surface.
Generally, SiC whiskers can be classified
into three broad categories based on this
technique. One category is typified by a high
surface oxygen concentration. The XPS for this
type shows strong Si-O bonding typical of a
surface rich in silica. These types of surfaces
may be a result of the growth process when
oxygen is present or may be due to a post-
growth oxidation treatment commonly given
to whiskers produced by carbothermal reduc-
tion to remove excess carbon from the final
product. A second category of surface chemis-
try has predominantly Si-C bonding energies.
Such a surface is typical of a 'cleaned' material
that has been given a post-fabrication HF
treatment to remove any surface oxides. The
final major category also has strong Si-C
bonding like the 'cleaned' surface, but in
addition has excess surface carbon and
strong C-C bonding. Methods to produce
such surface chemistries include heat-treat-
ment of the whiskers (Tiegs and Lindemer,
1991) and thermal decomposition of a poly-
mer coating of the whiskers (Mroz et aI.,
1994). Alumina coatings on the whisker
surfaces have also been shown to improve
the mechanical properties of alumina matrix
composites (Kato et al., 1995). For alumina-
SiC and mullite-SiC composites, it has been
determined that the presence of excess surface

carbon on the whiskers enhances debonding
at the whisker-matrix interface and resulted
in materials with high fracture toughness. In
contrast, for Si3 N c SiC composites, whisker
surface chemistry was found to have no
effect on interfacial debonding because of the
large amounts of intergranular glass which
dominate the fracture behavior (Tiegs et al.,
1989).
MECHANICAL PROPERTIES
Silicon carbide (SiC) whiskers are nearly
single crystals and thus they are expected to
have very high tensile strengths (Mehan and
Herzog, 1970). Consequently, this makes
them excellent candidates for reinforcement
of composites. It is generally assumed that
the theoretical strength of perfect flaw-free
crystals would be on the order of one-tenth
of the elastic modulus. One would then
expect that SiC whiskers should have tensile
strengths (Tt > 40 CPa. However, tensile
strengths only up to (Tt = 20 CPa have been
reported and most, in fact, are in the range
of (Tt = 3-9CPa (Op het Veld and Veldkamp,
1970; Tiegs et al., 1990). Using composite
properties and back-calculating to whisker
properties, the strengths of some commer-
cially available SiC whiskers have been esti-
mated. These are summarized in Table 16.3.
The whisker strength calculated from compo-
site properties for the LANL whiskers is
essentially the same value obtained by direct
mechanical measurements: (Tt = 8.6 CPa vs
(Tt = 8.4CPa (Petrovic et al., 1985). Thus the
estimated strengths for the other whisker
types are believed to be reasonable. As
shown in Table 16.3, the observed whisker
strengths vary from (Tt = 4.8-8.6 CPa. Com-
parison of the strength values shows that the
VLS growth whiskers from LANL exhibited
the highest strength compared to the other
whiskers derived from the carbo thermic
reduction of silica or rice hulls.
Other mechanical properties of SiC whiskers
of interest include the elastic modulus
Silicon carbide whisker characterization 425
Table 16.3 Calculated mechanical properties for
selected SiC whiskers
Whisker Calculated Estimated
source strength, O"t flaw size
(CPa) (p,m)
ACMC 7.7 0.1-0.2
AMI 4.8 0.2-0.4
Tateho 7.4 0.1-0.2
Tokai Carbon 7.8 0.1-0.2
LANL 8.6
Huber 7.8 0.1-0.2
E :::::: 550 CPa and the fracture toughness
Kic = 3.23 MPa . m 1/2 (Petrovic and Hoover,
1987; Petrovic and Roof, 1984). Using these
values and the estimated strength of the
whiskers, flaw sizes can be calculated as
shown in Table 16.3. The calculated flaw
sizes can be quite large in comparison to the
size of the whiskers themselves. For example,
the strength limiting flaws in selected SiC
whiskers were calculated to be in the size
range of 0.1-0.4 pm, while the diameter of
the whiskers themselves were only slightly
larger. The strength limiting flaws correspond
to defects observed in many of the current
commercial whiskers which, in this size
range, include the core regions (which are an
accumulation of smaller inclusions) and also
voids located within some whisker types
(Allard, Pendelton and Brinen, 1986; Nutt,
1985, 1988; Tiegs et al., 1990). In addition to
these internal defects, excessive surface
roughness is known to decrease whisker
strength (Marsh, 1963; Van Tome, 1966). This
surface roughness is usually associated with
crystallographic phase changes and results
in stress concentrations. Because of their
economic importance, extensive investiga-
tions of the flaws in SiC whiskers derived
from rice hulls have been made using trans-
mission electron microscopy (TEM) (Nutt,
1985). The flaws consist of small, partially
crystalline inclusions (approximately 0.01 p,m
diameter) containing calcium, manganese
426 Whisker and platelet synthesis processes
and oxygen concentrated in a central core
region. While the individual inclusions are
well below the flaw sizes calculated from the
composite strengths, the accumulation of
inclusions in the core region are in the
appropriate size range for the critical flaw.
Similar observations of inclusions have been
made on types of whiskers not derived
from rice hulls (Allard, Nolen and Rawlins,
1989).
PLATELET SYNTHESIS
Platelet synthesis is primarily of interest for
the non-oxides SiC, TiB2 and B4 C for use in
composite materials. The first platelet material
to receive significant attention was SiC which
has recently been shown to increase both
strength and toughness when used as a re-
inforcing material in Si3N4 (Su, Chen and
Lin, 1995). The platelet material takes its
basic shape from the basal plane of the hexa-
gonal close-packed structure which in SiC is
the a-phase. Silicon carbide (SiC) has many
polytypes, but the structure of the SiC plate-
lets is primarily 6H with some 4H present.
There are many patents on the manufacture
Figure 16.7 SiC platelets as formed in the manufacturing process (xlOO).
of SiC platelets utilizing a variety of manu-
facturing techniques. However, it was not
until American Matrix and Carborundum
developed manufacturing processes for high
volume production that SiC platelets became
of interest as a commercial item.
The manufacture of SiC platelets is accom-
plished utilizing a carbothermic reduction
process. For example, a mix of fumed silica
powder and a carbon source, such as
graphite, is thoroughly blended in a V-
blender. The mix is then fired in an argon
atmosphere to 1873-1973K (1600-1700C)
where it is held for an extended period of
time (",10 h). The material is cooled and
remixed, then fired to 2473-2573 K (2200-
2300C). Platelets are formed during this
second firing.
The SiC platelet formation is facilitated by
the addition of catalysts, such as boron,
aluminum and lanthanum. These are typically
added to the mix in the form of compounds,
such as B20 3, which are rapidly accom-
modated by the matrix.
During the formation process, the platelets
will typically bond together at the interfaces.
An SEM photomicrograph of the platelets as
 Platelet synthesis 427

Figure 16.8 Silicon carbide platelets showing interlocking of the platelets and multiple plates growing
from the same crystal (x500).

formed is shown in Figure 16.7. In addition, it right angles or 60 angles corresponding to

is common to observe more than one platelet
out of the same crystal structure. An example
of three platelets growing out of the same
basic crystal structure is shown in Figure
16.8. Note that the platelets appear to be at
the hexagonal crystal structure. On the other
hand, an interface where two platelets have
come in contact during the process and have
begun to sinter together at the interface is
shown in Figure 16.9.

Figure 16.9 Silicon carbide platelets (thickness 8 Jim) that have sintered together at the interfaces (x2000).
428 Whisker and platelet synthesis processes
Figure 16.10 Silicon carbide platelets which have been infiltrated with squeeze cast aluminum alloy A357
(x 100).
The platelet bonding during the processing
can be an advantage if the material is sub-
sequently used as a preform for metal matrix
composites or chemical vapor infiltration. A
photomicrograph of an SiC platelet preform
which has been infiltrated with A357 alumi-
num alloy is shown in Figure 16.10.
Most utilization of SiC platelets, however,
are in the form of a free-flowing powder.
The platelets are normally mixed with metal
or ceramic powders then subsequently pro-
cessed. Consequently, the platelets are nor-
mally deagglomerated in a subsequent step
by a light ball milling process. This results
in some uneven corners and slight edge
chipping. A typical example of the finished
platelet product is shown in Figure 16.11.
Boron carbide (B4C) is another material
which is being offered in the form of platelets.
In the case of B4 C, the platelets can be made
much smaller than SiC. The smaller diameter
of these platelets is beneficial in achieving
better properties in ceramic matrix composites.
Disk-shaped B4 C platelets are shown in Figure
16.12. They are only about 0.2 pm thick.
A third material that readily forms into a
platelet shape is titanium diboride (TiB 2). A
typical process for making TiB2 platelets is to
mix Ti0 2, B20 3 and carbon, then fire to about
1973 K (1700 0c).
Zirconium diboride (ZrB 2) platelets are
manufactured using processes similar to
those described above.
Platelets have some advantages compared
to whiskers and fibers in utilization in com-
posite materials. The platelets are free flowing
and consequently can be easily mixed with
other powders. The platelet shape appears
to be inherently safe to work with. They
offer the optimum shape for crack deflection,
 Platelet synthesis 429

Figure 16.11 Deagglomerated silicon carbide platelets after light ball milling (xlOO).

Figure 16.12 Boron carbide platelets.

430 Whisker and platelet synthesis processes
which is a primary mode of toughening
of ceramic composites. Although platelet
composites have been around for a shorter
time period than whiskers or fibers, they
offer good long term potential for selected
applications.
ACKNOWLEDGMENTS
Research sponsored by the US Department of
Energy, Assistant Secretary for Conservation
and Renewable Energy, Office of Trans-
portation Systems, as part of the Ceramic
Technology Project of the Materials Develop-
ment Program, under contract DE-AC05-
840R21400 with Martin Marietta Energy
Systems, Inc.
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FIBER SYNTHESIS PROCESSES 17
Jonathan Lipowitz

INTRODUCTION A limited number of routes to non-oxide

ceramic fibers are available. They include
This chapter reviews the preparation, compo-
chemical vapor deposition (CVD) processes,
sition, structure and properties of ceramic
in which a ceramic composition is thermally
fibers derived from polymeric precursors.
deposited from the vapor phase on a fiber
Those fibers which have reached a commercial
core (Wawner, 1988). This process is used to
or developmental status will be emphasized.
prepare silicon carbide fibers on a heated
The intent is to show the close relationship
tungsten or carbon fiber core according to:
between process, structure and properties for
ceramic fibers which have been derived from (17.1 )
polymers (Figure 17.1).
The reactions actually used are considerably
Ceramic fibers are desired for reinforcement
more complex, involving addition of
in continuous fiber ceramic matrix composites
CH3 HSiCl2 or (CH3 hSiCl2 to CH3 SiC13, as
(CMC) intended for high temperature use
well as H2 and propane. This process, for
in both oxidative and non-oxidative atmo-
reasons of economics, and because a heated
spheres (Mah et al., 1987; Mazdiyasni, 1990).
fibrous core is required, produces fibers
Controlled interfacial weak bonding between
ranging from 70 to 140/-lm in diameter. Such
fiber and matrix permits non-brittle fracture
fibers do not have sufficient flexibility for
of CMCs with fiber pullout, resembling a
weaving or knitting into preforms for compo-
woody fracture. Fibers having low electrical
site use.
conductivity and low dielectric constant are
Another approach to non-oxide fibers
also being investigated for use in radiation
involves extrusion (spinning) of various
transparent structures such as radomes.
ceramic powders in a polymeric binder. An
Some advantages of the polymer route to
example is the slurry spinning of silicon car-
ceramic fibers include:
bide powder in a binder containing polycarbo-
1. control of fiber purity; silane (Silverman et al., 1991). It is difficult to
2. control of ceramic morphology (amor- obtain ceramic fibers below 30/-lm diameter,
phous or crystalline) and crystallite size; required for weaving and knitting, because
3. ability to prepare continuous fibers of fine the largest grain size of the powder cannot
diameter 30 p,m) suitable for weaving be more than a small fraction of the fiber
and knitting; diameter for strength and integrity during
4. ability to prepare new metastable composi- slurry spinning. Furthermore, tensile strength
tions unobtainable by other means. is limited to ITt ~ 1.4 GPa because the largest

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
434 Fiber synthesis processes
Structure
Performance ~----+--7 Properties
Process
Figure 17.1 The interrelations between structure,
process, properties and performance for materials.
crystallites present serve as critical strength-
limiting flaws.
PROCESS
GENERAL PROCESS
Though the process scheme for preparing
ceramic fibers from organometallic polymers
is simple in principle, the requirements to
obtain high tensile strength fibers are rather
stringent. Almost all routes have used a
similar process scheme which is shown in
Figure 17.2. A polymer is synthesized, melt-
spun to fiber and cross-linked (cured) to
prevent melting on subsequent pyrolysis
to ceramic fiber. This process is related to
that used to prepare carbon fibers from
acrylonitrile (Fitzer and Heine, 1988).
As a rule of thumb, tensile strength, (Tu in
flaw-free brittle materials can reach 10% of
the elastic modulus, E. Thus, for fibers of
E = 200 GPa modulus, an ultimate tensile
strength of (Tt = 20 GPa is the upper limit. An
average tensile strength of (Tt = 2-3 GPa can be
attained after considerable process optimiza-
tion. The strongest fibers attain strengths of
about (Tt = 6 GPa. Tensile strength (Tt is con-
trolled by the nature of the flaws; their size,
shape and location in the fiber (Properties sec-
tion below). In a general sense, a single flaw of
1 p,m effective size in a 1 inch (25.4 mm) fiber
gage length (standard ASTM test method
D-3379-75) will limit tensile strength to
approximately (Tt = 1.5 GPa (Haider and
Clark, 1986; Salinger et al., 1988). For a 10 p,m
diameter fiber, this represents a flaw popu-
lation of only 0.3 ppm by volume. Flaws
commonly develop in ceramic fibers from
particulate impurities, including gelled poly-
mer, from voids and from spinning-induced
defects and mechanical damage during spin-
ning, pyrolysis and other fiber handling
operations (Haider and Clark, 1986; Salinger
et al., 1988).
Fractography, which involves capture and
examination of the primary fracture surfaces
during tensile testing, can be used to deter-
mine the type and location of the critical
flaw which led to fracture failure (Properties
section below). Fractography is a powerful
technique for determining the source of
failure in order to implement process changes
which remove or reduce that flaw population.
However, another flaw population will be
found to again limit strength at a higher
average value.

Organometallic
Organometallic
Preceramic
Reactants
Polymer

Synthesis Spinning Crosslinking Pyrolysis

and (Cure)
Purification
Figure 17.2 Typical processing scheme for preparation of ceramic fibers from organometallic polymer
precursors.

Desirable polymer properties for conver-
sion to ceramic fiber include:
1. a polymer which can be pyrolyzed to the
desired ceramic composition (though com-
position may be modified by choice of cure
chemistry or by use of reactive gases
during pyrolysis);
2. a high purity polymer with minimal par-
ticulate content (particulates interfere with
spinning and introduce critical flaws);
3. a highly branched polymer increases cer-
amic char yield (Schilling, Wesson and
Williams, 1983);
4. a polymer which can be readily spun into
fibers, displaying rheological and thermal
stability during melt spinning;
5. a polymer capable of facile cross-linking to
an infusible fiber after spinning;
6. an air- and moisture-stable polymer.
The spinning process generally consists of
melt spinning at elevated temperature fol-
lowed by drawing under tension to finer
diameter. Multiple spinneret holes are usually
used to increase throughput. Dry spinning, or
spinning from solution followed by solvent
evaporation, may be used to spin thermally
unstable polymers.
The cross-linking, or cure, process can be
accomplished by chemical, thermal or radia-
tion methods. A non-softening polymer fiber
is required during pyrolysis to prevent loss
Cured Polymer
Fiber
Approximate Density 1100 kg/m 3
Mass 1100kg
Volume 1 m3
Figure 17.3 Schematic of polymer pyrolysis process.
Process 435
of shape or interfiber fusion. The cure process
often modifies polymer composition and thus
the ceramic composition by introducing addi-
tional elements in the cross-links. A common
example is oxygen introduced during thermal
air cure.
The pyrolysis process (Figure 17.3), gener-
ally performed in an inert atmosphere such
as argon or a potentially reactive atmosphere
such as nitrogen, converts the cured polymer
fiber to a ceramic product. The process
involves simultaneous loss of several hundred
volumes of gas per volume of initial polymer
and a three- to fourfold volume shrinkage.
The simultaneous shrinkage and loss of
pyrolysis gases leads to a ceramic fiber
which has a density below theoretical for its
composition and displays a closed nanopor-
ous structure (Lipowitz et al., 1990). Indeed,
pyrolysis of preceramic polymer shapes
having larger dimensions than found in
fibers often leads to formation of macroscopic
foams (Walker et al., 1983).
Pyrolytic weight loss begins at about 573 K
(300 DC), though volatiles may be evolved at a
lower temperature. The maximum rate of
weight loss during pyrolysis is often seen at
about 773-873 K (500-600 DC), a temperature
regime in which bond rearrangement reac-
tions and free radical homolytic cleavage
reactions can rapidly proceed. Most weight
loss is complete at 1073 K (800 dc), though
Ceramic Fiber
Approximate Density 2400kg/m 3
Mass 730 kg (33% mass loss)
Volume 0.30 m3
Volume of pyrolysis gases is
485m 3 , assuming loss of volatiles
at an average molecular weight of
50 and an average temperature of
800 K (527C)
436 Fiber synthesis processes
hydrogen may continue to evolve to about
1500 K (1227C). Oxygen and nitrogen (if
present) are lost above 1700 K (1427C) in
thermal degradation reactions (High Tem-
perature Phenomena section below). Pyrolysis
in ammonia has been used to fully or partially
remove carbon from polymers to produce
nitride or oxynitride fiber (Okamura, Sato
and Hasegawa, 1987; Rabe and Bujalski, 1988).
SPECIFIC PROCESSES
Many organosilicon polymer precursors to
ceramics have been described in the literature;
they have been recently reviewed (Baney and
Chandra, 1988). Though many precursors
have been prepared, relatively few have
been pyrolyzed to well characterized ceramic
products and even fewer to high quality
ceramic fibers having useful mechanical
properties. The polymer route has been used
primarily to prepare silicon carbide-like
(Laine et al., 1995) or silicon nitride-like fibers
and silicon carbonitride blends.
Si-C-O fiber
The first silicon carbide-like ceramic fiber to be
developed from a polymer precursor was
reported in 1975 (Yajima, Hayashi and
Omori, 1975). A non-stoichiometric, black
silicon carbide fiber containing oxygen and
excess carbon was prepared from a poly-
carbosilane precursor. As later developed,
the polycarbosilane was synthesized from a
dimethylpolysilane obtained by reaction of
dimethyldichlorosilane and sodium:
xMe2SiCl2 + 2xNa ----> (Me2Si)x + 2xNaCl
(17.2)
. ceramic fiber is produced as a tow consisting
(Me2SiCH2)y(MeHSiCH2)z
(y/z = 1-2)(Mn = 1000-2000) (17.3)
where Mn is the number average molecular
weight in daltons. Rearrangement of the
polysilane to the polycarbosilane (equation
17.3) was originally performed in an autoclave.
In later work, the polydimethylsilane was
thermally rearranged using several wt%
added diphenylborosiloxane, prepared from
diphenyldichlorosilane and boric acid (Yajima,
1983). The borosiloxane addition permits re-
arrangement of the polysilane to a polycarbo-
silane at 623 K (350C) and 0.1 MPa (1 atm)
pressure rather than at 723 K (450C) and
about 1 MPa (10 atm) as required previously.
The structure of polycarbosilane is not
linear, as shown, but was later proposed to
consist of a highly branched planar structure
based on nuclear magnetic resonance (NMR)
data (Figure 17.4). In addition, the structure
contains some Si-Si bonds (Hasegawa and
Okamura, 1983, 1986). It is probable that the
structure is actually three-dimensional.
High and low molecular weight fractions of
the polymer were removed by solvent
extraction and distillation, respectively. This
fractionation is claimed to improve spinability.
Cure and pyrolysis under tension were also
reported to improve tensile strength by produ-
cing straighter fibers (Yajima, Okamura and
Hasegawa, 1981). The fiber is then melt spun
at about 573 K (300 DC), cross-linked by oxi-
dation in air at 448-473 K (175-200C) and
pyrolyzed to 1473 K (1200 0c) in nitrogen or
argon (Yajima et al., 1978; Hasegawa, Iimura
and Yajima, 1980; Hasegawa and Okamura,
1983,1986). This technology has been commer-
cialized by Nippon Carbon Company (Japan)
to produce several silicon carbide-containing
fiber grades under the trade name NicalonTM.
The synthesis of polycarbosilane has been
reviewed (Wynne and Rice, 1984). The struc-
ture and properties of Nicalon fiber have also
been reviewed (Bunsell et al., 1988). Nicalon
of 500 filaments in 500 m (1640 ft) lengths on a
spool. Organic sizing agents are generally
applied to minimize abrasion damage and to
maintain tow integrity.
A modification of polycarbosilane was
obtained by reaction of titanium tetrabutoxide

H
CH 3 H
CH
\ /
Si
/ \
CH 3 H
Figure 17.4 Proposed structure for polycarbosilane. (Hasegawa, Y. and Okamura, K., 'Synthesis of
continuous silicon carbide fiber. Part 4. The structure of polycarbosilane as the precursor,' J. Mat. Sci.,
21(1),321-28, 1986. Reproduced by permission of Chapman & Hall, London, UK.)
with polycarbosilane (Yajima et al., 1981;
Yamamura et al., 1988). The titanium appears
to be bonded to the silicon through oxygen by
infrared spectroscopy. The ceramic fibers,
cured and pyrolyzed similarly to those from
polycarbosilane (PCS), currently contain 1-
3 wt% Ti, considerably less than in the earlier
fibers (Yamamura et al., 1988). This fiber has
been commercialized by Ube Industries, Ltd,
(Japan) as Tyranno ceramic fiber.
Several approaches to the preparation of
polycrystalline silicon carbide fibers which
contain little or no oxygen have recently
been made. Japanese workers cross-link
polycarbosilane fiber using electron beam or
,),-ray irradiation and thus produce a low
oxygen 0.5 wt%) ceramic fiber (Takeda et
al., 1991). These silicon carbide fibers show
considerably improved elastic modulus and
thermal stability compared to Nicalon fibers
which contain rv10wt% oxygen.
Toreki, Batich and Choi (1991) dry spun a
higher molecular weight polycarbosilane
(Mn = 5000) blended with several wt% of a
vinylic polysilazane in toluene and obtained
an infusible polymer fiber which was pyro-
lyzed without cross-linking. Thus, no oxygen
Process 437
is introduced since a cure step is not required
and ceramic fibers are comparable in struc-
ture, oxygen content and thermal stability to
those prepared by radiation cross-linking of
polycarbosilane.
Another approach to polycrystalline silicon
carbide fibers involves addition of several
wt% boron to a preceramic polymer capable
of producing silicon carbide on pyrolysis to
high temperature (Deleeuw, Lipowitz and
Lu, 1991; Lipowitz, Rabe and Zank, 1991;
Rabe and Lipowitz, 1991). Various organo-
silicon polymers, including siloxanes, can be
used as precursors. The addition of boron
permits shape retention and densification at
temperatures (1673-1873K, 1400--1600C),
where fibers undergo loss of nitrogen (as N 2 )
and oxygen (as CO and SiO). The fibers
produced in this manner exhibit the properties
(density, elastic modulus, fracture toughness,
coefficient of thermal expansion, thermal
stability) expected for a polycrystalline,
stoichiometric silicon carbide fiber. Massive
grain growth and pore growth accompanies
gas loss in non-boron-containing fibers and
all useful strength is lost above 1773 K
(1500C).
438 Fiber synthesis processes
Si-N-C fiber
An Si-N-C ceramic fiber has been prepared
from a polysilazane precursor (LeGrow et al.,
1987, 1988). The polymer is prepared by
reaction of trichlorosilane with an excess of
hexamethyldisilazane:
HSiCl3 + Me3SiNHSiMe3
H H H
I I I 1400C). Crystallization to a-Si3N4 fibers was
----t (Me3Si-)13 (-Si- )21( -N- ho( -N-)12
(17.4)
This highly branched polymer is probably
three-dimensional, with Mn ~ 2000 and
Mw ~ 10000 (LeGrow et al., 1987, 1988).
Trimethylchlorosilane was distilled from
the reaction mixture which was heated to
523-573 K (250-300 DC). The resinous hydrido-
polysilazane product had a softening tem-
perature of about 373 K (100C). Melt-spun
fiber was cured with reagents such as trichlor-
osilane (Cannady, 1985a,b). Cured fibers were
pyrolyzed to approximately 1473 K (1200C)
in nitrogen.
Si-N and Si-N-O fibers
It has been known that white, translucent Si-N
and Si-N-O ceramic fibers can be prepared
from a wide variety of preceramic polymers
by performing the pyrolysis in ammonia
(Okamura, Sato and Hasegawa, 1987; Rabe
and Bujalski, 1988). However, fiber strength
has not been particularly high, being limited
to about O"t = 1.8 GPa. A recent patent shows
that cure and ammonia pyrolysis of polycar-
bosilane or polysilazanes performed under
tension gave a higher fiber strength of
O"t > 3GPa (Okamura and Hasegawa, 1990).
A polysilazane, of unknown structure, was
prepared from cyclic dimethylsilazanes by
treatment with potassium hydroxide:
(17.5)
(Me2SiNHh or 4 KOH , polysilazane
573 K (300 'c)
(Mn ~ 1500-2000) (17.6)
Amorphous silicon nitride fibers were
obtained using non-oxidative cure methods
such as electron beam or ,-ray irradiation and
pyrolysis to 1573 K (1300 DC). Pyrolysis was per-
formed in ammonia to 1173 K (900C), followed
by pyrolysis in argon to 1573-1673K (BOO--
observed on pyrolysis to 1673K (1400C) for
polycarbosilane (PCS)-derived fibers. Unlike
the PCS-derived fibers, polysilazane-derived
Si-N fibers remained amorphous on pyrolysis
to 1673K (1400C). Previous work showed
marked strength loss on crystallization to a-
Si3 N 4. The earlier work (Okamura, Sato and
Hasegawa, 1987) also showed that silicon oxy-
nitride fibers were obtained if fibers were air
cured before pyrolysis in ammonia.
Amorphous silicon nitride fibers have also
been prepared from a perhydropolysilazane
precursor (Funayama et ai., 1990; Yokoyama et
ai., 1991). The perhydropolysilazane precursor
was prepared by reaction of dichlorosilane-
pyridine adduct with ammonia. The polymer
was dry spun in xylene solution and fibers
were pyrolyzed in ammonia (Yokoyama et ai.,
1991) or nitrogen (Funayama et ai., 1990) to
1173-1773K (900--1500C). Crystallization to
a-Si3N4 with strength loss occurred at 1473-
1773K (1200-1500C), depending on details
of polymer preparation. Tensile strengths up
to O"t = 4.3 GPa were obtained for amorphous
fibers and an elastic modulus of E = 220 GPa
was found.
COMPOSITION AND STRUCTURE
INTRODUCTION
Before discussing the rich nanometer-scale
structure of these polymer-derived fibers, it
is necessary to describe methods used to
determine composition of these non-stoichio-
metric, generally non-crystalline ceramics. A
 Composition and structure 439
Table 17.1 Typical elemental analyses (wt%) of recent samples of commercial and developmental ceramic
fibers

Fiber a Si C N 0 Other Total

Nicalon (Si-C-O) 58 31 0.1 10 B,0.03 99.1

(Nippon Carbon Co., Tokyo, Japan)
Tyranno (Si-C-O-TO 53 31 0.4 13 Ti, 1.8 99.2
(Ube Industries, Ltd, Tokyo, Japan) B,0.02
HPZ (Si-N-C-O) 59 10 28 4 CI,O.5 101.5
(Dow Corning Corporation, Midland, MI)

a The convention used is to list silicon first followed by additional elements in decreasing atomic abundance.

total elemental analysis, including oxygen, is
first performed (Lipowitz et al., 1987).
Carbon, hydrogen and nitrogen are deter-
mined by high temperature combustion
analysis to totally combust these refractory
ceramics. Oxygen is determined by a carbo-
thermic reduction method. Silicon, chlorine
and trace metals are determined by a sodium
peroxide fusion followed by analysis by
atomic absorption spectrometry or by induc-
tively coupled argon plasma. The closeness
of total analysis to 100wt% can be taken as
an indication of accuracy. In general, a 95-
102% total can be obtained. Typical total
analyses for several fibers are shown in
Table 17.1. The small amount of nitrogen in
Nicalon and Tyranno fibers occurs because
pyrolysis is performed in nitrogen.
A useful way to look at the composition is by
calculation of a hypothetical thermodynamic
composition. This is done by considering the
thermodynamically stable compounds of sili-
con (and titanium) which are similar to those
actually found in the ceramic: TiC, a-Si02
(quartz), a-Si3N4' ,a-SiC (cubic), C (graphite)
and Si (metallic). The elements are then
assigned to silicon and titanium based on
increasing boG of formation (Table 17.2).
Thus, oxygen should first be assigned to
titanium and then to silicon. Though Ti02 is
the most thermodynamically stable of all poss-
ible compounds in the Si-Ti-C-O-N system,
amorphous TiC appears to be formed from a
Ti02 -like species at 1073-1473K (800-1200C)
in Tyranno fiber (Babonneau et al., 1990; Soraru
et al., 1990). Crystalline TiC is observed above
1473 K (Babonneau et al., 1990). Thus, oxygen is
first assigned to silicon and carbon is assigned
to Ti. Nitrogen is next assigned to silicon and
then carbon to silicon. Excess carbon (or sili-
con) is in its standard state. Thermodynamic
compositions are shown in Table 17.3.
X-ray diffraction (XRD) patterns for these
ceramic fibers are shown in Figure 17.5. It is
apparent that the fibers are not in their
stable, crystalline thermodynamic state, but
are in a primarily amorphous, metastable
state. The HPZ fiber is completely amorphous
and the Nicalon and Tyranno fibers appear to
contain nanocrystallites of ,a-SiC. Based on
Scherrer line broadening measurements
using the (111) reflection at 2() = 36 (CuK a ),
,a-SiC crystallite size is about 1.7 nm for
Table 17.2 Gibbs free energies of formation of
some crystalline compounds in the Si-Ti-N-C-O
system
Compound/ llG f298
element (J/mol)
a-Ti0 2 -889.4
a-Si02 -856.4
a-Si3N 4 -647.3
TiC -18D.4
,a-SiC -70.9
Si 0
Ti 0
C 0
440 Fiber synthesis processes
Table 17.3 Hypothetical thermodynamic composi- where Pi, Vi are densities and volume fractions
tion for ceramic fibers in mol% (wt%) of phase i, respectively (Lipowitz et al., 1990).
Equation 17.7 closely approximates the true
Fiber a-Si02 a-Si3 N 4 (J-SiC C TiC
theoretical density if phases and densities
Nicalon 10.8 0.06 60.3 28.8 used closely resemble those present in the
(18.9) (0.25) (70.7) (10.1) ceramic fibers. Thus, amorphous (a) and
Tyranno 13.6 0.2 48.7 36.2 1.3 crystalline phases and densities shown in
(24.6) (1.0) (59.0) (13.1) (2.3) Table 17.4 are used. The phase is assumed to
HPZ 8.6 34.3 32.7 24.4 be amorphous if crystalline x-ray peaks are
(7.4) (69.4) (18.9) (4.2)
not detected.
The ceramic fibers exhibit no orientation
effects as is generally observed for carbon
the Nicalon fiber and even smaller for the and polymer fibers. The low molecular
Tyranno fiber. Though the thermodynami- weight, globular amorphous polymer is
cally stable composition in Table 17.3 does not capable of orientation during spinning
not represent the actual structure of these and the amorphous ceramic phase is also
metastable fibers, it is useful in interpreting incapable of orientation.
the characterization results for these ceramics. All of these fibers contain three or four
Using a volume additivity equation, a theo- phases and exhibit a rich nanostructure:
retical fiber density, Pt, can be calculated:
1. an amorphous continuous phase;
Pt = LPiVi (17.7) 2. dispersed iJ-SiC nanocrystallites in Nicalon
and Tyranno fibers;

Tyranno

Nicalon

HPZ

30
20 (Oeg.)

Figure 17.5 X-ray diffraction patterns for ceramic fibers (CuK" radiation).
 Composition and structure 441
Table 17.4 Density of phases 3. a disperse excess carbon phase;
4. a disperse, globular nanopore phase.
Phase' Density, p
(kg/m 3 )
AMORPHOUS PHASE
Si02 (a) 2200
Si3 N 4 (a) 3000 HPZ ceramic fiber remains amorphous by XRD
SiC (a) 3000 to a pyrolysis temperature of T > 1673 K
SiC(,B) 3200 (1400 C). A 29Si magic angle spinning nuclear
C(py)
Si(c)
2200
2330
magnetic resonance spectrum e
9Si MAS
NMR) shows a single broad signal (Figure
TiC(c) 4900
17.6) which spans the entire chemical shift
a a = amorphous; py = pyrolytic; c = crystalline. range from the upfield Si04 tetrahedral
Source: Lipowitz, J., Freeman, H.A., Chen, R.T. and structure at {j = -110 ppm to the downfield
Prack, E.R., 'Composition and structure of ceramic
fibers prepared from polymer precursors,' Adv. Ceram. SiOC3 structure at {j = +10 ppm (Lipowitz et
Mat., 2(9-10), 1819-31, 1987. Reproduced by permission al., 1987). There are 13 additional mixed
of the American Ceramic Society, Westerville, OH. Si(O,N,C)4 tetrahedral structures possible (15

-46

i I I I I
o -50 -100 -200 PPM
Chemical Shift, Ii

Figure 17.6 29Si MAS NMR spectrum of powdered HPZ ceramic fiber.
442 Fiber synthesis processes
total) which lie between these limits. The peak In Nicalon ceramic fiber, there are five
at 8 = -46 ppm matches the literature value possible oxygen and carbon-bonded tetra-
found for amorphous silicon nitride. It is hedral structures about silicon; Si04 , Si03 C,
therefore assumed that the covalent structure Si02C2, SiOC3 and SiC4 All are present in a
consists of mixed bonding of oxygen, nitrogen deconvoluted 29Si MAS NMR spectrum
and carbon atoms, Si(O,N,C)4' to silicon. In (Figure 17.8). The largest signal present (D)
the infrared spectrum, only Si-O, Si-N and at -15.3 ppm, representing the SiC4 structure,
Si-C bonds can be seen. A model for the is close to the value reported for ,B-SiC at
covalent HPZ ceramic structure is shown in 8 = -18.3 ppm. The intensity of this signal is
Figure 17.7. consistent with the thermodynamic composi-
Such a covalent structure would be tion, indicating that SiC is the major compo-
expected to exhibit considerable strain, and nent present. A peak, due to the mixed
indeed the electron paramagnetic resonance carbon and oxygen bonding to silicon, can
spectrum shows considerable unpaired elec- also be seen in the Si 2p x-ray photoelectron
tron density (Lipowitz and Turner, 1991), spectrum of Nicalon fiber (Lipowitz et al.,
which can be interpreted as dangling bonds 1987; Porte and Sartre, 1989). The peak
with a contribution from unpaired electrons appears at a binding energy between that
in the carbon phase. for Si02 and SiC. Further characterization of
this phase has been performed by the
extended x-ray absorption fine structure tech-
. . . . . . 1 ,,/ \... . nique (EXAFS) and the radial distribution
N N N function method (RDF), using the silicon
-0. . . . . I \ / /
c- absorption edge (Laffon et al., 1989). A struc-
" N /' Si / Si - ....... / ture in which the silicon oxycarbide phase is
/ ' N .... distributed between the ,B-SiC crystallites
)N N / ....... N ./. . . was proposed.
"/N-Si
\ I /' S'I ........ N - Tyranno fiber exhibits a 29Si MAS NMR
spectrum similar to the Nicalon fiber
- N/ . . . . . N - Si - N ..... ....
(Murthy et al., 1989). All five tetrahedral struc-
/ N - Si / I Si ......... c""-
tures about silicon appear to be present.
/-c/ \N......... N
......C
/ \
N
\ ....
/' I / . . . . N / \ /\ I .... ,a-SiC PHASE
/" 'Si Si-N_
-C'- I / \ \ A minimal criterion for confirmation of ,B-SiC
/' I ...... N C 0 in ceramic fiber is detection ofthe (111), (220)
I /1 \ I and (311) intense reflections in the x-ray
diffractogram (XRD). Alternatively, detection
Figure 17.7 Schematic of the amorphous phase of
the HPZ ceramic composition. Each Si atom is tetra- of these three scattered beams in a small area
hedrally bonded to carbon, oxygen and nitrogen electron diffraction (SAD) pattern is sufficient.
atoms in a random manner. Only Si-C, Si-O and Apparent crystallite size has been estimated
Si-N bonds are present. Each C atom is tetrahed- using the Scherrer line broadening method.
rally bonded to four Si atoms; each N atom is The half width of the (111) reflection has
bonded to three Si atoms and each 0 atom is been primarily used, though it is recom-
bonded to two Si atoms. These rules do not take
into account occasional vacancies or dangling mended that consistency of crystallite size
bonds detectable by electron spin resonance (ESR) from the half width of the (220) and (311)
experiments or occasional C-H bonds present and reflections also be considered (Chaim, Heuer
detectable by infrared spectroscopy. and Chen, 1988). Two grades of Nicalon fiber
 Composition and structure 443

Tetrahedral Structure Ii, ppm

A Si0 4 -108.6
B Si0 3 C -72.1
C Si0 2C2 -32.6
o SiC4 -15.3
E Si0 3 -5.8

I i I I i I I i I
20 o -20 -40 -60 -80 -100 -120 -140
Chemical Shift, Ii

Figure 17.8 Deconvoluted 29Si MAS NMR spectrum of powdered ceramic grade Nicalon fiber.

are currently being marketed. A ceramic grade
intended for CMC use and a high volume
resistivity (HVR) fiber. The apparent crystal-
lite size of recent fiber samples ranges from
,,-,0.8 to 4 nm. The lower limit represents
extreme line broadening and a structure
generally considered to be amorphous and is
seen in high volume resistivity grade (HVR)
Nicalon. Typical crystallite size of the ceramic
grade (CG) fiber is ,,-,2 nm.
Larger crystallite sizes are found in Nicalon
fibers pyrolyzed or heat-aged to higher tem-
peratures and in fiber samples having lower
oxygen content. As composition approaches
stoichiometric for SiC, crystallite size increases
on heating to a fixed temperature.
The Tyranno fiber contains "-'1.5 nm crystal-
lites of tJ-SiC, somewhat smaller than in
Nicalon fiber. Earlier samples of Tyranno
fiber, which tended to be high in oxygen
(,,-,20wt%) and in titanium content (>3wt%),
were generally considered to be amorphous
or marginally crystalline as prepared.
Other techniques which have been used to
measure crystallite size include dark field
transmission electron microscopy (TEM) and
high resolution, lattice imaging TEM (Chaim,
Heuer and Chen, 1988). Ceramic grade
Nicalon contains 35vol% (40wt%) tJ-SiC
(Lipowitz et al., 1987). This measurement,
based on a total integrated x-ray profile
analysis, provides indirect evidence for a
dominant amorphous phase.
CARBON PHASE
The presence of elemental carbon in these
fibers can be inferred from the calculated
thermodynamic composition (Table 17.3).
Carbon has been detected by Raman spectro-
scopy in Nicalon and HPZ ceramic fibers
(Lipowitz et al., 1987; Sasaki et al., 1987). Two
bands characteristic of Sp2 carbon phases are
seen at ,,-,1600cm- 1 (graphite-like carbon)
and 1350 cm- 1 (unorganized carbon). From
the intensity ratio of the two bands, an
444 Fiber synthesis processes
apparent crystallite size in the a-axis (polyaro-
matic plane) was estimated at 4 to 5 nm. The
absence of the (002) graphite reflection at
2() = 25 suggests a high degree of disorder
between the polyaromatic planes or long-
technique (Maniette and Oberlin, 1989).
Turbostratic carbon nanocrystallites (basic
structural units, BSU) were proposed in
which the characteristic a-axis length is
rv 1 nm with two or three planes stacked. The

range disorder due to the presence of only a
few stacking planes.
The 13C MAS-NMR spectrum of Nicalon
fiber in Figure 17.9 shows a characteristic
broad signal for polyaromatic carbon at a
chemical shift {j = +140 ppm as well as a car-
bide carbon signal at {j = +22 ppm (Lipowitz
and Turner, 1991). Literature values for gra-
phite aI).d silicon carbide are {j = +155 ppm
(broad) and +15 to +23 ppm for the various
SiC polytypes, respectively. The 13C MAS
NMR spectrum of pure ;1-SiC has not yet
been detected, apparently due to an extremely
long relaxation time, T 1
The carbon phase in Nicalon ceramic grade
fiber has been imaged using a dark-field TEM
BSUs tend to lie parallel to the ;1-SiC crystallite
faces and parallel to the fiber surface. They are
not detected in Nicalon HVR fiber.
NANOPOROUS PHASE
Typical experimental densities, p, found for
these fibers and densities calculated, PC! from
the volume additivity equation (17.1) are
shown in Table 17.5. A pore volume fraction,
p
cp = I - - (17.8)
Pc
is also shown. Note that porosity is calculated to
be presented in all of these fibers. Small-angle
and wide-angle x-ray scattering measurements

+22 ppm

+140 ppm

400 300 200 100 o -100 ppm

Chemical Shift,l>

Figure 17.9 13e MAS NMR spectrum of powdered ceramic grade Nicalon fiber.

Table 17.5 Density and porosity of commercial
ceramic fibers (Lipowitz et aI., 1990)
Fiber DensitY.., Calculated Calculated
density,
P (kg/rrf) pore
Pt (kg/m3 ) fraction, cp
Nicalon ceramic 2600 2770 0.06
grade
Tyranno 2400 2770 0.13
HPZ 2400 2900 0.17
(SAXS, WAXS) show that Nicalon and HPZ
ceramic fibers contain globular nanopores
(Lipowitz et al., 1990). Porosity measurements
of Tyranno fibers have not been reported, but
it is expected that these fibers will show similar
pore structure.
Spherical equivalent pore diameters appear
to be about 1.5 nm in HPZ and Nicalon
fibers. Average pore diameter increases, but
pore fraction decreases as pyrolysis tempera-
ture increases. Similar pore structures have
been recently proposed in amorphous Si-N
and Si-N-O ceramic fibers (Yokoyamo et al.,
1991).
Mercury porosimetry measurements and
Brunauer-Emmett-Teller (BET) surface area
measurements do not detect open porosity in
Nicalon and HPZ fibers. However, TEM
examination of HPZ fibers detected closed,
globular pores of about 30-50 nm in diameter
(Sawyer et al., 1987). Pores are detectable
by TEM only if the pore diameter is a
substantial fraction of the sample thickness.
Self-supporting samples are generally 100 nm
or more in thickness. Thus, only the larger
pores can be detected by TEM techniques.
Porosity is a consequence of the pyrolysis
process in which a large volume of pyrolysis
gas is evolved during densification and trans-
formation of polymer to ceramic. Pyrolysis of
polymer having minimum dimensions larger
than that of fibers or films leads to formation
of foams. The density increase and loss of
gases results in a threefold volume shrinkage
during pyrolysis of fiber. It is believed that
Composition and structure 445
nanometer-scale channels are produced
throughout the pyrolyzing fiber to permit
escape of pyrolysis gases. These nanochannels
collapse to globular pores on further heating
due to a viscous flow process. Thermo-
dynamically, reduction of surface area and
thus reduced surface energy accompanies
the collapse of nanochannels to globular
pores. In support of this hypothesis, HPZ
ceramic fiber pyrolyzed to 1173 K (900C)
undergoes rapid hydrolysis followed by
slow oxidation on exposure to air at room
temperature, whereas pyrolysis to 1273 K
(1000C) leads to air stable fibers (Lipowitz
et al., 1990). It is believed that surface-
connected nanochannels present in high sur-
face area fiber pyrolyzed to 1173 K (900C)
lead to hydrolytic and oxidative instability.
Surface connected porosity is lost on further
pyrolysis to 1273 K (1000 C).
The consequences of porosity include an
elastic modulus, E, lower than that predicted
for the fully dense ceramic as well as
irreversible shrinkage of fibers on initial
heating above the maximum pyrolysis tem-
perature due to further densification. An
example of this shrinkage effect is shown in
Figure 17.10.
The volume fraction of each phase in these
fibers is shown in Table 17.6. Note that in all
cases, the predominant phase is amorphous.
In ceramic grade Nicalon fiber, there is
71 wt% SiC structure present from calculation
of the thermodynamic composition. This is
distributed as 40 wt% ,8-SiC (from x-ray
measurement) and 31 wt% amorphous SiC.
The amorphous SiC component is assumed
to exist primarily in Si(C,O)4 tetrahedral
structures.
LARGE SCALE STRUCTURE
Ceramic fibers are often supplied as a tow
consisting of several hundred to several
thousand filaments on a spool. A sizing of an
organic polymer (1-2 wt%) is often applied for
abrasion resistance and ease of handling.
446 Fiber synthesis processes

Temperature (K)

773 1273 1773

5r---:-~~---:~~~~-:~~---'

-5 -, .... .... . ,-:, .. , .. ....... .~ .... ,... ,-,

.
..
.s~ ::
-10 .............:............. ~ ............ ~ ............ , ..... .
c:
o
'u;
[ij
~ -15 ............ .:........ .. .... ..: .. .......... .:.. .. .. .. , ..... ..: .. -........ ..:.............. ..: ........... .
w . . . . . .
.
. .
.
. .

(ij
E ...
it . 20 ............ ~ ....... ... .. .; ............ ~ .... ..... .... ; ... ....... . ~ ... -.- .. .. --.; ... ........ .
.... ~~

'c (Pyrolyzed to
=> .. 1373 K)
-25 ...... .... .. ~ ............ .: ............ ~ ............. : .... ... ..

-30 ..... .. ..... ~ ............ . ~ ........ .... ~ .. ........... ~ ............ ~

... .. .. ..
. ... . ... .
.
... . ..
.
-35 L---~----------~-----.__----.--~~~--~
o 1000 2000 3000
Temperature (OF)

Figure 17.10 Average thermal expansion for ceramic fibers showing irreversible shrinkage and densi-
fication near the pyrolysis temperature. (Data courtesy of S. Starrett, Southern Research Institute,
Birmingham, AL.)

On a larger size scale than the nanophases PROPERTIES

described previously, these fibers contain
Ceramic fiber properties to be discussed
compositional gradients in the surface region.
include tensile strength, Ut, Young's or elastic
Nicalon fiber exhibits a carbon-rich surface
modulus, E, fracture toughness, K1CI coefficient
layer of ",60 nm thickness by scanning Auger
of thermal expansion, Ct, high temperature
depth profiling (Chang, Zangvil and Lipowitz,
phenomena and electrical properties. Some
1989). The organic sizing had been removed by
properties are shown in Table 17.7.
solvent extraction. Silica-like surface features
have been found on Nicalon fibers in which
sizing was removed by a brief flame exposure.
TENSILE STRENGTH
HPZ ceramic fibers have an oxygen-rich
surface layer of 0.1-O.7/--tm thickness (Chang, Ceramic fibers are brittle and undergo cata-
Zangvil and Lipowitz, 1990). strophic failure as do other ceramics. Tensile
 Properties 447
Table 17.6 Calculated volume fraction of each Fibers are generally tested individually
phase using a universal testing machine at 25 mm
gage length (ASTM D-3379-7S). The primary
Fiber Phase
fracture surface in tensile tests can be con-
Amorphous veniently captured (Li, 1990) and examined
(a) (3-SiC C TiC Pore to provide information on the nature of the
critical flaws present. Fractography, or frac-
HPZ 0.78 0.05 0.17 ture analysis of primary fracture surfaces, is
Nicalon 0.49 0.33 0.12 0.06 a powerful technique used to determine the
Tyranno 0.75 _a 0.11 0.01 0.13
nature, origin and cause of critical flaws
a The volume fraction of this phase is estimated at about (Goda and Fukunaga, 1986; Sawyer et ai.,
0.2. The amorphous phase would then be reduced by this 1987; Bunsell et ai., 1988). Fractography can
amount.
often lead the way to processing improve-
ments which eliminate a flaw population
strength, (Tt, is controlled by critical flaws and result in an increase in strength.
(fracture-initiating flaws) in brittle materials Tensile strength of polymer-derived cer-
as shown by the Griffith equation, amic fibers is often controlled by particulate
impurities in the polymer which form critical
(17.9) flaws in the interior of the fiber (Salinger et ai.,
1988). Another common source of flaws is sur-
where c is the effective flaw size. The fracture face damage during processing.
energy, 2,,(, is that required to form two new A consequence of the Griffith theory is that
fracture surfaces. Size, shape and location of the fracture strength of brittle materials,
the flaw determine the effective flaw size. including ceramic fibers, is statistical and
These primarily amorphous fibers exhibit a dependent on the probability of encountering
classical, glassy primary fracture surface a flaw capable of causing fracture in the
when broken in tension (Figure 17.11). A volume of material under maximum stress,
smooth fracture mirror surrounds the critical at any given stress. For this reason, the
flaw, or fracture-initiation site. The mirror strength of ceramic fibers is volume depen-
radius decreases as stress at fracture increases. dent and increases with decreasing fiber
The fracture mirror is surrounded by a region diameter and decreasing gage length
of hackle created as the fracture planes twist (Sawyer et al., 1987; Bunsell et al., 1988). The
from their original orientation. Hackle lines strength distribution is described by Weibull
point to the critical flaw region. statistics (Goda and Fukunaga, 1986; Bunsell

Table 17.7 Typical properties for some commercial and developmental

ceramic fibers

Ceramic Tensile Young's Diameter Coefficient of

fiber strength, modulus, df thermal
at E (mm) expansion a
(CPa) (CPa) (ppm/K)

Nicalon 2.8 180 10-20 4

Tyranno 3.2 200 10-12
HPZ 2.8 200 10-12a 3

a Equivalent circular diameter for this oval cross-section fiber.

448 Fiber synthesis processes
Figure 17.11 SEM image of glassy primary fracture surface of HPZ ceramic fiber showing critical flaw,
fracture mirror and hackle.
et al., 1988). The Weibull modulus, m, is a
measure of the breadth of the strength
distribution of a sample. The higher the
Weibull modulus, the narrower the strength
distribution.
YOUNGS MODULUS
Young's modulus, or elastic modulus, E, is a
material property, dependent on composition
and structure, which can be theoretically
modeled from a detailed understanding of
composition, chemical bonding, microstruc-
ture and porosity. Reliable measurement of
modulus requires high accuracy in measure-
ment of strain. Because strain to failure is
only about 1%, high accuracy is difficult to
achieve. The most common technique, the
compliance method, corrects the total dis-
placement measured on a universal testing
machine by excluding strain due to
10 JL '111
components other than the fiber itself (ASTM
0-3379-75; Li and Langley, 1985).
FRACTURE TOUGHNESS
The fracture toughness, or critical stress
intensity factor, Klct is the minimum stress
concentration at the crack tip required to pro-
pagate a catastrophic crack.
KJc = (2/'E)1/2 (17.10)
Note that KIc is the numerator in the Griffith
equation (17.9). The fracture toughness can
be estimated from the slope of a plot of tensile
strength vs (mirror radius)1 /2, assuming a
constant ratio between critical flaw size and
mirror radius, which is generally observed
(Sawyer et al., 1987). Data for Nicalon and
HPZ ceramic fiber give a value of KIc::::::
2MPa m 1/ 2. This value is typical for many
o
oxide glasses and provides further evidence,

in addition to the glassy fracture surface, that
the phase which controls fracture behavior in
these fibers is a continuous, glassy phase.
HIGH TEMPERATURE PHENOMENA
As discussed earlier, these fibers are thermo-
dynamically metastable and undergo com-
positional change at high temperature
Properties 449
(Luthra, 1986; Langley, LeGrow and Lipowitz,
1990; Vahlas, 1994). Equilibrium gas phase
composition and pressure above a thermo-
dynamically stable Si-N-C-O composition
are shown in Figure 17.12. The major gases
formed are N 2, CO and SiO.
Material properties at elevated temperature
may change reversibly or irreversibly (Rugg,
Giannuzi and Tressler, 1994). Reversible

PTotal
N2
CO

SiO

-!
5

CD
Si
.c CN
a.
fI)
SiN
Si;14
.sca
0

-
D.
C)
10
CN2
Si2

0
...I
Si 3

.15 .......---~IIIIII!::t------+-----t

19 -1-----+-----+----....
1600 1700 1800 1900
T(K)
Figure 17.12 Equilibrium vapor pressure in the Si-C-N-O system from Si02 (a), a-Si3N4' ,B-SiC, C(s) solid
phases.
450 Fiber synthesis processes
properties are measured at elevated tempera- 2SiC + 302 ----> Si02 + 2CO (17.19)
ture, though in practice some irreversible
degradation may occur. Irreversible proper- Si3N4 + 302 ----> 3Si02 + 2N2 (17.20)
ties, other than creep, often result from thermal Thermal stability of these fibers can be
degradation and may be measured after cool- measured by tensile strength retention after
ing to room temperature. High temperature thermal aging in inert (Ar) or reactive (air)
measurements of single-fiber strength and atmospheres (Figure 17.13). Under inert con-
modulus have been obtained primarily in air ditions, fibers undergo carbothermic reduc-
because of experimental limitations. Rapid tion (equations 17.11-17.13) to form CO and
heating and equilibration times were used to some SiO. Fibers which contain nitrogen lose
minimize thermal and oxidative degradation. N2 above 1673K (1400C, equation 17.16).
Some model thermodynamic degradation Many investigations into the effects of
reactions are shown below: thermochemical exposures on the microstruc-
ture and mechanical properties of ceramic
Si02 + C ----> SiO + CO (17.11)
fibers have recently been made (Bhatt, Garg
Si02 + 2C ----> Si + 2CO (17.12) and Hull, 1994; Yun, Goldsby and DiCarlo,
1994; Gogotsi and Yoshimura, 1995). Coarse,
Si02 + 3C ----> SiC + 2CO (17.13)
crystalline SiC grains are formed along with
SiO + 2C ----> SiC + CO (17.14) CO and some SiO on heating Nicalon or Tyr-
anno fibers in an inert atmosphere above
2Si02 + SiC ----> 3SiO + CO (17.15)
""' 1573 K (1300C) (Mah et al., 1984; Clark
Si3N4 ----> 3Si + 2N2 (17.16) et al., 1986; Sawyer et al., 1986; Bunsell et al.,
1988; Fischbach, Lemoine and Yen, 1988; John-
Si + C ----> SiC (17.17)
son et al., 1988; Murthy et al., 1989). Tyranno
3SiC + 2N2 ----> Si3N4 + 3C (17.18) fibers also form TiC crystallites above 1573 K

3 _ Initial
jg! 100 hJ1273 KiAir
1m 2 hJ1673 KlArgon

o Nicalon

Figure 17.13 Room temperature tensile strength of ceramic fibers before and after aging at specified con-
ditions of time, temperature and atmosphere. Note the typical variations in initial strength with different
fiber lots.

(1300C). At these temperatures, reactions
17.11-17.17 proceed more rapidly than diffu-
sion of gases away from the fiber. A boundary
layer is formed which inhibits gas loss. Thus,
loss of CO from Nicalon fiber and crystalliza-
tion of large SiC grains proceeds from the sur-
face inward (Mah et ai., 1984).
Degradation in vacuum proceeds very
rapidly (Mah et ai., 1984) because the bound-
ary layer inhibiting gas loss is eliminated. A
high pressure argon atmosphere inhibits
Nicalon strength loss by slowing gas diffusion
from the fiber (Jaskowiak and DiCarlo, 1989).
Carbon monoxide inhibits Nicalon and
Tyranno strength loss on aging by inhibiting
reactions 17.11-17.15 (Bender, Wallace and
Schrodt, 1991; Bibbo, Benson and Pantano,
1991).
A nitrogen atmosphere also inhibits degra-
dation of fibers by nitridation of the near-
surface region (Clark et ai., 1986; Zangvil et
ai., 1992):
3Si02 + 6C + 2N2 ----> Si3N4 + 6CO (17.21)
(17.22)
thus inhibiting loss of even non-nitrogen-
containing gases.
Oxidation in air proceeds by a passive
oxidation mechanism in which diffusion of
oxygen through a growing silica layer is often
the rate-determining step (equations 17.19,
17.20). Continued oxidation is inhibited as the
silica layer thickness increases. Parabolic
oxidation kinetics are found, in which the
thickness of the growing silica layer is pro-
portional to t 1/ 2, where t is time (Filipuzzi
and Naslain, 1991). At low oxygen pressures
(for example, below 30 Pa (0.23 torr) at 1673 K
(1400C)), catastrophic active oxidation may
occur:
SiC + O 2 ----> SiO + CO (17.23)
2Si3N 4 + 302 ----> 6SiO + 4N2 (17.24)
However, passive oxidation conditions are
most commonly encountered. The growing
silica layer, which is initially amorphous,
Properties 451
may crystallize above 1375 K (1100C) to
high cristobalite. On cooling, the high to low
cristobalite transition causes cracking and
spalling of the silica layer (Sawyer et ai.,
1986). If the silica layer is of appreciable thick-
ness (",111m), the cracks may serve as
strength-limiting flaws. Oxidation under
mild conditions (~1273 K, 1000C) may lead
to increased fracture strength because of the
flaw-healing effect of the smooth silica surface
layer. A phenomenon often observed to
reduce tensile strength is fusion of adjacent
filaments by the growing silica layer. Evolu-
tion of CO during oxidation, especially in
carbon-rich fibers at higher temperatures
(~1473K, 1200C), can build up sufficient
pressure to create strength-limiting bubbles at
the silica-fiber interface (Sawyer et ai., 1986;
Kim and Moorhead, 1991).
Other gases, such as H2 and H 20, can also
degrade fibers and cause strength loss (Fili-
puzzi and Naslain, 1991; Kim and Moorhead,
1991).
OTHER PROPERTIES
A coefficient of thermal expansion of a =
3.1 ppm/K (Nippon Carbon Co., product
literature) is reported for Nicalon ceramic
grade fiber. The same value is reported for
an older, high oxygen grade of Tyranno fiber
for the range 273-773 K (0-500C) (Textron
Specialty Materials, product literature). The
coefficient of thermal expansion for HPZ
ceramic fiber is a = 3 ppm/K over the range
300-1300K (27-1127C) (Dow Corning Cor-
poration, product literature).
Reported heat capacities are Cp = 720 and
680 JIkg. K, respectively, for Nicalon ceramic
grade and HPZ ceramic fibers, respectively, at
298 K (25C). The values for the older Tyranno
fiber is Cp = 790 (at 330 K, 57C) and
Cp = 1170 JIkg . K (at 673 K, 400C). Thermal
conductivity is given as k = 12 W 1m K for
Nicalon ceramic grade fiber.
Little information is available in the litera-
ture concerning the electrical properties of
452 Fiber synthesis processes
ceramic fibers obtained from polymeric pre-
cursors. Nicalon fibers are available with
volume resistivities, n, varying from n =
0.5 ohm cm for a low volume resistivity
(LVR) grade to n > 1 x 106 ohm cm for high
volume resistivity (HVR) fiber (Dow Corning
Corporation, product literature). The ceramic
grade fiber has n = 1 x 103 ohm cm. A
volume resistivity n = 1 x 103 ohm cm was
reported for the older, high oxygen Tyranno
fiber (Ube Industries, product literature). The
dielectric constant of HVR Nicalon is reported
to be c:' = 6.4 and is 9.2 for the ceramic grade
(Dow Corning Corporation, product litera-
ture). The volume resistivity of HPZ ceramic
fiber is n = 1 x 107 -1 X 1013 ohm cm and
the dielectric constant is c:' = 5.8-6.8 (Dow
Corning Corporation, product literature).
APPLICATIONS
A major application of ceramic fibers is as a
reinforcement material in composites. Matrix
materials include ceramics and glasses,
metals and plastics. Useful properties of
ceramic fibers in composites include high ten-
sile and compressive strength, high elastic
modulus, chemical inertness and high tem-
perature capability, especially in oxidative
atmospheres.
Though plastic matrix composites (PMCs)
cannot take full advantage of the inherent
thermal stability of ceramic fibers, they are
nevertheless desired for electrical properties
in aerospace applications and have been
reviewed (Reinhart, 1987). The mechanical
property profile of PMCs has led to some
applications in sporting goods such as
racquets, skis, golf clubs and fishing rods. A
strong, reinforcing bond between fiber and
matrix is desired to maximize the strength
and stiffness imparted by the ceramic fiber.
This is readily achieved using an oxidized
ceramic fiber surface since the silica surface
is similar to that of glass fibers commonly
used to reinforce plastic matrices. Similar
coupling agent technologies can be utilized.
In metal matrix composites (MMCs), ceramic
fibers are also desired to add strength and
stiffness. Effective wetting of the fiber by the
matrix is important to develop a strong inter-
facial bond. Many metals form metal silicides
on reaction with silicon-containing ceramic
fibers. It is then necessary to apply non-reactive
coatings on the fibers to prevent such reactions.
In ceramic matrix composites (CMCs), the
main function of the ceramic fiber is to
impart toughness by modification of the
brittle, catastrophic failure of the glass or
ceramic matrix material. This is achieved by
creating weak, controlled bonding between
fiber and matrix, often by use of a fiber coating
(Mah et al., 1987; Mazdiyasni, 1990).
The weak bonding between fiber and matrix
deflects crack propagation from the matrix to
the fiber-matrix interface rather than through
the fiber. The large increase produced in frac-
ture surface area dissipates energy, leading to
fiber pullout and fiber bridging of matrix
cracks. This results in an energy-absorbing
'graceful' failure rather than a catastrophic
failure.
The high temperature properties of ceramic
fibers are also used in filter media, insulation,
gasket materials and belting. Nicalon and Tyr-
anno fibers, which display semiconductor
properties, have also been shown to have
utility as infrared sensitive detectors and
thermistors having rapid response due to
their low mass (Muto et al., 1990a,b).
FUTURE DEVELOPMENTS
The development of fibers with new composi-
tions and improved physical, mechanical,
thermal and electrical properties is expected
to lead to new applications. Increased market
volume should lead to large decreases in fiber
cost for these low volume specialty products,
and consequently to a further impetus to
broadened applications.
Improved understanding of thermo-
mechanical stability phenomena is develop-
ing, including details of catalysis of high

temperature critical flaw formation. These
advances are leading to fibers displaying
improved thermomechanical properties
under non-oxidative conditions.
The development of small diameter, weav-
able polycrystalline silicon carbide fiber
having improved high temperature properties
as well as twice the elastic modulus of current
non-oxide fibers is expected to eventually
lead to utilization of CMCs in high efficiency
aerospace engines (Lipowitz et al., 1994). How-
ever, further improvements in CMC properties
and fabrication techniques are also required to
attain the full potential of composite toughness
and high temperature performance, particu-
larly in oxidative atmospheres.
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PART SEVEN
PRE- /POST-SYNTHESIS PROCESSING
Pre- and post-processing unit operations
around the reaction step involve much of the
same types of equipment - mills, calciners
and chemical purification equipment for pre-
paring reactants of the proper purity and size
or for finishing final product powders to meet
required specifications. In addition, many prod-
uct powders are blended with sintering addi-
tives and sold as easily flowable spray-dried
formulated products. These operations are pre-
sented in Part Seven. Various types of mills for
fine grinding are presented in Chapter 18.
Impurities which are either present in the raw
materials or are introduced during the grinding
operation can be removed by chemical leach-
ing. Other impurities, such as carbon, residual
oxides, metals or halides may be present as an
excess unreacted component or a by-product
for certain reactions (Parts Two to Six). These
can be removed by chemical reaction purifica-
tion operations (oxidation using air or acid/
base leaching) which are reviewed in Chapter
19. Finally, Chapters 20 and 21 discuss the pre-
paration of slips (dispersion of solids in liquids)
to prepare non-oxide powders for spray drying
(Chapter 20) and the spray-drying operations
themselves (Chapter 21) for either aqueous or
organic-based systems.
SAFETY ISSUES
Prior to start-up, all unit operations need to be
inspected by a properly organized pre-start-
up safety committee which needs to review
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
such considerations as reactive chemicals,
area monitoring, process control strategy,
personal protective equipment requirements,
waste handling and process procedures.
SIZE REDUCTION
Mechanical guards need to be in place around
rotating components of size reduction equip-
ment. Along with this, automatic shut-off
devices need to be installed so as to cut
power to the equipment if inspection doors
are opened while it is operating. Because size
reduction equipment is often noisy and gener-
ates dust, operators should wear proper
hearing and respiratory equipment. In order
to maintain safe area noise levels, it may be
desirable to locate the equipment in a separate
remote location or to place it in special sound-
insulated rooms. Freshly produced fine dust
may contain a large specific surface area
which is highly active chemically, posing
health hazards and sometimes fire or explo-
sion hazards. Poisonous or explosive
vapors can escape when grinding in organic
liquids. Special disposable protective clothing
may be worn by operators during product
collection operations. Building ventilation
systems need to be properly sized for
removing dusts through outside dust collec-
tors. If inert gases are used in the milling
operations to prevent oxidation of the
powders, it is essential that the equipment
is not maintained in closed areas without
458 Pre-/Post-synthesis processing
proper ventilation and area oxygen monitors
properly functioning.
PURIFICAnON
The removal of carbon by oxidation requires
high temperatures and produces carbon mon-
oxide (CO) which must be properly handled
and disposed of (Part Two). Other impurities
are removed chemically using corrosive
liquids (acids, alkalis) and/ or reactive gases.
Extreme care should be used when under-
taking any of these processes. To guard
against potential hazards (e.g. chemical
burns, thermal burns, explosions, asphyxia-
tion"etc.), all of the materials being used and
the chemistry involved must be thoroughly
understood. Proper protective equipment
should be worn, particularly when handling
strong acids or bases. This includes goggles
or face shields, gloves, shoes and coveralls
all fabricated from suitable materials. In addi-
tion, appropriate atmospheric monitoring
systems should be installed and used to warn
of any leaks in the process. If inert gases are
used, proper area oxygen analyzers should
be functioning continuously.
SOLIDS DISPERSION AND SPRAY DRYING
Non-oxides are often dispersed by milling or
shearing in an organic media. Since these
liquids are most often flammable organic
solvents, both safety and environmental
hazards are of concern. The proper electrical
classification for all motors and other electrical
equipment needs to be specified. Proper
area ventilation systems need to be in
place and all operators need to be dressed
in the proper clothing based upon the
characteristics of the solvents being handled.
Personal respiratory equipment can combine
canisters which are suitable for both dusts
(high efficiency particulate air (HEPA) filters}
and solvents (activated carbon) which are
within acceptable concentrations for their
use.
Conventional spray drying uses heated air
to evaporate liquid. The air and resulting
vapor are exhausted to the atmosphere. This
is dangerous when organic solvents are used
because the mixture of air and organic solvent
vapor can easily be within the explosive limits.
Further, release of the vapors to the environ-
ment is illegal, not to mention expensive. The
solution to these concerns is to close the loop
on the spray-drying process (Figure 21.7).
Once the dried powder is separated from the
drying gas, the solvent is condensed and the
gas is returned to the heater for reuse. Since
the drying gas is being recirculated, an inert
gas such as N2 can be used, eliminating the
possibility of combustion of the solvent
within the drying system.
SIZE REDUCTION 18
Leonard G. Austin and Peter T. Luckie

INTRODUCTION and the power draw are approximately con-

stant, independent of the feed rate to the
Smashing solids with machinery to make
machine. In this case, a low feed rate gives
them smaller is an inherent part of our tech-
the material a long time to be acted upon in
nological society, and occurs in a wide range
the device, and the specific energy, i.e. the
of industries involving an astonishing variety
energy input per unit mass of product, is
of materials and applications. It is one of
high, so that the product size distribution is
the two methods employed to manufacture
finer than at a higher feed rate. In once-
fine powders, the other being chemical
through machines, a low feed rate gives a
precipitation from gas or liquid. It must be
small amount of material mass in the device,
realized that unlike the design of heat exchan-
and the power draw is correspondingly low,
gers, distillation columns etc., there are no
so that the specific energy and the product
sets of fundamentally based process design
size distribution do not change much.
equations for comminution machinery. The
The choice between batch operations or
design equations which do exist are generally
continuous operation is often quite clear
empirical and simply codify past experience.
from the scale of the process. Small scale pro-
It is difficult to apply the basic laws of strength
cesses tend to be in the batch mode because of
of materials to the complex dynamic forces
its simplicity and flexibility and because small
which are used to stress particles to the
scale processes do not warrant the cost of
point of fracture within practical comminu-
control systems or skilled operators. Large
tion devices, and the fracture behavior of
scale systems are nearly always continuous
different materials is widely variable and
because of the greater output per unit time
hard to categorize without extensive empirical
and per unit capital expenditure, and because
testing.
moving large quantities of material from one
place to another is more easily done in a
steady-state continuous design. The choice is
SOME GENERAL DEFINITIONS
more difficult for intermediate scale systems,
AND PRINCIPLES
but the preference will be for continuous
There are two major categories of size reduc- operation.
tion equipment: 'once-through' devices and It is easy to understand the principle that no
'retention' machines. In retention machines, one machine can be suitable for all of the var-
which are those of major interest to us here, ious ranges of size reduction. The concept of
the hold-up of material mass in the device 'stages of size reduction' follows naturally.

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
460 Size reduction
The engineering principles involved are as
follows.
1. The number of stages is chosen that
reduces the largest size of feed down to
the desired product size specification in
steps where each machine in each stage
operates in its efficient region.
2. The capital cost and operating complexity
increase with the number of stages, so
overall grinding efficiency can be sacrificed
with the choice of fewer stages if economic-
ally justified.
Often, the exact quantification of these
principles is not easy or even necessary. The
comparison of costs between performing
more size reduction in one stage with a big
machine, followed by a smaller machine in
the next stage versus the opposite, is often
within the accuracy of the cost estimates. On
the other hand, the number of stages can
usually be determined without equivocation
if sufficient test data are available.
The first piece of information necessary is
the feed size of the material, since the selected
machine must be big enough to accept and
break the largest pieces in the feed. However,
when attempting to develop rules in quantita-
tive form it becomes apparent that defining a
'feed size' to each stage solely by the maxi-
mum size is not satisfactory. Real breakage
processes will give a complete range of size
of product fragments even when breaking
feed lumps of a single size, so the feed to
the next stage must be described by a size dis-
tribution. Sometimes the specific surface
area (m2 I g) of the material is used as an
index of the size distribution. However,
specific surface area is strongly influenced by
the number of particles at the finer end of the
size distribution. In some applications, the
size distribution is characterized by a single
size such as the mean size or the size at
which 80 wt% of the material is smaller.
Neither the 80%-passing size nor the specific
surface area is an absolute index of the size
distribution, but such an index can be a
useful number to be correlated empirically
with the desired performance of the material.
The true description is the total size distribu-
tion, since a change in the shape of the distri-
bution will change the rheological properties,
packing properties etc., even for the same
80%-passing size or specific surface area.
The second piece of information is the
desired size reduction ratio, that is, the final
size specification. It is normal to split the
specification of the product size qualitatively
into five broad categories: coarse size reduc-
tion means a product top size greater than
about 5 mm (rv it- in); intermediate means a
top size between 5 mm and 0.5 mm (rv -ft to
rv -l4 in); fine grinding is a top size between
500 11m and 50 J-tm; very fine grinding between
50 J-tm and 5 J-tm; and ultrafine grinding from
5 J-tm to submicron size. Obviously, it is often
necessary to reach the required product
specification in several stages, using different
equipment in each stage. To decide on the
stages requires an estimate of the size reduc-
tion ratio possible in each stage, which in turn
requires a knowledge of the strength and
abrasiveness of the material.
The arbitrary definitions of very fine and
ultrafine grinding are based on the distinction
that fine grinding to a product of 80 wt% less
than 50 J-tm can be carried out at reasonably
low cost in conventional ball mills, but exten-
sion of the size reduction to the order of 80%
less than, e.g. 10 J-tm, is a much more expensive
operation. Extension to 1 J-tm size is normally
only feasible for very high value products
since the specific grinding energy (kW hi
kg) consumption becomes very large. The
approximate rule that each ten times decrease
in the size range involves an additional six
times energy increase means that grinding to
80%-passing sizes of 100 J-tm, 10 J-tm and 1 J-tm
increases the specific grinding energy in the
ratios 1: 6 : 36. For a desired production rate,
the capital costs will increase in approxi-
mately the same proportion.
There are two types of energy inefficiency
involved in size reduction. The first is when

the machine conditions are poorly matched to
the required duty so that the fraction of input
energy used to produce breakage is less than
it should be. We will call this type a 'direct'
inefficiency. The second, which we will call
an 'indirect' inefficiency, is when the machine
functions well but energy is used to over-
grind some of the product, which is already
fine enough, to product which is too fine.
Then the energy cannot be used to grind the
feed to the desired product, so an inefficiency
results.
Another major engineering principle
involves the decision whether or not to oper-
ate a mill in 'closed circuit', with the product
passed through a size 'classifier' which splits
out one product stream of finer material and
returns another stream of coarser material
back to the feed to the mill. There are several
possible arrangements of an external classifier
with a comminution device. It is also possible
to have internal classification, i.e. within the
device itself. The principle can be stated as
follows.
3. Closed circuit operation is advantageous
when the product must be less than a
specified size and it is also undesirable to
have a large fraction of relatively fine
material, either because it is a disadvantage
in the end use or because it is an indirect
inefficiency in the energy use.
The basic idea is to take the broken material
out of the system before that fraction which is
already sufficiently fine has the chance to be
rebroken and become too fine. This is avoid-
ance of the 'over-grinding' which produces
excess relatively fine material. The limiting
product size distribution - the size distribu-
tion which meets the top size or 80%-passing
size specification and contains the minimum
amount of relatively fine material - is only
achievable when the system uses a 'perfect'
classifier, i.e. one that separates all product
particles smaller than the cut size of the classi-
fying device and returns all particles greater
than the cut size back to the comminution
Some general definitions and principles 461
device. Under these conditions, the shape of
the product size distribution is only depen-
dent upon the feed size distribution and the
basic breakage pattern of the material. Thus,
for a given feed, the shape of the product
size distribution can only be changed by
changing the method of fracture, thereby
changing the basic breakage pattern of the
material.
Although it is rare to see a product speci-
fication which incorporates more than one or
two points on the product size distribution,
there are many applications where the final
product should contain a minimum of fines.
Fines can make flow of a dry powder difficult,
increase the viscosity of a slurry excessively,
absorb too much reagent and give problems
in filtration, thickening, dust collection etc.
While closed circuit grinding with an efficient
classifier makes the shape of the product
size distribution steeper and reduces the
amount of excessive fines in the final product,
equipment which basically produces a narrow
size distribution due to its breakage action
certainly has an advantage for the require-
ment of minimum fines. In general, the use
of an efficient classifier is almost as important
as that of an efficient mill. Unfortunately,
there are very few classifiers which operate
efficiently in the very fine and ultrafine
region, so that the advantage of recycling of
oversize to the mill is not often possible for
very fine material.
On the other hand, if the quality of the
product is enhanced by fines and high specific
surface area, then a machine which basically
gives a flatter size distribution is to be pre-
ferred. Flatter size distributions can also be
produced by splitting the product from the
comminution device, and returning some por-
tion to the feed, i.e. closed circuit grinding
with totally inefficient classification.
It is common experience that intermediate
and fine grinding are often enhanced by
grinding in liquid, by factors of 1.3 to 2
depending on the conditions. Very fine and
ultrafine grinding are usually far more
462 Size reduction
efficient in wet systems and if the material is to
be used in slurry form, then wet grinding is an
obvious choice. However, if the material has
to be a dry powder after grinding, then the
cost and feasibility of filtration, drying and
deagglomeration must be considered. Again,
some types of mills are not suitable for
slurry grinding and even sufficient moisture
content to make the ground material sticky is
a detriment to the behavior of the mills. Thus
the moisture content and flowability of the
ground material are factors to be considered,
since it may be an advantage to choose a gas-
swept system with sufficient heat in the gas to
dry the solid. Of course, a sweeping gas can
also be of a temperature to cool the solid.
Grinding in a liquid may enhance or prevent
chemical reactions with the highly reactive,
freshly fractured surfaces. For example, grind-
ing in an inert liquid may be employed in
special cases where there is a fire or explosion
hazard. Wear losses for steel media in tum-
bling mills are higher in wet grinding, but
for ceramic media, wet grinding gives lower
losses.
The amount of heat generated as grinding
becomes finer can be substantial. When a
solid is stressed to the point of fracture, all
of the solid contains stored strain energy,
but only the strain energy in the immediate
location of the fracture will be used to break
chemical bonds. The rest of the strain energy
is relaxed by the fracture and appears pri-
marily as heat in the material. When there is
a large specific grinding energy there is a
large release of heat in each kilogram of
material. This is removed from the mill by
the hot solid itself, any liquid or gas carrier,
and by heat losses from the mill exterior.
Since the heat generated within the grinding
chamber is proportional to its volume while
the heat passes are proportional to the
chamber area, there may be a scaling problem
in going from a small to a large mill, requiring
expensive cooling systems. Thus, a mill that
uses large quantities of gas per kilogram of
solid has a major advantage since the gas
absorbs the heat and keeps the solid cool,
irrespective of mill size.
In many applications, the contamination of
the ground product by the wear products of
the media or mill shell is of little concern,
although it may still be economically justified
to use higher cost materials in order to reduce
maintenance costs due to wear. In other
cases of specialty grinding, the possibility of
contamination is of prime importance in the
selection of equipment or the materials of
construction.
In some instances, it is desired to use one
piece of machinery on a variety of different
materials according to market demand. In
this case, the ease of cleaning the equipment,
the ease of start-up and close-down, and
the ability of the equipment to be adjusted
to different demands are then important
considerations.
Some mill designs cannot be scaled to larger
sizes because of mechanical or heat limita-
tions, which means it is necessary to have
many small mills in parallel to obtain a
larger output. The economy of scale is then
not available. If a group develops a great
deal of process know-how with a mill which
cannot be scaled, they run the risk of this
knowledge being irrelevant when a larger
market develops and expansion is required.
This, then, is another factor to consider when
selecting a particular type of mill.
COMMINUTION AND FRACTURE
MECHANICS
In principle, the basic science involved in com-
minution is fracture mechanics and strength
of materials. However, the manner in which
forces are applied to cause breakage in a mill
is usually so complex that the mathematical
formulations of fracture mechanics are rarely
applicable. The discipline of strength of
materials is well advanced in describing the
stress states of simple geometries subjected
to relatively simple stresses or strains, and
is extremely valuable in predicting failure

conditions for structures, but the design of
comminution equipment is still largely based
on experience and empiricism. Nevertheless,
it is valuable to understand the basic ideas
about how materials break and some quan-
titative relations have been found to be of use.
We are normally concerned with poly-
crystalline or amorphorous solids, not with
perfect single crystals, so that the materials
approximate isotropic solids on a macroscale,
with uniform stress-strain properties in
different directions. From a 'brittle' fracture
viewpoint, elastic-brittle solids such as non-
oxide ceramics deform linearly and reversibly
with applied stress up to the point of fracture.
Molecular structures with a regular three-
dimensional array of strong chemical bonds
between the atoms or groups in the structure
form rigid, hard, strong materials.
It is found that the tensile stresses required
to give fracture are usually orders of magni-
tude less than those predicted for ideal
solids. The answer to this problem was
formulated by Griffith (1920, 1924). He postu-
lated that real solids contain microscopic
imperfections (flaws) that give points of weak-
ness from which fracture propagated. He
made four basic assumptions.
1. Stress concentration occurs at the tip of the
flaw.
2. At the point of failure the solid is stressed
to where the intermolecular bonds at the
tip are stretched to breaking point by local
tensile stress.
3. The stress state is reproduced at the tip for
an infinitesimal expansion of the flaw.
4. Energy for expanding the flaw as a propa-
gating crack is available from stored strain
energy due to the stressed or strained state
of the solid.
With these assumptions he was able to predict
that failure would occur at applied stresses far
less than expected for ideal flawless solids, if
the flaws were assumed to be long, thin cracks
(Griffith cracks) under tensile stress perpendi-
cular to the length.
Comminution and fracture mechanics 463
The critical stress to cause fracture depends
not only on the fundamental physical proper-
ties of the material and the length of the
Griffith cracks of the solid, but also on the
geometry of the system, since the bulk critical
stresses necessary to stretch the crack tips to
the fracture point clearly depend on the
geometry of the stress application as well.
Obviously, pure compressive stress around a
flaw does not cause it to open and will not
cause crack propagation; hence, tensile stress
is necessary for brittle failure. It might be
thought that tensile stress would not exist
under conditions of bulk compression. How-
ever, more detailed analyses considering
random orientations of the flaws show that
tensile stresses can be produced at the tip of
a Griffith crack at a suitable orientation even
under conditions of bulk loading force by a
compressive force.
The failure of brittle materials has the fol-
lowing major features.
1. Pure brittle failure is almost independent of
temperature, but as temperature increases
to where dislocations are sufficiently
mobile the failure may change to slip,
and, hence, lower strengths at higher
temperatures. For brittle failure with a sig-
nificant plastic energy term, the strength
increases with increased temperature due
to the increase of the size and energy
absorption of the plastic zone around the
tip of the flaw, then decreases if failure
changes to slip.
2. For failure from Griffith cracks, a smaller
particle has a smaller probability of con-
taining a large flaw and will be relatively
stronger. Therefore, as brittle materials
break, the remaining fragments are stronger
because the larger flaws have broken out.
3. Loading of brittle materials with uniform
triaxial compressive stress, hydrostatically
for example, leads to greatly increased
strength, or prevents failure, by reducing
local tensile forces and preventing cracks
from opening.
464 Size reduction
4. When triaxial compression is used to make
a solid less likely to fail, if the solid does fail
at a high (non-uniform) stress, the large
amount of stored strain energy will lead
to greater disintegration and a finer set of
fragments.
Since many comminution processes operate
on particles of very roughly spherical shape,
the stress-strain analysis of spheres is of
particular interest. The simplest solution
(Timoshenko and Goodier, 1952) assumes a
perfectly elastic solid loaded top and bottom
between rigid, frictionless platens, and it
neglects the flattening of the sphere against
the platens at the two points of contact. The
stresses at any point in the sphere are not
constant and, for this point loading, the maxi-
mum tensile stresses in the solid occur along
the loaded central axis. The tensile stresses are
tangential to the horizontal radii, so that
cracks will propagate along vertical radial
planes to form segments like those of an
orange.
Assuming that there is a sufficient density
of Griffith cracks in any region of the solid in
which the maximum tensile stress occurs, the
critical load value which produces fracture
corresponds (via an equation) to a critical
tensile stress which is the one-dimensional
tensile strength of the material. If a sphere
always fractured when the maximum tensile
stress reached the same critical tensile stress
irrespective of sphere diameter, then it can
be shown that the specific fracture energy
would be independent of sphere diameter.
On the other hand, others (Rumpf, 1965;
Steir and Schonert, 1972) have examined the
solution which applies close to the circle of
contact between a platen and the sphere.
This predicts circular cracks near the contact,
which may coalesce to a cone with the base on
the platen and the tip pointing to the center of
the sphere. This cone can act as a wedge to
split open the sphere even when the sphere
is placed under a hydrostatic confining pres-
sure to give sufficient compression to negate
the usual tangential tensile stresses (Habib,
Radenkovic and Salencon, 1966). Experimen-
tal results from compression of small glass
spheres showed behavior fairly close to the
expected pattern, although the strain at a
given loading was greater than predicted
due to some plastic flow or perhaps micro-
cracking before complete disintegrative
fracture. Experimental results on irregular
quartz particles quite clearly showed jumps
in deformations (sudden increases in strain)
due to microcracking, a larger fracture occur-
ring, followed by another smaller fracture at a
somewhat higher stress, then final disintegra-
tion. Before complete rupture occurred, the
particle could be unloaded and reloaded to
give a stress-strain curve much like that
for the glass sphere, but displaced to start at
the permanent strain produced by the prior
partial fractures.
It must be appreciated that the Griffith crack
theory was derived for conditions where
the change in crack length led to a rapidly
accelerating crack because the release of
strain energy was increasingly greater than
the energy required to break bonds. For
small particles, however, it cannot be assumed
that a flaw is so much smaller than the particle
that the particle appears to be infinite in size.
The crack tip of a large flaw may then run into
a region of compressive stress, or into a region
where there is still tensile stress but the energy
available is less than that required to continue
the crack, before it can accelerate to a high tip
energy. The crack is arrested and the solid can
be stressed to a higher strain until a smaller
flaw becomes stress-activated to failure.
Theory predicts that the strength of a
compressed sphere will depend on the size
of the largest flaw existing in the volume at
the center of the sphere which has high tensile
stress. If the maximum size of a flaw (Griffith
crack length) is much less than the size of this
'activated' volume, then 'strength' will not
vary with sphere diameter since the proba-
bility of finding this 'weakest', largest flaw in
the region is unity. However, if the density of

flaws is low, a small sphere will have a lower
probability of such a flaw existing in its small
activated volume, a smaller flaw will deter-
mine the strength, and the sphere will be
stronger. Stronger, in this context, means
that the tensile strength (calculated from
the theoretical equation relating failure load
to tensile strength and sphere diameter)
increases as diameter decreases.
Exactly this type of result was found by
Kanda, Sano and Yashima (1986), with a rela-
tively small change in mean tensile strength
for compression of quartz spheres down to
400 Mm in diameter, then large increases in
mean tensile strength as smaller and smaller
quartz particles were tested. It was necessary
to break 100 particles to get a mean strength
with a low standard deviation of error of the
mean, which again shows the probabilistic
nature of the distribution of size and density
of pre-existing flaws.
The size distribution of the suite of frag-
ments produced on fracture is as important
as the fracture itself, and there exists no
known theory for its prediction. A crack can
propagate slowly if it runs into a region of
compressive stress which closes the tip.
However, theory predicts, and experiment
confirms, that a fracture propagating under
sufficiently high local tensile stress rapidly
reaches a high velocity, of the order of the
velocity of sound in the solid. This leads to a
stress wave which propagates from the crack
tip and this stress wave in turn initiates more
fracture at flaws in the path of the crack. This
leads to bifurcation of the crack, with bifurca-
tion of each of the new arms, and so on, to give
a 'tree' of cracks through the solid. This, of
course, leads to a set of product fragments of
different sizes, and the shape of the size distri-
bution of these fragments is referred to here as
the basic fracture pattern of the material.
The shape of the size distribution from a
comminution process is strongly influenced
by the basic fracture pattern, since even in
repeated breakage this shape tends to be
conserved. Materials which break with a
Comminution and fracture mechanics 465
tendency to chipping and abrasion will pro-
duce a flatter size distribution, while those
that fracture more completely will have a
steeper distribution. Chipping refers to the
knocking-off of projections and angularities,
leading to a more rounded particle plus
irregular-shaped fragments, while abrasion
is the tearing out of tiny fragments from a
particle surface by wear processes, leading to
preservation of the particle shape as it
decreases in size. Materials which fracture
with a high degree of crack branching and
high degree of microcracking around the
crack tips will also produce broad size distri-
butions. Similarly, machines or types of stress
application which aid chipping, abrasion,
crack branching and microcracks will also
produce broad to flat size distributions. The
morphology of particles (angularity etc.) pro-
duced from disintegrative fracture is different
from that of particles produced by chipping
and abrasion.
The energy associated with the rapidly
moving stress wave of a propagating crack
can be sufficient to pass the crack through
macroscopic grain boundaries and through
regions of bulk compressive stress, although
scanning electron microscope examination of
fracture surfaces shows a variety of surface
features, not a microscopically smooth sur-
face, demonstrating that the fracture follows
lines of weakness on a microscale. If fracture
followed grain boundaries, then grinding of a
composite of two materials would rapidly
separate the two materials, 'liberating' one
from the other. This is not often found in
practice and it is more usual to find composite
particles in the product until the particle sizes
approach the grain sizes. Of course, the
decrease in mean size as grinding proceeds
means that a bigger proportion of the atoms
of the solid have the properties of surface
atoms, which are different from the bulk prop-
erties of the solid, even though the shape of
the size distribution may be preserved. It is
worth noting that freshly fractured surfaces
are highly active before adsorption from
466 Size reduction
ambient gases or liquids de-activitate them to
some extent.
A real milling situation will give a set of
fragments which is a weighted mean of the
distributions produced by the range of
impact forces in the machine. In addition, it
must be recognized that the impact or stress
in a size reduction device is rarely applied to
a single particle and is usually simultaneously
acting on a number of particles or a bed of
particles. This also has the effect of averaging
the result of higher and lower impact forces.
HARDNESS AND SPECIFIC ENERGY
FOR GRINDING
The correct choice of a particular type of size
reduction equipment for a particular duty,
and the correct choice of the size of the
machine for a specified capacity, depends
not only on the size of the feed material and
the required reduction ratio but also on the
properties of the solid being comminuted.
Most types of size reduction machines will
give higher capacities for a weaker material;
other types will require the same size of
machine for a specified capacity, but the
power to the machine will be less for weaker
material.
The terms 'hardness' and 'softness' are used
very loosely and it is desirable to define a
more explicit terminology. A material can be
hard in the sense of being abrasive but soft
in the sense of being easily broken when in
the form of large lumps. We will use the
term 'hard' for material with high cohesive
bonding forces, low ductility and high rigid-
ity, and 'strong' for a material which is also
difficult to grind. Such a material will also
often be 'abrasive'. A material which is
basically hard but relatively easy to grind
because of a high degree of pre-cracking or
faulting is 'hard but weak'. A material can be
'soft' with low abrasiveness and low rigidity,
due to ductility, yet be difficult to grind and
thus also be termed 'strong'. The term
'tough' is sometimes used for this case.
Other materials are 'soft and weak', and will
normally have low abrasiveness. Thus, the
Brinell number of a material might be expected
to correlate roughly with its resistance to abra-
sion, but not necessarily with its grindability if
its strength involves macroproperties such as a
structure of large Griffith cracks.
In general, it is recognized that the variation
of the ease of size reduction with particle size
is a function of the change of strength of the
particles with size due to change in flaw struc-
ture, and the change in the efficiency of trans-
fer of mill energy to the strain energy which
causes fracture. However, a feature which is
often observed experimentally is that very
fine and ultrafine grinding is more difficult
than expected from extrapolation of results
on larger sizes. The difficulty of very fine
and ultrafine grinding can be analyzed as
follows.
First, a small particle clearly has a smaller
probability of containing large flaws. As grind-
ing proceeds, breakage occurs from large flaws,
and the smaller fragments produced thus have
fewer and smaller flaws. In principle, very
small particles approach close to ideal strength,
thus the loading intensity (stress) must be
increased to cause fracture.
Second, if one considers the physical act of
stressing particles in any real industrial
machine, it is clear that it becomes more and
more difficult to capture the particles to stress
them as they become smaller. For example,
consider when lumps 10 cm3 in size are
reduced to 10 p,m in size, the fracture media
collision has to strike 1010 0f the small particles
to strike the same mass as for one lump.
Third, it is possible that the cohesive forces
which exist between very small particles
impart special properties to the bed as a
whole so that all particles are less well situated
to receive an impact when fines are present.
(This is different from the previous reason
because it is a physico-chemical effect, not a
simple geometric effect.)
Fourth, it is possible that small particles in
contact under high stress can regrow together.

A distinction must be made here between
simple agglomeration and regrowth. True
regrowth involves the reformation of chemical
bonds between surfaces to give a strong,
dense, refuzed particle. This requires a high
degree of ductility of the particles, so that
the surfaces squeeze into intimate contact. It
is known that very fine grinding can increase
the standard state enthalpy content of a solid,
which suggests massive disorganization of the
structure, so that very fine particles may be
quite ductile. Agglomeration, on the other
hand, does not require ductility and always
gives porosity within the reformed particle.
VERY FINE AND UL TRAFINE GRINDING
Ball mills, equipped with ceramic liners and
grinding media for non-contamination, have
been used 'since ancient times' to produce
fine ceramic powders. However, researchers
studying the preparation of newer very fine
and ultrafine non-oxide ceramic powders,
report that conventional ball milling is not
sufficiently effective. It is well known that
ball milling becomes less efficient as fine
material is allowed to accumulate in the
charge (e.g. Austin et al., 1990). It is certainly
possible to produce material economically in a
ball mill in closed circuit with high efficiency
classifiers with cut sizes of 5-10 JLm and high
circulation ratios that keep fines stripped out
of the mill. However, the necessary equipment
is large for a relatively small output because
of the low power density of conventional
tumbling ball mills. Where contamination
is a problem, there is a large capital invest-
ment in the mill charge consisting of 25-
50mm (rv l-2in) diameter balls made from
the ceramic being ground. It is difficult to
down-scale such a system to small outputs
of laboratory test equipment.
To overcome these problems, it is generally
necessary to move to higher power densities
(kW 1m3 of mill or kW Ikg of media), which
represent higher velocities of impact and a
more rapid rate of input of grinding energy to
Very fine and ultrafine grinding 467
the material being ground. The major groups of
machines which will take the product from
conventional ball milling and prepare from it
very fine or ultrafine material are:
media mills with accelerated media: stirred
media mills and vibration mills;
fluid energy mills;
high speed hammer mills and centrifugal
impactors.
High power densities lead to high rates of
heat release, and excessive temperature rise
is avoided appropriately in each type of
machine. To avoid boiling in a wet system it
is usual to cool the mills with a cooling
jacket and/or circulate the mill contents
through a cooled external reservoir of slurry.
The high rates of grinding also lead to high
rates of wear and, since wear increases expo-
nentially with velocity, the wear rates of
media and linings per kilogram of product
are generally higher than in conventional
systems (Masaki and Wada, 1993).
STIRRED MEDIA MILLS
Interest in stirred media mills for very fine and
particularly ultrafine grinding of specialty
ceramic powders continues to grow steadily.
The recent literature is dominated by new
designs that minimize contamination by con-
structing the mill parts that come into contact
with the powder from the same material as
that being ground, and by new process condi-
tions, such as the use of autogeneous grinding
(using larger pieces of the material to be
ground as the grinding media) and grinding
aids (in order to use slurries with high solids
loading). For example, an all-polymer version
of the turbomill, a rotor I stator stirred media
mill design, has been used to process non-
oxide powers such as SiC, Si3N4 and TiB2
(Hoyer, 1994) by autogeneous grinding.
The basic idea of a stirred ball mill is to
replace the gravitational force of a tumbling
ball mill with higher force by replacing the
natural circulation of balls in the tumbling
468 Size reduction
ball mill by a forced higher rate of circulation.
This is accomplished by stirring the mill con-
tents with pins or discs fitted on a rotating
shaft in a vertical or horizontal orientation,
usually without rotating the mill case. The
maximum possible velocity reached by the
media is that of the rim of a disc or end of a
pin, but it is likely that actual velocities are
much less. The horizontal orientation is pre-
ferred for rapid resuspension of the sedimen-
tation which occurs on shutdown. Angled
discs and pumping loops are employed on
vertical units in order to lift material. The
shaft and pins or discs as well as the shell
lining can be made of the material to be com-
minuted to avoid contamination, if the
material is abrasion resistant. Some manufac-
turers claim that their discs can be made of
plastic even when grinding abrasive solids
because of the lack of particle-disc contact.
One type of stirred ball mill is illustrated in
Figure 18.1. There are dry and wet batch ver-
sions and wet circulation and continuous ver-
sions. The batch and circulation versions are
particularly suited for grinding in flammable
or explosive liquids. The media materials
which can be used on specialty ceramics
include boron carbide (B4C), tungsten carbide
Figure IS.l Batch impeller type stirred ball mill.
(WC), silicon carbide (SiC), silicon nitride
(Si3N 4) and aluminum nitride (AlN). The
size and density of the media have a strong
effect upon the rate of size reduction. Becker
(1990) reports grinding Si3N4 powder with a
mean size of 5.6 JLm (90 wt% < 14.5 JLm) to a
mean size of 1.0 JLm (90 wt% < 2.2 JLm) in 2 h
in a wet (deionized water) batch mill using
6mm (Min) diameter Si3N4 media.
Herbell, Glasgow and Orth (1984) con-
structed a jacketed (for cooling) test mill of
41 (1.06 US gal) volume, 20cm (7.9 in) internal
diameter, using Si3N4 for the body, arms and
media. Only the stirrer shaft (2.6 cm (",lin)
diameter) was uncoated steel. The filling
conditions were 6.16kg (13.6lb) of 6.3mm
(0.25 in) diameter balls, 21 (0.53 US gal) of
ethanol and 400 g (O.88lb) of fine (5 m 2 I g)
Si3N4 powder. The mill speed of lOOrpm
was a tip speed of 0.8m/s (31.5in/s). The
Brunauer-EmmeU-Teller (BET) surface area
increased linearly with grinding time at
about 1 m 2 I g per hour, up to 17 m 2 I g after
12 h. The media contained nearly lO wt% of Y
and the ground product showed significant
increases of C, 0 and Y content, clearly indi-
cating wear dust from the media. No tempera-
ture, power or energy data were given.
Rabe and Link (1992) ground an Si3N4 feed
in a small mill (0.81 (0.21 US gal)) constructed
of an abrasion-resistant polyamide. The stir-
ring pins and media were of sintered Si3N4
(containing AI, Y, 0) and the steel shaft
was coated with the polyamide. The filling
conditions were 600 g (1.32lb) of 1.5-2.5 mm
('" t\-lzin) diameter balls, 200g (0.44lb) of
ethanol and 100g (O.22lb) of fine (9m 2 /g)
powder. The mill speed of 1000rpm was a
tip speed of 5 ml s (16.4 ftl s). The BET surface
area increased linearly with grinding time at
2 m 2 I g per hour, reaching 55 m 2 I g after 24 h.
After 6 h of grinding, the product size distri-
bution (by Sedigraph) was 100 wt% < 2.5 JLm
and 50 wt% < 0.34 JLm. There were small
increases in Fe, AI, Y and C content due to
pickup of wear dust, and 0 content almost
doubled in the 24 h grind; the alpha phase

Figure 18.2 Continuous disc type stirred ball mill.
decreased almost 20% due to amorphization.
It was suggested that 0 increase could be
avoided by ultradrying of the system. No tem-
perature, power or energy data were given.
Another type of mill which has projecting
pins on the case and on the rotating discs to
give additional shearing action is shown in
Figure 18.2. The unit shown is a continuous
unit with a screw feeder, which is supplied
with solid and a liquid. Media are retained
by the narrow annular gap (a few tenths of a
millimeter), through which the slurry dis-
charges, formed between the top rotating
disc and the top of the case. Horizontal
units of up to 2.5 m 3 (88 ft3) in active volume
and 2250kW (3017hp) maximum power, i.e.
almost 100kW /m3 (3.8hp/ft3) power density,
are also available. Le HUi;ln The and Schubert
(1992) studied the autogenous grinding of SiC
in a seven-disc vertical mill of this type (0.71
(2.7 US gal) volume), using a screened size of
SiC as the media. The media was preground in
a vibration mill, presumably to round it by
chipping. The discs were of SiC, the stirrer
shaft was covered with corundum and the
vessel was coated with polyurethane. The
feed was 100wt% < 50/Lm, 95% < 30/Lm,
50% < 8/Lm and 10% < l/Lm (Sedigraph).
Very fine and ultrafine grinding 469
Three slurry concentrations were tested:
7.5, 13.5 and 23.8 vol. % solid in water, and
temperature was maintained at 293-295 K
(20-22 C) by circulation of the slurry through
the mill and an external cooler. Net mill power
was measured but values were not given,
although values corresponded to a specific
grinding energy range of 0.3-2 kW . h/kg
(0.2-1.2hp h/lb) at a rotational speed of
3000 rpm (6.6 m/ s (21.7 ft/ s) tip speed). The
product median size (d p50 ) value over this
range, corresponding to 20-180 min of grind-
ing, decreased from about 4/Lm to about 1 /Lm.
The rate of decrease was highest for the lowest
slurry concentration. However, as the authors
pointed out, the capacity of the mill (to a
specified dp50 of the product) is not highest
for this value since fewer kilograms of solid
are being ground for lower slurry concentra-
tion. The capacity, kg (of product) / t, which
is equal to kg (of hold-up)/t, was approxi-
mately constant for the three slurries.
A media size of 0.8 mm (iz in) (mean of V2
screen interval) was slightly more efficient
than a media size of 1.2 mm (i4 in) and much
more efficient than one of 0.4 mm (it in). It
appeared that 0.4 mm (itin) SiC media were
not capable of breaking the largest feed sizes
since these persisted in the product size dis-
tribution. For the 0.8 mm (iz in) and 1.2 mm
(i4in) media, d p50 (/Lm) >=:; 2.04/(SE)o.7, where
SE is the specific grinding energy, irrespective
of changes in other variables. Tests were also
carried out with the stirrer and discs replaced
by a central cylindrical rotor to give an
annular gap mill. Higher power intensities
can be obtained with this type of mill. At
298K (25C), 2000 rpm (7.9m/s (25.9ft/s) tip
speed) and a gap of 10mm (0.39 in), the rela-
tion between dp50 and specific grinding energy
was improved to dp50 >=:; 1.60/ (SE)O.6, but for a
5mm gap (8.9m/s (29.2ft/s) tip speed) the
relation was as before. This demonstrated
that efficiency decreases if too high energy
intensity is used, other factors being the
same, as is well known from other studies on
high speed stirred mills.
470 Size reduction
Malghan, Minor and Lum (1991) used a hori-
zontal disc mill of 11 (0.379 US gal) volume with
six discs (6.4 cm (2.5 in) diameter), each contain-
ing three 1.2 cm (,..,0.5 in) diameter holes to aid
in flow. All components were of Si3N 4. Loading
by 2mm (~in) diameter Si3N4 balls was 75%,
based on a bed porosity of 44%, leaving a
slurry volume in the mill of 580 cm3 (35.4 in3).
Feed slurry, containing Si3N4 powder of 4 m 2 /
g BET area at a solid concentration of 40 vol. %in
water with 150 ppm of polyacrylate dispersant,
was drawn from a tank (1350 cm3 (82.4 in3,
and product returned to the tank for recycling.
Thus a total test time of t corresponds to the
total mass of solid being ground for a time of
[580/(580 + 1350)]t, i.e. 0.3t. It was found that
the specific surface area increased linearly
with test time at a rate of 3.43 m 2 / g per hour,
at 2600 rpm (8.7m/s (28.5ft/s) tip speed), i.e.
11.4 m2 / g per hour of grinding time. However,
it was also stated that doubling the feed rate
from 240cm3/min (14.6in3/min) to 480cm3/
min (29.3in3/min) halved the residence time
and thus required double the test time to obtain
a certain specific surface area, a statement which
does not make sense in a closed loop system.
Increasing the rotational speed from
2000 rpm to 2600 rpm at the same feed rate
reduced the grinding time by one-half. This
can be compared with the equation by Patton
quoted by Becker (1990) that grinding time is
inversely proportional to the square root of
the rotational speed, which predicts that the
grinding time should reduce by 1.14, not 2.
The observed increase in grinding rate corre-
sponds more closely to (rpm)3. Another feature
of interest is that grinding in isopropyl alcohol
at a concentration of 12 vol. % of solid gave a
somewhat shorter grinding time. However, as
argued previously, this is deceptive because
the mass being acted upon is much less, by a
factor of 12/40 in this case. Unfortunately, no
power measurements were quoted, but it
appears that grinding in water was far superior
to the grinding in alcohol.
The feed material had an unusual bi-modal
size distribution, containing about 7 wt% in
the 2-30/-Lm size range and the rest smaller
than 2/-Lm. The roughly cubical shape of the
larger sizes became more rounded with
grinding time, indicating chipping, and the
particles persisted even though the finer
sizes were reducing in size to give the
observed increase in specific surface area.
We conclude that the 2mm (~in) media size
was not large enough to break the large size
except by gradual chipping. Again, this is in
direct contradiction to the equation of Patton
quoted by Becker (1990) that grinding time
decreases as media diameter decreases.
Obviously, the best media mixture depends
on having enough large media to break the
largest feed sizes efficiently and enough
small media to break the smaller feed sizes.
Patton's work (1979) is based on the dis-
persion of pigment agglomerates and clearly
does not apply to grinding of strong materials.
When stirred mills are used with fine
particulate media, they are called sand mills
(developed originally to break up pigment
agglomerates for the paint industry). With
very fine media, they are called media mills
(a very non-informative name!). The optimum
media size depends on the strength of the
material being ground, the density and
hardness of the media and the rotational
speed. Qualitative rules are as follows.
Strong materials require hard media.
Weaker materials require somewhat smaller
media.
Very weak materials can be advantageously
ground with larger, less dense media, such
as Nylon or Teflon.
Denser media normally pull more power
(other factors being equal) and the higher
power density reduces grinding time.
Media size can be reduced somewhat for
higher density media.
Smaller media diameter requires higher
rotational speed (tip speed) which increases
power density (stirred ball mills fall in the
range 2.5-lOm/s (8.2-32.8ft/s), sandmills
in the range 10-15m/s (32.8-49.2ft/s.

Since larger media size is necessary for
larger particles, but larger media are difficult
to maintain suspended by the stirring action, it
is clear that these mills are specifically for fine
feed material only.
As yet there does not appear to be any quan-
titative equations for optimizing these types of
systems. They are usually operated in the wet
grinding mode and the concentration of solid
and its size distribution in the mill affects the
viscosity, which in turn affects the power
draw and the velocity of media, which
in turn affects the breakage rates (Gao and
Forssberg, 1995). The volume of the mill
filled by media is usually 80-90% based on
the dry packing of the solid, to allow for
expansion during operation. Powder, as
slurry, fills the spaces between the moving
media. The amount of solid being acted on
in the mill varies with the concentration of
solid in the slurry and capacity results
should be expressed not as grinding time
(which is only a valid comparison for the
same mass) but as kg/m3 per hour. If results
are expressed as the specific grinding energy
to give a desired product, the power (kW) for
the mill under the test conditions must be
quoted and a mill power equation is necessary
to design the production mill.
VIBRATING MEDIA MILLS
Vibrating media mills have also been used to
produce very fine, non-oxide ceramic pow-
ders. Like stirred media mills, the mill shell
and media have been constructed of the
same material in order to minimize contami-
nation. A vibratory mill can be regarded as a
variation of a planetary mill in which a cylind-
rical mill is operated in a force field generated
by gyrating the cylinder about an axis. In the
case of a planetary mill, the mill is rotated
about a point outside of the mill and it must
also be rotated about its own axis in order
to cause tumbling of the media. In the case
of centrifugal and vibration mills, the mill
tube itself does not rotate, since this is not
Very fine and ultrafine grinding 471
necessary if the center of the radius of gyration
lies within the cross-section of the mill tube.
The ratio of the gyration diameter to the mill
tube diameter is around 0.4 for centrifugal
mills while for vibration mills it is less than
0.15. The media in a centrifugal mill tumbles
in a manner somewhat similar to a conven-
tional tumbling mill. In a vibration mill the
media is more dispersed through the mill
volume and travels in a circular motion
around the center of the mill. It is usual to
have two or four parallel mills connected
together to reduce off-balance forces on the
support springs.
A horizontal vibrating ball mill is illustrated
in Figure 18.3. The vibrations are transferred
by the walls of the container to the balls, and
each individual ball follows the same short
trajectory during each complete vibration.
Apart from this motion, the whole mass of
media describes a slow circle in the opposite
direction from the circular vibration, which
results in mixing of the material being
ground. The main size reduction is brought
about by the impact between the balls them-
selves and between the balls and the mill
wall. The forces generated are a multiple of
the acceleration of gravity and in practice it
has been shown that an effective size reduc-
tion can be obtained with about five times
the acceleration of gravity. These accelerations
are obtained by adjusting the speed and the
amplitude of the gyration. In most cases, the
best effect is obtained with a high speed and
a small amplitude, since the higher speed
increases the frequency of the impacts which
are necessary for the size reduction. An
increase of the amplitude is only effective if
a relatively coarse feed material has to be
reduced.
Grinding media of various geometries and
compositions are available. As with stirred
media mills the minimum grinding time is
obtained with dense grinding media, and the
spherical shape has proved to be the best. The
size of the media is primarily determined
by the feed size and the ultimate fineness
472 Size reduction

Figure 18.3 Continuous horizontal vibrating ball mill.

required. A ball diameter of 12-15 mm If a grinding size limit exists it is extremely

("" ! - ~ in) is usual in the majority of cases. fine. Similarly, Tanaka et al. (1986) have shown
The most effective media filling is generally that even a conventional tumbling ball mill
about 80% of the total container volume. will produce submicron particles of BaTi03
There is no difference in the specific grinding by batch wet grinding, providing the ball
energy or product size distribution between diameter is reduced as the material becomes
the horizontal or vertical machines, other finer. Starting with a feed of less than 16 p,m,
factors being constant. 192h of grinding gave a top size of 2p,m
In their work on properties of ground SiC (i4
(Coulter Counter) using 2 mm in) diameter
powders, Kanno and Narkano (1992) wet A12 0 3 media, and the BET area increased lin-
ground 20 m 2 / g SiC powders in a vibration early with time to more than 20 m 2 / g. Another
ball mill with the mills and balls made of SiC type of vibrating media mill is shown in
ceramics. The milling liquid was methanol; the Figure 18.4. The grinding chamber is a vertical
media diameter 10 mm (~in). The grinding cylinder or annulus which is filled with
times varied from 6 to 120 h, but they found grinding media (e.g. 12mm (",,!in) diameter
no change in the particle size distribution
after 48 hand 96 h, with a 50 wt% size of
0.25 p,m. Transmission electron photomicro- Table 18.1 Vibration ball mill results
graphs (TEM) suggested that production of
Time Particle size Grinding energy
ultrafine particles by the grinding had reached (min) d p50 (/-Lm) (kW.h/kg)
a limiting particle size which could not be
broken further. However, Wen, Chen and Liu 0 360 0
(1988) ground a titaniferous magnetite sand in 10 60 0.05
a 70W (",,0.1 hp) vibrating ball mill of 11 (0.379 80 4.8 0.4
(i
US gal) volume with 9.5 mm in) steel balls, at 640
2560
0.25
0.052
3
12
a slurry concentration in water of 10 vol. %. 10240 0.011 46
Screening, scanning electron microscopy
(SEM) and scanning transmission electron Source: Wen, S.B., Chen, c.K. and Liu, H.5., 'Size reduc-
microscopy (TEM) were used for size measure- tion of magnetite sand to nanometer powder in a labora-
tory vibration mill,' Powd. Technol., 55, 11-17, 1988.
ment in coarse, fine to very fine and ultrafine Reprinted with kind permission from Elsevier Science
grinding, giving the results shown in Table 18.1. SA, Lausanne, Switzerland.

Figure 18.4 Batch vertical vibrating ball mill.
cylinders). A vibration mechanism is attached
to the base of the grinding chamber and the
energy from the vibrating mechanism is
imparted to the grinding media via the
movement of the mill case. The vibrating
mechanism consists of an electric motor
having a heavy shaft mounted in heavy-duty
roller bearings. At each end of the shaft are
attached 'out-of-balance' weights. The top
weight, which is in the same horizontal plane
as the top of the suspension springs, is con-
nected to the motor shaft in a fixed position.
The top eccentric weight causes a gyration of
the grinding chamber about a vertical axis,
while the bottom eccentric weight provides
a gyrating tilt. This motion causes a three-
dimensional high frequency vibration.
Unlike the other vibrating mills, this mill
has the same level of mill power per mass of
media (power intensity) as a conventional ball
mill, so even with its higher efficiency for very
fine grinding it still requires long periods of
grinding time in order to get micrometer-size
material. The vibrating action causes the
cylinders to pack closely and the cylinders
wear down along the radius. It is not very
Very fine and ultrafine grinding 473
convenient for conversion to continuous
operation because of the low porosity of the
bed of close-packed cylinders. Units are
available up to 40 kW.
FLUID ENERGY MILLS
The basic principle of fluid energy milling is
the high speed collision of particles with a
target or with each other, with the particle
velocity being produced by the expansion of
compressed gas through a nozzle, usually
employing air at about 700 kPa (rv 100 psi) or
steam up to 2000 kPa (290 psi). With stronger
materials, it is advantageous to have a feed
that is less than 250-75 /lm top size; with abra-
sive materials such as SiC, it is advantageous
to have a feed that is less than 75-45/lm. The
high volumes of air used by these mills mean
that there is normally no problem of over-
heating of materials such as can occur with
the high speed stirred media mills. The input
energy eventually is converted to low level
heat when the moving air is stagnated to the
atmosphere, since this converts the kinetic
energy of movement to heat, but the solid is
removed from the air stream before this
occurs. Because of the high circulating ratio
produced by internal or external classification,
the mills produce relatively steep shapes of
product size distributions. The mills are
generally very noisy.
A loop type mill where the feed powder is
picked up by Venturi action and fired into an
elongated doughnut-shaped chamber where it
is accelerated by the expanded gas is shown
in Figure 18.5. The change of pressure on
expansion is by a factor of 20: 1 to 200: 1.
Particles leaving the grinding chamber are
deaccelerated in the increased cross-section
region, which is lined with replaceable wear
liners of cast steel coated with tungsten
carbide or chromium boride. The centrifugal
action in the classifying section stratifies the
coarser particles at the outer periphery where
they are recirculated back to the grinding
chamber. The flow direction of the fluid
474 Size reduction
I ------ll-- __ fluid
Figure 18.5 Continuous loop mill.
carrying finer particles, traveling in the inner
periphery of the torus, is suddenly reversed
and only the finest particles leave the mill in
the outlet gas flow. Units go up to 1650
standard 1/s of air (",3500scfm), that is, about
500 kW (671 hp). The volume of circulating
gas is 5-10 times the amount of gas being
introduced. The same size of unit will use
up to 4500kg/h (9912lb/h) steam, which
is an energy equivalent of about 3700 kW
(4962hp). For very fine grinding, an appro-
priate external classifier is incorporated. The
cost of grinding is greatly reduced if the spent
steam can be re-utilized in some other part of
the plant.
Another major type of fluid energy mill is
the pancake type illustrated in Figure 18.6.
The mills grind and classify in a single shallow
cylindrical chamber with dished heads, built
up to 0.75 m (2.5 ft) in diameter. The high
pressure air or steam is introduced through
peripheral jets, spaced at regular intervals
around the periphery of the grinding cham-
ber. The axis of each jet is tangent to the
circumference of a smaller, tangent circle.
The most efficient tangent circle jet angle is
60. This means that for a 0.75 m (2.5 ft)
diameter mill, the tangent circle is 0.5 m
(",20 in) in diameter. During operation, a
high speed vortex is generated, and material
powder
Figure 18.6 Continuous pancake mill.
to be pulverized is injected through a Venturi
feeder into the vortex near the peripheral wall.
High velocity gradients near the jets cause the
suspended particles to collide and grind one
another by impact. The grinding fluid exits
through an outlet at the center of the chamber,
drawing the fine particles with it to the
collection system. The larger particles are
kept in the grinding area by centrifugal
force. The cut size of the internal classification
depends on the velocity of the grinding fluid
since a higher velocity will give more cyclone
action and reduce the cut size. The outlet zone
can also be adjusted in height to aid classi-
fication. A high solid feed rate has the
opposite effect since it will increase the effec-
tive density of the solid-air stream, and the
laws of expansion through nozzles show that
the higher density means lower velocity. Thus
the finest product is produced by a high fluid/
solid ratio, but there must be a minimum feed
rate of solid to insure sufficient mill loading
for particle collisions. This mill can easily be
lined with polyurethane, we or, for non-
contamination, with the same material being
ground. It is readily taken apart for cleaning.
Another fluid energy mill design which has
recently been introduced is the fluidized bed
jet mill illustrated in Figure 18.7. It is an
opposing jet design. Multiple air jets, aimed
at the center and opposing each other, are
positioned around the circular grinding
chamber. Particles are fed into the bottom of
the grinding chamber, and, with the help of a
center jet aimed vertically, become part of a
 Criteria to be considered in selection of equipment
.... powder
fluid
Figure 18.7 Nozzle section of the grinding chamber
of a fluidized bed mill.
constant level bed of material maintained in
the chamber. Ground material and air rise
into radial vane classifiers which reject large
particles back into the bed and allow the fine
particles in the air stream to exit. The speed of
the multivaned rotors determines the fineness
of the product.
Ghosh (1993) reports that fluidized bed jet
mills consistently produce ceramic powders
with a 50%-passing size in the 10-1 /-lm range
with reactive surfaces and low contamination.
The contamination is minimized by utilizing
urethane liners and ceramic nozzles and
classifier rotors. He claims that the fluidized
bed jet mill gives a lower specific grinding
energy for a given dp50 value than a pancake
mill. Capacities of three mills of different
size are quoted in Table 18.2.
HIGH SPEED HAMMER MILLS AND
CENTRIFUGAL IMPACTORS
High speed hammer mills are very versatile
mills with high power densities. They are
available in a range of sizes from laboratory
scale upward. For very fine and ultrafine
grinding, high tip speeds are necessary,
typically 100m/s (328ft/s). The high speed
rotation pulls air (or controlled atmosphere)
into the machine with the feed, and the
powder flows through the built-in high
speed rotating classifiers in the air stream.
The high air flow ratio removes the heat of
475
Table 18.2 Fluidized bed jet mill grinding results
Material Outlet, d p50 Capacity (kg/h) of model
(11 m)
200 400 600
SiC 4.8/4.0 45 105
Si3N4 1.5 10
TiB2 2.0 25
ZrB2 8.0 20
Source: Ghosh, B., 'Fluidized bed jet milling of ceramics,'
Am. Ceram. Soc. Bull., 72(5), 51-54, 1993. Reproduced
by permission of the American Ceramic Society, Wester-
ville,OH.
grinding and there is usually no heat problem
with grinding of brittle materials. It appears
that the mills have not become popular in
the specialty ceramic field, presumably
because of high rates of abrasion, the difficulty
of making or coating components with the
same material as that being ground and
because they cannot be used for wet grinding.
Instead of the powder being struck in air sus-
pension by high speed hammers, centrifugal
impactors throw the powder against anvils. It
is difficult to accelerate very fine powders with
a spinning disc, so particle velocities do not
necessarily reach the 300 m/ s (984 ft/ s) tip
speed of the disc and recirculation with fine
classification is necessary for fine grinding.
CRITERIA TO BE CONSIDERED IN
SELECTION OF EQUIPMENT
The general objective is always the same: To
produce a product of suitable quality, at a
desired capacity, with a minimum of cost
(including capital, labor and maintenance), at
an acceptable level of reliability, under safe
conditions for personnel and the environ-
ment.' However, this kind of statement of
objective is too vague to be of much use to
the process engineer who has to make the
selection. This is because of the wide vari-
ability from process to process of the weight-
ing factors for each criterion involved in the
statement when applied to size reduction.
476 Size reduction
QUALITY OF PRODUCT
It is not possible to proceed along the design
path without a specification of what product is
desired. However, the complexity of the
specification is widely variable depending on
t~e end use f~r the product. For example, a
fme powder mIght be required to have a maxi-
mum top size, a precise median size, a mean
shape factor within a certain range, a desired
specific surface area, and impurity levels in
the parts per million range.
CAPACITY
A design must specify a capacity (kilograms
per hour or per working day, liters per hour,
num~er of batches of a specified size per
working day etc.). It is normally crucial that
this capacity is achieved, especially for a low
value, continuous type of process since under-
capacity may eliminate the profit margin.
MINIMUM COST
There are three main factors to be considered.
The first is the specific grinding energy of
the process which determines the cost for
electricity per unit mass of product. Values
ofkW h/kg are quoted for size reduction
equipment for common materials and a cer-
tain size reduction. The second factor is the
capital cost, which determines the debt
expense per unit mass of product. It must be
always remembered that a highly efficient
process with a low specific grinding energy
may be quite uneconomic if it is obtained by
very low plant capacity. The third factor is the
cost of maintenance, supervision etc. Simple,
robust equipment gives lower costs in this
category.
LEVEL OF RELIABILITY
The acceptable level of reliability varies
widely from process to process, being of
crucial importance for a low value process
where the rest of the fixed costs have to be
paid even when the failure of a piece of size
reduction equipment has closed down the
process. Even when constant repair does not
cause an undue financial burden, there is a
strong incentive to choose a piece of equip-
ment which is reliable over a more efficient
or cheaper unreliable machine.
SAFETY AND ENVIRONMENTAL FACTORS
These cannot be ignored. Nearly all size reduc-
tion equipment is potentially mechanically
dangerous to operators, but generally the man-
ufact~rers go to great lengths to ensure safety,
even m the event of failure of a component. On
the other hand, operators can remove safety
guards, open inspection doors while the
machine is operating etc., and it can be advis-
able to have automatic shut-off devices in some
~ypes of eq~ipment. Size reduction machinery
IS often nOISY and the provision of safe noise
levels for the operators can add extra costs to
be considered in comparing one machine
with another.
Mills also often produce dust and the
health aspects of the dust inhalation by per-
sonnel must be considered, as well as any
longer range environmental deterioration. It
~ust be recognized that freshly produced
fme dust may contain a large specific surface
area which is highly active chemically, posing
~ealth hazards a~d sometimes fire or explo-
SIon hazards. POIsonous or explosive vapors
can escape when grinding in organic liquids.
The choice of a particular machine over
another is sometimes made solely from
safety considerations.
REFERENCES
Austin, L.G:, Y:keler, M., Dumm, T.F. and Hogg, R.
(1990) KmetIcs and shape factors of ultrafine
grinding in a laboratory tumbling ball mill. Par-
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Becker, J.E. (1990) Stirred ball mills. Ceram. Eng. Sci.
Proc., 11(11-12), 1827-37.

Gao, M. and Forssberg, E. (1995) Prediction of
product size distributions for a stirred ball mill.
Powder Technol., 84, 101-06.
Ghosh, B. (1993) Fluidized-bed jet milling of
ceramics. Am. Ceram. Soc. Bull., 72(5), 51-54.
Griffith, AA (1920) Phenomena of rupture and
flow in solids. Phil. Trans. R. Soc. (Lond.), A221,
163-98.
Griffith, AA (1924) The theory of rupture, in Proc.
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Habib, P., Radenkovic, D. and Salencon, J. (1966)
Rupture des roches ecrasees entre les plateaux
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Herbell, T.P., Glasgow, T.K. and Orth, N.W. (1984)
Demonstration of a silicon nitride attrition mill
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Hoyer, J.L. (1994) Turbomilling: a processing tech-
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Kanda, Y., Sano, S. and Yashima, S. (1986) A con-
sideration of grinding limit based on fracture
mechanics. Powder TechnoI., 48, 263--67.
Kanno, Y. and Narkano, K (1992) Electron micro-
scope and x-ray diffraction studies on the fine
structure of ground beta-silicon carbide powders.
Powder Technol., 71,59--64.
Le Huan The and Schubert, H. (1992) Autogenous
grinding of silicon carbide in stirred mills with-
out grinding aids. Aufbereit.-Tech., 33(10), 541-50.
References 477
Malghan, S.c., Minor, D.B. and Lum, L.S.H. (1991)
Silicon nitride powder milling kinetics in a high-
energy agitation ball mill. Powder Technol., 67,
201-06.
Masaki, H. and Wada, S. (1993) Wear of media balls
during the ball milling of silicon nitride powder.
J. Ceram. Soc. lpn., 101(Feb.), 221-23.
Patton, T.C (1979) Paint Flow and Pigment Dis-
persion, 2nd edn, Wiley-Interscience, New York.
Rabe, T. and Link, D. (1992) Attrition milling of
silicon nitride powder under conditions for
minimal impurity pickup. Ceram. Int., 18, 161-
66.
Rumpf, H. (1965) Die einzelkomzerkleinerung als
grundlage einer technischen zerkleinerungs
wissenschaft. Chemie-Ing. Techn., 37, 187-202.
Steir, K and Schonert, K (1972) Verformung und
bruchphanomene unter druckbean spruchung
von sehr kleinen aus kalkstein, quartz und
polystyrol. Dechema Monogr., 69(1297), 167-92.
Tanaka, K, Minai, K, Wakino, K and Dei, L. (1986)
The submicron grinding of BaTi03 by ball
milling. J. Soc. Mater. Sci. lpn, 35, 54-58. (English
trans. (1987) Kona, 5, 1824.)
Timoshenko, S. and Goodier, J.N. (1952) Theory of
Elasticity, 2nd edn, McGraw-Hill, New York,
pp.372-84.
Wen, S.B., Chen, CK and Liu, H.S. (1988) Size
reduction of magnetite sand to nanometer
powder in a laboratory vibration mill. Powder
Technol., 55, 11-17.
CHEMICAL PURIFICATION
Kevin J. Nilsen and Alan W. Weimer
EFFECT OF CHEMISTRY ON PROCESSING
AND PROPERTIES
The chemistry of a starting non-oxide powder
has a large effect on the processing and
properties of densified parts. In general, the
properties that make non-oxides so attractive
for advanced applications are invariably
decreased with the presence of chemical
impurities. Some of the properties affected
are final density, strength (high and low
temperature), creep resistance, corrosion
resistance, thermal conductivity and wear (tri-
bologicaD properties.
For example, the presence of iron in silicon
nitride (Si3N 4) in any significant proportion
can decrease the high temperature properties
of the final part (Bennett and Houlton, 1979;
Shuster, 1988) and also act as a flaw origin
(Pasto, 1984; Figure 19.1). Silicon (SO reacts
to form other metallic silicides which decrease
the activity and the high temperature strength
of Si3N4 (Elliott, Gleiser and Ramakrishna,
1963).
A second example is the effect Si has on the
thermal conductivity of aluminum nitride
(AlN). The Si reacts to form secondary phase
silicates which then act as phonon scattering
sites which decrease the thermal conductivity
(Figure 19.2) of AIN parts (Knudsen et al.,
1992).
A third example is the effect oxygen and
transition metals have on the densification
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
19
behavior of solid-state-sintered silicon carbide
(SiC). The densification of SiC, using boron
additives and carbon as sintering aids, is
adversely affected by oxygen in the follow-
ing way. Too much oxygen, present pre-
dominantly as silicon oxide species, causes
the densification to be adversely affected
by evaporating and condensing in the
neck regions at the particle contacts (Kriegs-
mann, 1987). This inhibits the densification
process (Figure 19.3). Transition metals (par-
ticularly iron) inhibit densification of fJ-SiC
during sintering by enhancing exaggerated
grain growth which entraps porosity (Figure
19.4).
A fourth example is the adverse effect
carbon has on the sintering of Si3N 4. The
decreased densification has been attributed
to the carbon reducing the oxide present on
Si3N4 to volatile SiO. The subsequent change
in glass composition deleteriously affects
Si3N4 sintering (Hausner and Peitzsch, 1984;
Woetting and Ziegler, 1986) and high tem-
perature oxidation resistance (Knoch and
Gazza, 1979) of Si3N4 materials.
A final example is the adverse effect
chlorine and fluorine can have on the dis-
solution of nitrogen in the glassy phase of
Si3N4 (Asayama et al., 1994; Drew, 1989;
Isozaki et al., 1994). The decreased dissolution
of nitrogen in the glass prevents grain-
boundary phase crystallization in sintered
bodies and results in decreased high
480 Chemical purification

(a) (b)

8000
Si

Fe

AI Au Pd
Au

0.0 10.0
Energy (keV)
(c)

Figure 19.1 (a), (b) Metallic-inclusion-type defect at fracture origin in sintered silicon nitride shown
in scanning electron micrographs of fracture surfaces; (c) energy dispersive x-ray spectrum of inclusion
in (b). (Pas to, A.E., 'Causes and effects of Fe-bearing inclusions in sintered Si3 N 4 : J. Am. Ceram. Soc., 67(10),
C-178, 1984. Reproduced by permission of the American Ceramic SOciety, Westerville, OH.)

temperature strength. In addition, the pres- ORIGIN OF CHEMICAL IMPURITIES

ence of fluorine on the surface of Si3N4 has
been found to have undesirable effects on
aqueous processing (Drew, 1989).
These examples illustrate the importance of
chemical purity to achieve high performance
properties in non-oxide systems.
In addition to chemical purification, another
reason to post-treat non-oxide powders is to
enhance their processing and/or to protect
the powder surface from degradation. The
need for treatment of non-oxide powders is
due to their inherent instability in air
described later in this chapter.
The primary chemical impurities that can be
present in non-oxide powders are carbon,
oxygen, metals and halogens.
The presence of free carbon or carbon-
containing impurities in non-oxide powders
results from: (1) carbon-containing raw
materials, binders or solvents used in the
synthesis processes, (2) carbon impurities in
the reaction environment such as that present
in high temperature graphite furnaces, or (3)
the liner material in milling or classification
operations.
 Origin of chemical impurities 481

200

100

o+-----~------~----~------~-----,--~
0.0 1.0 2.0 3.0 4.0 5.0
Silicon Dioxide (wt%)

Figure 19.2 The effect of silicon on the thermal conductivity of AlN. D, sintered at 2068 K (1795C) for
1000 min, cooled at 0.5 K/min; . , sintered at 2068 K (1795 C) for 240 min, cooled at 10 K/min; /::"., sintered
at 2098 K (1825 C) for 60 min, cooled at 10 K/ min. (Adapted from Knudsen et ai., 1992.)

The origin of oxygen in non-oxide powders (metals). The oxygen substituted in the lattice
can be categorized by: (1) oxygen substituted of the powder is a function of the synthesis
in the crystal lattice of the powder particles, (2) conditions (kinetics and thermodynamics).
surface oxygen and (3) metal oxide impurities However, the presence of surface oxygen is

Before Sintering
Silica Surface layer Silicon Carbide Particle

During Sintering

After Sintering

Condensed Silica in neck region

Figure 19.3 The densification of SiC is inhibited due to evaporation/condensation of the silica surface
layer in the neck region.
482 Chemical purification

(a)

(b)

Figure 19.4 Micrograph of sintered ,B-SiC showing exaggerated grain growth due to iron impurity
(xIOOO): (a) 800 ppm; (b) 350 ppm.
 Removal of carbon 483
not only a function of the synthesis but also of methods. Physical methods such as froth
the instability of non-oxide powders at room flotation (Matis, 1994; Niemi, 1995) have the
temperature (Matje and Schwetz, 1989; Nilsen, advantage of allowing re-use of the carbon if
Riman and Danforth, 1989; Thompson, 1990). desired. This method is particularly effective
For a given oxide layer thickness, total powder in removal of free carbon because of the
oxygen concentration is directly proportional substantial difference in the wettability
to the specific surface area of the powder (i.e. characteristics of free carbon and most non-
the smaller the particles, the higher the con- oxide powders (Goldberger and Reed, 1984).
centration of oxygen). Also, smaller particles, Chemical methods, such as oxidation, allow
due to their higher specific surface energy, more complete removal of the carbon, but
react faster than larger particles. can also lead to substantial oxidation of the
In general, the oxidation of ceramic powders non-oxide powder surfaces as noted above.
results more from hydroxylation than direct For instances where a large excess of carbon
oxidation at room temperature. However, oxi- is used in the synthesis, oxidation might
dation of non-oxide powders becomes preva- follow a froth flotation process. The advantage
lent at the higher temperatures in air (>773 K; here is that a large amount of carbon could be
>500C) which are used to remove excess recycled back to the front end with the physi-
carbon from them. It is typically this oxygen cal separation. Then, a high purity product
which must be removed from most commer- powder could be achieved with an oxidation
cially available higher performance powders process to remove the remaining free carbon.
(particularly powders with surface areas greater Oxidation will be described in more detail
than 5 m 2 / g) (Frisch, Munnich and Thiele, 1990; since it is a preferred method for ultimate
Greskovich and Palm, 1980; Suzuki, 1957). carbon removal.
The metal impurities present in synthesized Free carbon removal by oxidation is a
non-oxide powders are often a consequence of relatively simple step which is normally
the raw materials purity. For example, a coarse carried out as an 'air burnout', provided the
SiC powder is generally synthesized from low ceramic powder is oxidation resistant at
purity sand and coke in large Acheson furnaces moderately high temperatures (typically 773-
(Chapter 4). Further size reduction processing 1273 K; 500-1000 C). The burnout is described
(Chapter 18) of this powder is carried out to by the reaction
make it a useful powder for high performance
(19.1)
applications. Additional metal contaminants
can be introduced from metallic grinding The amount of free carbon which must be
media or mills used in the size reduction steps. removed during the 'burnout' can vary from
Halogen impurities present in non-oxide only a fraction of a percent to as much as
powders may be the result of halogenated 50% or more of the raw product. On a small
starting raw materials (e.g. SiCI4 ) for powder scale, the carbon removal step is normally
synthesis or they may be introduced during done in batch tube furnaces where the
powder post-processing steps (e.g. HF or oxidation reaction is controlled with tempera-
HClleaching). ture, atmosphere (air/N2 ratio) and gas flow
rate. The furnace gas effluent and temperature
profiles from a typical batch carbon oxidation
REMOVAL OF CARBON
with air are shown in Figure 19.5 (Sepulveda,
Folkerts and Kelly, 1989). Larger scale
FREE CARBON
applications normally employ fluidized bed
Free carbon can be removed from non-oxide (Enomoto et al., 1991; Kato, Sugiyama and
powders by either physical or chemical Enomoto, 1983; Kato et al., 1989), rotary tube
484 Chemical purification
100 1273

80 1073
~
0

"0
E Temperature S2'
C- 60 873 I="
0
~
~
"E
Q)
u
e
:J

Q)
c: 40 673 a.
0 E
() Q)
C/) I-
ttl
C!' 20 473

0 0
0 50 100 150
Time, t(minutes)
Figure 19.5 'Air burnout' of carbon from crude carbothermally synthesized AIN powder. (Adapted with
permission from Sepulveda, Folkerts and Kelly, 1989.)

(Miyazaki, Miyagi and Shibahara, 1989; Shaf-
fer, Blakely and Janney, 1987) and moving bed
(shaft furnaces) reactors.
Rate of removal
The removal rate of free carbon is dependent
upon its reactivity, access to oxygen and
the allowable oxidation temperature and
atmosphere conditions for the product
powder.
Air oxidation of carbon is chemical reaction
rate limited at temperatures within the
desirable range for removal from non-oxide
powders (Figure 19.6) (Tu, Davis and Hottel,
1934). Air velocity has no effect on the rate
of reaction, which in the temperature range
973-1373 K (700-1100C) is described by
(Parker and Hottel, 1936)
P02 ) (184000)
rc = 942.7 ( T~/2 exp - RgTp (19.2)
where Tp is the particle temperature. Accord-
ing to equation 19.2, the rate of oxidation
per unit reaction surface area is given by a
linear law.
It has been shown (Sepulveda, Folkerts and
Kelly, 1989) that free carbon can be removed
from non-oxide powders manufactured by
carbothermal reduction within several hours
(Figure 19.7) at temperatures above 773K
(500C) and preferably within 1 h or less
(Shaffer, Blakely and Janney, 1987) at higher
oxidation temperatures (Table 19.1). In
addition to temperature, the reaction time
depends upon the amount of free carbon in
the crude product powder and P0 2 in the oxi-
dizing gas atmosphere.
Carbon reactivity depends primarily upon
the carbon source (gas black, graphite,
charcoal, petroleum pitch, pyrolyzed solvent
residue etc.) and particle size (or surface
area). Graphitic carbon is much less reactive
than most other carbon types (Davis and
Hottel, 1934; Turkdogen and Vinters, 1970).
Hence, an increase in the degree of graphiti-
zation of the carbon may make the residual
free carbon more difficult to remove. This
suggests, for example, that carbon impurities
 Removal of carbon 485

0.50 r----~--___,r_--_r_--_,_--__r--~-___r.;:::_____,

'"0
x
cr 0.10
'"E
0,
e-
O>
16
a: 0.06
c:
0

~CD
a:
0.04

0.02

0.01 900
1000 1200 1400
Temperature (K)

Figure 19.6 Effect of air velocity on combustion rate of carbon: A = 0.0351 m/ s; B = 0.0752 m/ s;
C = 0.274 m/ s; D = 0.389 m/ s; E = 0.50 m/ s. (Reprinted from Tu, C.M., Davis, H. and Hottel, H.C.,
'Combustion rate of carbon. Combustion of spheres in flowing gas streams,' Ind. Eng. Chern., 26(7), 749-
57, published 1934 by the American Chemical Society, Washington, DC)

may be more difficult to remove from non- Access to oxygen

oxide powders which have been synthesized
at higher temperatures relative to those
synthesized at lower temperatures since the
degree of graphitization may increase with
increased process temperature.
The access of carbon to oxygen is highly
dependent upon the degree of coating of the
unreacted carbon by any product powder
layer which may form or the reaction of
486 Chemical purification
100~-----------------------------r __ ~~ __---U~----,

80

10
E 80
CD
a::
c
0
-eIII
()
40
~
'1.1.
'#.
20

Oc----u~-----+----~------+_----4_----~----~
o 20 40 80 80 100 120 140
Time, t(minutes)
Figure 19.7 Fraction reacted vs time curves showing the effect of temperature on carbon oxidation from crude
carbothermally synthesized AlN. (Adapted with permission from Sepulveda, Folkerts and Kelly, 1989.)

carbon and its inclusion in the product
powder lattice. For example, in the synthesis
of SiC by carbotherrnal reduction of silica
(Si02 ), the SiC layer grows towards the
center of the carbon particle via a shrinking
core mechanism (Weimer et al., 1993). If
the free carbon is completely covered by
the SiC layer, mass transfer of oxygen
through the SiC limits the degree of carbon
oxidation.
It can be seen in Figure 19.8 (Shimoo, 1991)
that the removal of free carbon from raw SiC
synthesized using a fine carbon source (CB
and RG) is more difficult than removal from
raw SiC synthesized using larger carbon
(EG). It has been suggested (Shimoo, 1991)

Table 19.1 Removal of carbon from crude SiCa by air oxidation

Temperature (K (OC Free carbon (wt%) after oxidation time (min)

2.5 5 10 20

873 (600) 21.8 21.7

923 (650) 19.8
973 (700) 6.9 2.3
1073 (800) 9.3 0.3

a Crude free carbon = 24.1 wt%.

Source: Shaffer, P.T.B., Blakely, K.A. and Janney, M.A., 'Production of fine, high
purity, beta-SiC powder,' Advances in Ceramics, Vol. 21, Ceramic Powder Science (eds
G.L. Messing, K.S. Mazdiyasni, J.W. McCauley and R.A. Haber), pp. 257-63,
1987. Reproduced by permission of the American Ceramic Society, Westerville,
OH.
 Removal of carbon 487
~.-----------------------------------~

30

If-
12

Time, t(minutes)

Figure 19.8 Oxidation of carbon at 1023 K (750C) from crude carbothermally synthesized SiC powders
(Table 19.2). (Shimoo, T., 'Carbon removal and oxidation of SiC powder synthesized by carbothermic
reduction of silica: Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi (J. Jap. Ceram. Soc.), 99(9), 768-73,
1991. Reproduced by permission of the Ceramic Society of Japan, Tokyo, Japan.)

that this is most likely due to the differences
in the degree of coating of the unreacted
carbon by SiC layers. The raw SiC (RG) and
SiC (CB), synthesized from finer carbon
sources (Table 19.2) (Shimoo, 1991), have
achieved higher degrees of conversion. In the
SiC (EG) powder, where the coating by the SiC
layer is incomplete, the free carbon is more
easily oxidized (Figure 19.8 and Table 19.2),
but even so, the extent of carbon removal is
limited to 34%. Only the free carbon which is
in contact with the atmosphere diffusing
through the pores in the SiC layer is oxidized
and removed.
The mass transfer of oxygen through the
product SiC layer may be further inhibited
by the formation of a surface oxide film
(Si02) which results from the oxidation of
SiC according to
SiC(s) + ~02(g) ~ Si02(s) + CO (g) (19.3)
It has been found (Andrews and Riley, 1991;
Gulbransen and Jansson, 1972; Lamkin, Riley
and Fordham, 1992) that Si02 and silicate glass
films are formed on Si3N4 and SiC ceramics
during exposure to high temperature oxidizing
atmospheres, and oxygen transport through the
film is potentially a rate-controlling step.
488 Chemical purification
Table 19.2 Composition of crude SiC powders synthesized by carbothermal
reduction of Si02 , 5 h at 1973 K (1700 C)
Powder Precursor
carbon source
SiC (RG) Reagent graphite
(d p = 7.5 11m)
SiC (EG) Electrode graphite
(d p = 288J.Lm)
SiC (CB) Carbon black
(d p = 4.5J.Lm)
Source: Shimoo, T., 'Carbon removal and oxidation of SiC powder synthesized by car-
bothermic reduction of silica: Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi (J. Jap.
Ceram. Soc.), 99(9), 768-73, 1991. Reproduced by permission of the Ceramic Society of
Japan, Tokyo, Japan.
The removal of free carbon by oxidation
from the raw SiC (EG) powder over the tem-
perature range 923 < T < 1070 K (650 < T <
797C) is shown as an S-type curve in Figure
19.9 (Shimoo, 1991). In the initial stage, the
powder is heated and the reaction proceeds
steadily. In the second stage, the mass is
reduced almost linearly and in the final
stage, the reactive free carbon content
decreases and the rate of oxidation decreases
gradually. Total removal of the free carbon
will not be successful unless the carbon is
first exposed to the oxidizing atmosphere via
an effective milling step.
Nitrides, such as AlN and Si3N 4, are
generally synthesized by a different carbo-
thermal reduction mechanism (not carbon
shrinking core) relative to carbides, and
would not present the same degree of
difficulty in removing the free carbon. This
suggests, for example, that free carbon may
be more easily removed from raw AlN and
Si3N4 powders than from raw SiC powder
because it is more accessible to oxygen due
to the different carbothermal reduction syn-
thesis mechanisms.
Allowable temperature range
The maximum allowable temperature for
'burnout' depends upon the oxidation
SiC Si02 Free carbon
(wt%) (wt%) (wt%)
83.0 0.04 17.0
64.6 0.14 35.3
86.9 0.03 13.1
resistance of the product powder (Bellosi,
1994). Some ceramics are highly oxidation
resistant (e.g. Si3N4 and SiC) and can with-
stand relatively high oxidation temperatures,
while others (e.g. TiN, B4C and WC) are very
susceptible to oxidation. In addition, higher
surface area, finer-sized powders will be
more susceptible to oxidation than larger
sized, lower surface area powders.
The oxidation of various sized SiC powders,
by heating in air, is shown in Figure 19.10
(Iseki and Hase, 1985) over the temperature
range 573 < T < 1373 K (300 < T < 1100C).
The oxidation is characterized by a mass
increase due to reaction 19.3.
The temperature of the initial mass gain
decreases with higher surface area, finer-
sized SiC powders (Ramanathan et al., 1992)
and can be as low as the ignition temperature
of ordinary carbon (573-823 K; 300-550 C) for
ultrafine (200 m 2 / g) powders. These results
(Figure 19.10) (Iseki and Hase, 1985) indicate
a maximum air 'burnout' temperature for
SiC powders as a function of surface area.
Carbon 'burnout' 'at temperatures above the
maximum will result in yield losses via
reaction 19.3.
Other non-oxide powders behave similarly.
Significant oxidation of fine AlN powders
occurs at temperatures above approximately
1173K (900C) (Ramanathan et al., 1995;
 Removal of carbon 489
~ -,-------,------,-------,-------,-

30 1073 K~_-::::::;.__========L

24
"C
CD
>
0
E
CD
a:
c
..
0
.c 18
I'CI
0
CD
I!!
II.
~
CI

12

o ~~ ____- L_ _ _ _ _ _ ~ ______ ~ ______ ~

30 60 90 120
Time, t(minutes)

Figure 19.9 Oxidation of carbon at various temperatures from crude SiC (EG) powder (Table 19.2).
(Shimoo, T., 'Carbon removal and oxidation of SiC powder synthesized by carbothermic reduction of
silica,' Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi (J. Jap. Ceram. Soc.), 99(9), 768-73, 1991. Repro-
duced by permission of the Ceramic Society of Japan, Tokyo, Japan.)

Suryanarayana, 1990), while fine WC powders atmospheres is carried out according to

oxidize readily at much lower temperatures,
above approximately 673 K (400C) (Roebuck
et al., 1986).
Other atmospheres
Thus far only air oxidation or oxidation in air /
inert systems has been discussed. However,
other atmospheres (NH3, H 20, CO2 etc.) are
also possible, although less convenient and
more expensive. The carbon removal in these
C(s) + NH3(g) -+ HCN(g) + H2(g) (19.4)
C(s) + H 20(g) -+ CO(g) + H 2(g) (19.5)
C(s) + CO2(g) -+ 2CO(g) (19.6)
Reactions 19.4-19.6 require higher tempera-
tures and an energy input relative to reaction
19.1 as shown by free energy and enthalpy
considerations in Figures 19.11(a) and (b),
respectively. While reaction 19.1 is highly
favorable at all temperatures in the range
490 Chemical purification
40

1
36

32

28

24
~
~
c
'jU 20
."
III
III
III
:::E 16

12

0
473 673 873 1073 1273 1473
Temperature (K)

Figure 19.10 Mass gain of ,B-SiC powder heated in air at 5.8 K/min. Surface area of SiC (m2 / g):
1-FN = 200m2 /g, 1 = 32.2; 2 = 13.7; 3 = 4.4. (Adapted from Iseki and Hase, 1985.)

600 < T < 1600K (327 < T < 1327C), reac-
tions 19.4-19.6 are only thermodynamically
favorable at higher temperatures. Reactions
19.4, 19.5 and 19.6 require temperatures in
excess of approximately 1265 K (932C), 950 K
(677C) and 973 K (700C), respectively. While
reaction 19.1 is exothermic, generating approxi-
mately 395 kJ / mol carbon removed, reactions
19.4-19.6 are all endothermic and require an
energy input to remove carbon. Free energy
change and enthalpy considerations shown in
Figures 19.11(a) and (b) were obtained from
calculations made using the FACT (Thompson,
Pelton and Bale, 1985) database.
Ammonia (NH3) has been used to remove
free carbon from Si3N4 and SiC according to
reaction 19.4 at 1350 K (1080C) (van Dijen
and Pluijmakers, 1989). The advantage of
this process is that fine SiC is not oxidized to
Si02 (reaction 19.3) as it is during an 'air
burnout' (Figure 19.10) of carbon. The obvious
disadvantages are the cost of NH3, the
requirement of a higher temperature (Figure
19.11(a and an energy input (Figure
19.11(b to initiate and sustain the reaction,
and the toxicity of produced HCN.
Nonetheless, NH3 has been shown
(Krumbe, Laubach and Gerhard, 1990) to be
 Removal of carbon 491
200

c + NH, ~ HCN + H,
100 .... . /

O +-----~--~----~~~~~--+---~~--~~--_+----~--~
::;
:
q,
~ -100
III
~
o
>0
e'-200
CD
I::
w
-300
C +0, ~ co,
-400

-~+_----~--_4----_+----~----+_----~--_4----_+----~--__4
600 700 800 900 1000 1100 1200 1300 1400 1500 1600
Temperature (I<)
(a)

c + NH, ~ HCN + H,
200 .... / ........................................................ . ......... . ............ .
C + CO, ~ 2CO
..... . . . . /' . . . . . . - - - - - - ---- ------. --. . . -. . -------. -. . . . . .
100 C + H,o ~ co + H ,

O +_----+-----+-----~---4-----4-----+-----+----~----~----~

I& -100
I::
III
~
o
>0 -200
CI.
-=
=-300
I::
W

C + O, ~ CO,
-400

_~ 4-----~----~----~----~----~----~-----+-----+-----+----~

600 700 800 900 1000 1100 1200 1300 1400 1500 1600
(b) Temperature (K)

Figure 19.11 (a) Free energy change (~G) and (b) enthalpy change (~H) vs temperature for reactions 19.1,
19.4, 19.5 and 19.6.
492 Chemical purification
Table 19.3 Effectiveness of NHrcontaining atmospheres for removing free carbon (adapted from
Krumbe, Laubach and Gerhard, 1990)

Powder Flowing Temperature Time Crude Finished

atmosphere (K caC)) (h)
wt% C wt% 0 wt% C wt% 0

AIN NH3 1473 (1200) 20 36.0 0.58 0.09 0.81

AIN NH3 1473 (1200) 2 22.0 0.81 0.16 0.68
Si3N4 90NH3-30N2 1523 (1250) 165 73.0 0.46 0.56 1.17
SiC-Si3N4 90NH3-30 N2 1473 (1200) 6 70.0 0.50 8.60 1.66

very effective in removing free carbon from
crude non-oxide powders such as AlN, Si3N4
and SiC in the 1473-1523 K (1200-1250 DC)
temperature range. It can be seen from the
results presented in Table 19.3 that the
residual oxygen content of the non-oxide
powders is minimal after the high tempera-
ture NH3 heat treatment. This carbon removal
by NH3 process has been used on a larger
scale to remove carbon from fine AlN
powder (Wakimura, Tanaka and Hiai, 1992)
synthesized from alkyl aluminum via an aero-
sol flow reactor process (Chapter 12).
Silicon nitride (Si3N 4) powders with differ-
ent bound carbon contents were treated by
first heating in Cl2 for between 1 and 4 h at
1273 K (1000C) and subsequently annealing
in air at 1073 K (800C). The results are
shown in Table 19.4. In the chlorine-treated
powders, the carbon content was reduced to
0.3-0.4%. A reaction between Si3N4 and Cl2
was not observed. No significant reduction
in carbon content was observed for those
powders which were not first heat treated
with C12

REMOVAL OF BOUND CARBON REMOVAL OF OXYGEN AND METAL

Bound carbon, such as that in the form of a
carbide like SiC, is much more difficult
to remove. Standard oxidation treatments
discussed above are ineffective. However, it
has been shown (Schonfelder et al., 1988;
Schonfelder and Franz, 1989) that, if the
oxidation follows a high temperature chlori-
nation (CI 2 ) step, the bound carbon can be
removed. The SiC is believed to react with
the Cl 2 according to
SiC(s) + 2Cl2 (g) --+ SiCl4(g) + C(s)
The produced carbon is then removed
according to equation 19.1 as gaseous CO2 ,
The dependence of the reduction of the bound
carbon content upon the temperature of the
chlorine treatment is shown in Figure 19.12. A
temperature of at least 1173 K (900C) in the
chlorination step is required to reduce the SiC
content in product Si3N4 powder.
IMPURITIES
FUNDAMENTALS OF TRADITIONAL
PURIFICATION (LEACHING)
Very little information concerning the funda-
mentals of leaching or minerals purification
of high surface area non-oxide powders is
available. However, the study of minerals
purification in general has been extensively
studied and there is an excellent review by
Wadsworth (1979). This section will give a
(19.7) brief overview of minerals purification and
point out the potential difficulties of directly
using the available models to describe the
leaching of non-oxide powders. Some of the
problems with the models for leaching of
ores are due to the fact that they were primar-
ily derived to explain the recovery of valuable
metals from ores (e.g. sulfides, oxides etc.). In
contrast, the leaching of non-oxide powders
 Removal of oxygen and metal impurities 493

1.0

0.9

c
~ 0.6
til
()
<f? 0.4
~

0.2

0.0 --1------,---~--___r--__,;__--...._--__r--

873 973 1073 1173 1273 1373 1473

Temperature (K)
Figure 19.12 Carbon content of Si3N4 powders after post-treatment in chlorine gas (Cl 2 ) at different
temperatures. (Adapted from Schonfelder et al., 1988.)

involves the removal of deleterious oxide and Reactions in solution (leaching process)
metal impurities. follow some steps, anyone of which may be
The purification or leaching of minerals rate limiting. The steps, as defined by
follows an activated process (i.e. an Arrhenius Glasstone, James and Eyring (1941), are: (1)
equation): diffusion of reactants to each other, (2) reac-
tion of reactants and (3) diffusion of the
krxn = ko exp ( - ~"r ) (19.8) products away from the reaction zone.
Solution reactions involving solid particles
The reaction rate constant, krxn' is linear with require the reaction to occur across an inter-
the log of reciprocal temperature. face (heterogeneous reaction). The reaction

Table 19.4 Carbon content of Si3N4 powders before and after oxygen-chlorine treatment steps
(adapted from Schonfelder et al., 1988)

C as prepared CI 2 exposure C after air exposure C after CI 2 and

(wt%) at 1273 K (1000 DC) only at 1073 K (800 DC) air exposure
(h) (wt%) (wt%)

6.7 1 0.3
6.7 6.1
1.2 4 0.4
1.2 1.0
1.5 1 0.4
1.0 2 0.4
0.9 3 0.4
494 Chemical purification
rate can be controlled by diffusion of the
reactants: through the liquid, across some
boundary layer or by surface reaction. The
diffusion coefficient in these systems can be
assumed constant due to an equilibrium thick-
ness being formed with respect to the amount
of agitation. The effect of agitation can be
eliminated by violent mixing, thus minimiz-
ing the boundary layer. However, this may
not eliminate diffusion as the rate limiting
step (i.e. the boundary layer may just be at
(Le. the reactions take place at an interface).
The three models are: 0) receding radius
(surface reaction controlled), (2) receding
radius with a boundary layer and (3) shrink-
ing core. Graphic representations of the
processes appear in Figure 19.13.
The kinetic models can be represented by
the first-order rate expression
Tt
dn
= -Ackrctsky (19.9)

some minimum value and not dependent on
further increased mixing intensity). The rate
limiting step is determined from the measured
reaction activation energy.
There are three basic kinetic models for the
leaching of ores. The models are all based on
the fact that the reactions are heterogeneous
where ni is the number of moles of species i,
A is the surface area of the ore (solid reactant),
c is the solution concentration, krcts is the
concentration of potential reactive surface
sites and ky is the rate constant.
Solving equation 19.9 for constant solution
concentration and for monosized spheres

C(50lution concontntionl

Rate Limiting Step

Surface Reaction
Rate Limiting Step
Diffu ion of re.ct.nt ~nd
products through liquid
bounduy layer

(a) (b)

C(50lution concentntionl

Diffu.ion of pmduct& out

(e)

Figure 19.13 Kinetic models for leaching particles: (a) receding radius (surface reaction controlled); (b)
receding radius with a boundary layer; (c) shrinking core. (Wadsworth, M.E., 'Hydrometallurgical pro-
cesses,' in Rate Processes of Extractive Metallurgy, pp. 133-97, 1979. Reproduced by permission of Plenum
Publishing Corporation, New York, NY.)
 Removal of oxygen and metal impurities 495
results in concentration at the interface being small
dR relative to the solution concentration,
cit = - V rnekrctskv = B (19.10)
dni - 47fRoRDe
(19.17)
where V rn is the molar volume of the dt F(Ro - R)
unreacted sphere, R is the radius of the
With respect to the velocity movement of the
sphere and B is the linear rate constant (e is
unreacted core radius, R, equation 19.17
assumed constant). Assuming Ro is the initial
becomes
radius of the sphere, the fraction reacted, Xi, is
dR -RoVrnDe
X=1_ R3 (1911) (19.18)
I R3 . dt FR(Ro - R)
o
Finally, after solving for the fraction reacted
Differentiating equation 19.11 and combining
it with the preceding equation results in and integrating (initial conditions Xi = 0;
t = 0):
dXi = -3eVrn krcts kv (1 _ X)2/3 (19.12)
dt Ro I 1 - ~X - (1 _ X)2/3 = 2Vrn De t
(19.19)
3 I I FR2
Integrating equation 19.12 for the initial condi- o
tion Xi = 0 at t = 0 gives Equation 19.19 shows that the rate of reaction
according to the shrinking core model is
1 - (1 - X i )1/3 = ksurft (19.13) influenced to a greater degree by the size of
For the reaction model involving a receding the starting particles than the other two
radius with a boundary layer, the kinetics models.
are similar to the surface reaction model and As. expected, the real world does not
are given by always fit into such easily defined models. In
contrast, real systems either do not generally
dXi = -3eVrnD (1- xi/3 (19.14) reach a steady-state situation or they are of
dt IFRo I
mixed kinetics. It is possible, however, to
where D is the diffusion across the boundary reach steady-state conditions if sufficient
layer, I is the rate limiting boundary thickness excess of the reactant solution is used relative
and F is the stoichiometric factor (the number to the solid particles. Mixed kinetics pre-
of moles of the fast diffusing species necessary dominate for non-oxide powders due to their
to create one mole of product). Integration tendency to form oxides in water and sub-
with the same initial conditions as before gives sequent dissolution. A steady-state mixed
1 - (1 - X i )1/3 = krect (19.15) kinetics model for diffusion through a liquid,
diffusion through products and surface
The activation energy must be determined in
reaction is
order to distinguish between the two models.
The shrinking core model has been found to dni 3eVrn
be best in explaining the dissolution of metals dt FlRo R6F(1 - (1 - Xi)1/3)
from oxide ores. In this model, the diffusion D+ Dprod-i
(1 X)1/3
through the remnant structure is presumed b
to be rate limiting (Figure 19.13(a and can Ro
+ ksurf (1 - Xi) 2/3 (19.20)
be given by
dni -47fR2 D de where Db is the diffusion of the bulk fluid and
(19.16)
dt F dR Dprod is the diffusion through the products of
Upon integration, for steady-state conditions reaction. Equation 19.20, integrated in the
between all values of R to Ro and for the same manner as previous equations, results
496 Chemical purification
in the rate being the sum of the individual rate
expressions.
In summary, the leaching of metallic and
oxygen impurities from non-oxide powders
is complicated by their small particle size
and their tendency to form soluble oxides/
hydroxides in aqueous systems.
APPLICATIONS
The leaching of Si3N 4 , SiC, boron carbide
(B 4 C) and AlN to reduce residual oxygen
and metals will be discussed.
Silicon carbide (SiC)
The removal of oxygen (i.e. silica) and metals
has been accomplished by high temperature
treatments in inert atmospheres. Caustic and
acid washes have also been used. The typical
early process for SiC purification was to heat
an aqueous suspension of SiC and sulfuric
acid (H 2 S04 ) in lead tanks for approximately
60 h. The acid was subsequently removed in a
rotary washer (Harty and Moore, 1923). An
excessive amount of fine-grained material
was lost in transfer from the mixing to the
washing operation. Further refinements
included single chamber washing to eliminate
this problem.
Hydrofluoric and hydrochloric acids (HF
and HCI, respectively) have also been used
to treat SiC. The use of hydrofluoric acid
(HF) has an advantage compared to other
acids in that residual silica is dissolved via
the interaction (Her, 1979):
(19.21)
The leaching of SiC with alkalis was also
known to remove both free silicon and silica
from SiC. For example (Prochazka and
Greskovich, 1978):
2NaOH + Si + H 20 ----+ Na2Si03 + 2H2 (19.22)
The fabrication of fully dense SiC parts by
pressureless sintering requires the use of high
purity sub micron SiC powder (Prochazka,
1974; Prochazka, 1977). Because of this, much
effort has been directed towards the fine grind-
ing of readily available coarse powders (Hoyer,
1989; Prochazka, 1987; Wittmer, 1989).
The purification of these powders has used
all of the above-mentioned techniques. Most
of the work describes the milling of the
powder and subsequent treatment to realize
a powder with less than 1 wt% oxygen and
low metals impurities. For example, a tech-
nique for making sinterable SiC from low
grade Acheson SiC included washing in hot
353 K (80 DC) 20 wt% potassium hydroxide
solution for 3 h. This was preceded by a
dilute HCl wash to remove metal impurities.
The final oxygen concentration was 0.38 wt%
O. The patented technique claims that NaOH
solutions or ammonia solutions under similar
conditions will not yield as Iowa final oxygen
(>1%) (Matje and Schwetz, 1986).
Another two-stage leaching process was
used to purify SiC powders that were first
milled in water with iron media (Wolf and
Klinger, 1990). The first leaching step used
HCI acid to remove iron milling contami-
nation along with residual Al and Ca com-
pounds (Table 19.5). The second leaching
step used dilute caustic soda to remove the
residual silica contamination (Table 19.5).
Using the same leaching process on powders
milled in alcohol resulted in iron contamina-
tion greater than 0.2 wt% Fe in the final SiC
powder. No explanation of this result was
proposed.
In addition to chemistry, chemical purifica-
tion has a significant impact on the physical
properties of the treated SiC (e.g. surface
area and particle size). The recovery rate for
a hot dilute acid followed by a hot NaOH pro-
cess has been reported to be 55 wt% for fine
grit size SiC (Table 19.6) (Theertha, Mohan
and Pawar, 1987). Ferromagnetic separators
have been used in dry and wet processing of
SiC powders, but only for particles greater
than ",40 J-Lm (Prochazka, 1987; Rowson and
Bahn, 1990). These large grains are not useful
as high performance ceramic powders.
 Removal of oxygen and metal impurities 497
Table 19.5 Results of a two-stage leaching process on milled SiC powder (adapted from
Wolf and Klinger, 1990)

Impurity Raw SiC Milled SiC After HCI leach After NaOH leach
(wt%) (wt%) (wt%) (wt%)

Iron 0.21 36.8 0.01 0.01

Aluminum 0.089 0.03 0.03
Calcium 0.001 0.002 0.002
Oxygen 3.36 3.4 0.5

The effect of acid concentration on SiC
powder total metals contamination residual
oxygen content and surface area has recently
been investigated. These results are shown in
Figures 19.14 and 19.15. The results indicate
that some fraction of the finer SiC particles is
being digested and is inversely proportional
to the acid concentration. This is consistent
with the higher oxygen concentrations follow-
ing the same trend as the surface area with
respect to acid concentration. However, the
metal impurity concentration is inversely
proportional to the acid concentration. Thus,
further work is required to optimize and
develop full scale processes for treatment of
fine SiC powders.
Other processes used to purify SiC powder
include using gaseous anhydrous HF and
BCl3 at temperatures between 400 and 1200 K
027-927C) (Brynestad et al., 1984). The best
results for oxide removal were found to be
with flowing HF at ,....,923K (,....,650C). Resid-
ual oxygen decreased from 15% to 0.4% in
1.3h.
The combination of inert heat treatments
followed with acid treatments was found to
be more effective in removing impurities to
levels needed for the semiconductor industry.
This technique requires powder to be less
than lOOl1m in size and the heat treatment
temperature to be between 1773 and 2473 K
0500-2200C). The purified powder had less
than 10 ppm of any metal impurity from a raw
powder with a starting iron concentration
greater than 800 ppm (Amino, 1990).
A recent approach to reducing the oxidation
sensitivity of ultrafine SiC powder and to
reduce their grain growth during densifica-
tion is to calcine them at high temperatures
0373-1773K; 1100-1500C) in N2 (Kaiser
et al., 1995) prior to air exposure. After the
N2 calcination, an Si3N4 layer could be
detected by infrared spectroscopy in reflec-
tion. Heat-treated densified parts were
harder due to smaller grain sizes. Grain
growth was inhibited by the heat treatment
which formed the Si3N4 surface layer on the
ultrafine SiC particles.

Table 19.6 Effect of acid/caustic wash on impurities of SiC fine-grained

powder

Percentage

SiC Si Free C

Feed 89.93 3.90 1.96 1.24 2.63

800 grit 96.30 1.30 0.70 0.90 0.23

Source: Theertha, G.N.A., Mohan, A.L. and Pawar, P.G., 'Beneficiation of silicon
carbide fines,' Bull. Electrochem., 3(1), 59-60, 1987. Reproduced by permission of
the Central Electrochemical Research Institute, Karaikudi, India.
498 Chemical purification
1.1 ~--------------------------~~-rrooo

1.0

900
c::Qj 0.9

~
0 0.8
~ SOD
0.7

0.6 +---~--~--~--~------~--~---+700
0 2 4 6 8
Acid Concentration (N)

Figure 19.14 SiC oxygen and impurity level as a function of acid concentration (HCl at 348 K (75 C) for 1 h;
initial SiC oxygen = 1.8 wt%; impurities >0.5 wt%; solids loading = 15 wt%).

additions to sinter to full density. Thus, the

In contrast to SiC, the post-processing of
Si3N4 has focused primarily on modifying
the surface chemistry to aid processing.
Examples include the controlled oxidation
of the powder and reaction with alkoxides as
well as acid and caustic washes to enhance its
colloidal behavior (Liden, 1991; Persson, 1987;
Stadelmann, Petzow and Greil, 1989).
Silicon nitride (Si3N 4) powders differ from
SiC powders in that they require oxide
amount of oxygen (i.e. silica) on the surface
is important to sinter Si3N4 to high density.
Since Si3N4 is generally produced from
higher purity reactants, purification processes
for it are not as prevalent as for SiC. However,
some treatments for modifying the surface of
Si3N4 powders have been attempted to make
them easier to process or to cause improved
part properties.
One of the first techniques for purifying
silicon nitride powders was the high

1.1 18

1.0 17
-
c::Qj
0.9 16
i--
to
~ ~
0 0.8 15 Qj
~ u

0.7 14 i
Ul

0.6 13
0 2 4 6 8
Acid Concentration (N)
Figure 19.15 SiC surface area as a function of acid concentration (HCl at 348 K (75 C) for 1 h; initial SiC
oxygen = 1.8 wt%; impurities >0.5 wt%; solids loading = 15 wt%).

temperature (1873 K, 1600C) heat treatment
(16 h) in flowing nitrogen at less than 4000 Pa
(30 torr). This treatment resulted in conversion
of the powder to the beta crystallographic
phase and decreased the oxygen concentra-
tion to approximately half of the starting
level regardless of the starting oxygen wt%
(i.e. initial oxygen from 5.46% to 2.78%). The
treatment also resulted in an increase in par-
ticle size as well as a reduction in the iron con-
tamination by 50%. The Si3N4 powder oxygen
concentration was minimized to decrease the
oxide glass content in a fabricated part, thus
increasing the high temperature strength.
Due to its water reactivity, Si3N4 processing
was carried out in an inert atmosphere at
room temperature (Wright and Niesz, 1974).
Other techniques for decreasing the Si3N4
oxygen content include aqueous HF and
NaOH treatments. In both cases, as the
temperature was increased, the Si3N4 loss
due to decomposition was reported to be sig-
nificant. Low temperature treatment with
caustic has been done successfully, but did
little to decrease the lattice oxygen. Typically,
only surface oxygen is reduced and it quickly
increases in air (note some attack of the Si3N4
was found even in the low temperature tech-
niques) (Prochazka and Greskovich, 1978). A
recent patent describes a technique to reduce
the oxygen pickup from milling in water by
using a mineral acid leach. The method uses
0.1-2N HCl or H 2S04 acids at temperatures
between 333 and 363 K (60-90C). The result-
ant powder oxygen concentrations are less
than 1.5 wt% (Brink and Lange, 1993).
Finally, other high temperature techniques
using hydrogen and hydrogen in argon have
been used. The use of hydrogen alone at
1573 K (1300C) caused the Si3N4 to be
reduced to silicon metal whereas the gas
mixture was more successful in reducing the
oxide surface layer (i.e. initial oxygen 4.1 %
reduced to 1.4%).
The gaseous mixture was found to be the
best technique for removing the oxygen layer
as compared to an aqueous HF treatment. The
Removal of oxygen and metal impurities 499
aqueous HF process resulted in powder that
was strongly agglomerated. The agglomer-
ated powder then had to be remilled prior to
fabricating green and dense parts (Boiteux,
1987).
In summary, Si3N4 can be purified, but it is
not as practical as leaching of SiC due to
material decomposition. The purification of
the starting feed raw materials and close
control of reaction conditions have been the
generally accepted route to make higher
purity (lower metals contamination and lattice
oxygen) Si3N4 powders.
Boron carbide (B 4 C)
Boron carbide (B 4C) is generally purified by
acid leaching. The reaction of boric anhydride
or acid with carbon in large arc furnaces
(Chapter 5) yields large masses of B4C that
must be milled. The impurities added during
milling and from the starting raw materials
are removed by acid leaching. Boron carbide
(B4C) made using Mg metal as a reactant
(Part Three) is typically leached with either
H 2S04 or HCl. The B4C is then rinsed with
hot water to remove Mg metal and MgB2'
This powder is then heat treated (1873 K;
1600C) for several hours in vacuum (1 Pa;
0.0075 torr) to remove carbon, nitrogen and
magnesium. The final product is milled and
acid leached as before (Thevenot, 1990).
Aluminum nitride (AIN)
Aluminum nitride (AIN) powder undergoes
hydrolysis to a much greater extent than
Si3N4 powder. It will undergo an accelerated
exothermic reaction in water under the right
conditions (Eisman, personal communication
1992; Komeya et al., 1990), thus making tradi-
tional aqueous leaching undesirable. In view
of this, the purity of synthesized AlN is gener-
ally governed by the purity of raw materials
used in its production.
A route to purify AlN has been developed
using a halogen gas stream (i.e. HF) in the
500 Chemical purification
presence of carbon or alternatively a haloge-
nated hydrocarbon gas stream. For example,
the impurities 97 ppm Ca, 15 ppm Si and
10 ppm Fe in a raw AlN powder were reduced
to less than 1 ppm after treating in a per-
flu oro ethane gas stream (lOm3 /min) at 273K
(OC) for 1 h. Parts fabricated from the
treated powder had properties far superior
(e.g. >280W/mK thermal conductivity) to
typical commercial AlN powders (Sawamura
and Uchikoba, 1988).
Aluminum nitride (AlN) has also been
processed to reduce its water sensitivity.
Typically this has involved controlled oxi-
dation of the powder surface in a manner
similar to that for Si3N 4 One method for pas-
sivating the surface is to oxidize the powder
between 773 K (500C) and 800 K (527C) in
dry air or in oxygen-inert gas mixtures. The
treatment is reported to inhibit hydrolysis up
to 400 h in 50% RH (relative humidity) at 298 K
(25C), whereas an untreated powder loses
50% of the starting A1N to an oxide species
after 300h (Tada et al., 1989).
SUMMARY
Non-oxide powder purity is controlled by
the purity of raw materials used in their syn-
thesis and the removal of contaminants by
acceptable post-processing methods.
Carbon is easily removed from many
oxidation resistant non-oxide powders by
oxidation in air at moderate temperatures
(773-1273 K; 500-1000C). The effectiveness
of the 'burnout' depends upon the reactivity
of the carbon, its particle size and its access
to oxygen. Care must be taken to control the
oxidation temperature so as to reduce the
surface oxidation of the product powder.
Oxygen and metallic impurities can then be
removed by conventional aqueous leaching
methods provided the non-oxide powders are
not susceptible to substantial hydrolysis. In
general, the carbides have a low susceptibility
to hydrolysis and are easily post-processed by
conventional means such as alkali or acid
washing. Leaching is usually a final step to
control product purity.
On the other hand, because of their amino
chemistry, the nitrides are more susceptible
to hydrolysis than the carbides. They are
difficult to post-process in a manner similar
to carbides. Hence, the purity of nitrides
tends to be fixed by the raw materials used
for their synthesis. The post-processing of
nitrides has focused primarily on the control
of their surface chemistry.
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SOLIDS DISPERSION IN LIQUIDS
Andrew G. Haerle and Kevin
INTRODUCTION
Spray drying is a cost-effective process for
granulating non-oxide ceramic powders.
Granulation is necessary to achieve good
powder flow properties. For a dry pressing
operation, good flow properties are essential
to obtain uniform die filling and high green
bulk densities. A variety of non-oxide ceramic
powders have been spray dried to produce
dense, flowable granules. Some of these
materials are SiC, Si3 N 4 , AIN, WC and
mixed carbides.
In order to obtain spray-dried powder, the
non-oxide powder, sintering aids and binders
must be incorporated into a liquid dispersion
medium. The dispersion state of ceramic
particles in a spray-drying slip significantly
impacts the capacity to spray dry pressing
granules. The dispersion state affects slip
solids loadings, transport properties, atomiz-
ing characteristics and overall spray-drying
efficiency. These parameters determine
the properties of the spray-dried granules
which, in turn, ultimately control the pressing
and sintering properties of the formed part.
Because of the importance of particle dis-
persion on spray drying, the fundamental
nature of colloid stability will be addressed
and applied to real non-oxide systems. This
will provide the basis for describing the
fundamental structural and transport
characteristics of non-oxide slips which are
relevant to the spray-drying process. Finally,
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
20
J. Nilsen
the interdependence of dispersion and slip
properties on each stage of the spray-drying
process will be discussed, and possible
effects on granule properties will be con-
sidered.
Basic knowledge of surface chemistry and
dispersion state of non-oxide powders pro-
vides the necessary basis for developing a
spray-drying process. The nature of the
spray-dried granules and the overall spray-
drying efficiency are dictated by the colloidal
stability and rheological properties of the
non-oxide slips. This chapter provides a start-
ing point for understanding the colloidal
dispersion behavior of non-oxide ceramics
and gives some practical examples for
imparting good dispersion characteristics to
the powder constituents.
DISPERSION
Since final densification of non-oxide ceramics
requires a large fraction of submicron par-
ticles, the dispersion theory associated with
colloidal particles is presented. The nature of
surface and its influence on particle-particle
interactions and the corresponding floccula-
tion theory are addressed. Since some non-
oxide powders react with or are incompatible
with water, colloid stability is addressed for
non-aqueous systems. Practical examples of
some non-oxide powder formulations will be
given.
506 Solids dispersion in liquids
The nature of the colloid surface directly
influences the degree of particle stability. Coll-
oid particles can obtain a charged surface when
brought into contact with an aqueous medium.
The mechanisms of surface charge generation
have been enumerated (Hunter, 1987):
1. Surface dissociation.
2. Ion adsorption from solution.
3. Crystal lattice defects.
A charged particle in an aqueous system
maintains electro neutrality since oppositely
charged ions (counter-ions) orient about the
particle. This arrangement creates a diffuse
double layer. In addition, a small proportion
of ions of like charge (co-ions) will reside in
the diffuse double layer. The simplest model
of the diffuse double layer is the one arrived
at separately by Gouy and Chapman (Gouy,
1910; Chapman, 1913). The Gouy-Chapman
model has many assumptions (Shaw, 1983).
However, the theory is successful at predict-
ing the potential as a function of distance
from the particle surface. Assuming a flat
surface of potential 'l/Jo, the potential 'l/J at a
distance x from the surface is given as
'l/J=2kBT In(l+''(exP(-KX)) (20.1)
z+e l-"(exp(-Kx)
where z+ is the lattice cation charge number
and e is the electron charge. The term "( is
given as
(20.2)
"( = exp (~~~ ) + 1
The Debye-Huckel approximation can be
applied when the term z+e'l/Jo/2kBT is much
less than 1. Equation 20.1 then reduces to
'l/J = 'l/Jo exp( -KX) (20.3)
The term K is the Debye parameter and is the
inverse of the double layer thickness. The
double layer thickness is taken as the point
where the repulsive energy decreases by a
factor of one exponent (Parfitt and Peacock,
1978). The Debye parameter is given by
K N A CZi
= (2e 2ckBT ) (20.4)
where N A is the Avogadro number (6.022 x
1023 mol- 1 ), c is electrolyte concentration, z
is the lattice counter-ion charge number and
c is the permittivity of the dispersion
medium. A schematic of the electrical double
layer which shows the potential as a function
of distance from the surface is given in Figure
20.1. Equation 20.4 shows that the double
layer thickness and, therefore, the particle dis-
persibility are dependent on the concentration
and charge of the electrolyte.
Stern (1924) proposed a model which
accounts for specifically adsorbed ions; a
situation which was unaccounted for in the
o Counter-ions
+ ~8 e
+ e e
+ + ~ e8 ~
Co-ions
+ e
e e
+ e e ~ e
+ e 8 e ~
+ + e ffi e e
+ 8 e ~
+ e ~
Figure 20.1 Model of diffuse double layer arrived
at by Gouy (1910) and Chapman (1913). (Gouy,
G., 'Concerning the surface electric charge of an
electrolyte,' Ann. de Phys. (Paris), 4(9), 257, 1910.
Reproduced by permission from Editions de Phys-
ique, Cedex, France. Chapman, D.L., 'A contribu-
tion to the theory of electrocapillarity,' Phil. Mag.,
25, 475, 1913. Reproduced by permission of
Taylor & Francis Ltd, London, UK.)
 Dispersion 507
Gouy-Chapman treatment. A further modi-
fication of the Stern model distinguishes
between an inner and outer Helmholtz
Particle Surface
f Stern Plane

Surface of Shear

plane. The outer Helmholtz plane represents

+: 8 8
the closest approach of the center of hydrated (t)
ions to the surface, and the inner plane is the
closest approach of the center of ions which
e 8
are dehydrated (in the direction perpendicu- ED
lar to the surface). Both of these models ED 8
divide the double layer into two parts sepa-
rated by the Stern plane which is located at a 8
hydrated ion radius from the surface (outer
8 ED
Helmholtz plane). Ions with centers that are EB 8
outside the Stern plane are considered to be
ED 8
in the diffuse part of the double layer. The
e e
Gouy-Chapman treatment describes their
behavior with 'O being replaced by 'd. A
schematic of the double layer is shown in .~
I
- .
" Diffuse Layer
Figure 20.2. Although 'd is generally less Stern Layer

than 'o, 'd can be greater than 'O if surface

active co-ions are adsorbed (Tadros, 1980).
The quantities 'O and 'd are not readily
measurable, whereas the electrokinetic poten-
tial (zeta potential) can be measured. The zeta Potential
potential () is the measured electric potential
at the shear plane of a particle in a liquid. The
zeta potential is derived from electrokinetic
theory using experimentally determined elec-
trophoretic mobility data. Its value is very
close to the potential at the Stem plane
(( ~ 'd), with any differences becoming more 1) _ _ 1/K-+
pronounced at high electrolyte concentrations Distance
or at high potentials (Shaw, 1983).
The discussion on charged surfaces pro- Figure 20.2 Schematic of the electric double layer
vides the basis for describing particle stability according to Stern (1924). (Stern, 0., 'The theory of
in suspension. The Deryagin-Landau and the electrolytic double layer,' Zeit. Elektrochem., 30,
Verwey-Overbeek (DLVO) theory estimates 508, 1924. Reproduced by permission of VCH
Verlagsgesellschaft mbH, Weinheim, Germany.)
the interaction energy of charged particles as
a function of their interparticle separation. It is
directly applicable to dilute suspensions, but For spheres of equal size and small double
is often used to interpret concentrated suspen- layer overlap, the repulsive energy between
sions due to lack of theory. The interaction particles can be calculated from the following
energy is the summation of the electrostatic equation (Hogg, Healy and Furstenau, 1966):
repulsion energy associated with double (20.5)
layer overlap and the attractive energy due
to van der Waals forces. The repulsive where a is the particle radius and Hd is the
energy is considered first. interparticle separation. For large interparticle
508 Solids dispersion in liquids
distances such that the potential of near
neighbors can be neglected, the repulsion
energy for equal spherical particles has been
given by Reerink and Overbeek (1954):
VR -- 327ra~T2'Y2
_? 2
(H )
exp -/'i, d (20.6)
e-z
Attractive forces between particles result
from interactions of the following types
(Heimenz, 1977):
1. permanent dipole-induced dipole inter-
action (Debye equation);
2. permanent dipole-permanent dipole inter-
action (Keesom equation);
3. induced dipole-induced dipole interaction
(London equation).
London dispersion forces are the most fre-
quently encountered van der Waals attractive
forces and apply to nearly all materials.
Hamaker has developed an equation which
gives the interparticle London attractive
energy, V A, as a function of interparticle
distance. The approximate expression for
spheres of equal radii at small interparticle
distances is
(20.7)
where AH is the Hamaker constant. The above
expression is an approximation and will
slightly overestimate the Hamaker constant
(Shaw, 1983).
The presence of a liquid medium between
particles reduces the attractive nature between
particles and reduces the Hamaker constant.
For two particles separated by a liquid
medium, the effective Hamaker constant is
given by
(20.8)
where Ap is the Hamaker constant of the
particle in vacuum and Al is the Hamaker
constant of the dispersion medium. A bound
surfactant layer on the particles can reduce the
attractive energy by a factor of 5-50 times
(VoId, 1961).
Particle-particle interaction energy curves
are obtained by summing the attractive and
repulsive energies V A and V R over a range of
interparticle distances. The total interaction
energy, VT , is given by
VT = V R + VA (20.9)
Two typical interaction energy curves, one
with a large repulsive energy and one with a
low repulsive energy, are depicted in Figure
20.3. Both curves show a deep primary
minimum energy well at small interparticle
distances, indicating that the particles which
are allowed to come into close proximity will
attach to each other. The strength of the attach-
ment is dependent on the depth of the well. It
is the height of the maximum in the inter-
action energy curve which prevents particle
attachment and directly controls the stability
of colloidal dispersions. Brownian motion
causes particles in suspension to impinge on
each other. If the energy barrier to flocculation
is high, the probability of a particle having
enough thermal energy to overcome the
energy barrier and attach to another particle
is low, and the suspension does not flocculate
rapidly. The height of the potential energy
barrier controls the dispersion characteristics
and therefore the stability of non-oxide slips.
COLLOID STABILITY
The stability of colloidal suspensions in the
absence of a potential energy barrier between
particles (i.e. diffusion controlled) is described
by
f( = 4kBT (20.10)
3/-L
When there is a repulsion barrier between
particles, the stability constant must be modi-
fied by a factor W, called the stability ratio:
f(
W= 1(' (20.11)
The value for the stability ratio is given by
W = 2a J exp
oo
2a
( V T ) dRd
kB T R~ (20.12)
 Non-aqueous media 509

VT = VR + VA
VR1 > VR2
\
\
\
\ VR1
+ \
\
\
\
\
,,
,,
,
"""",
........ .....
......
...... ......
----===-
VT r-rJf-------'::......:::::::::=========......-:-::
-------- --------------
0

....... ----
"""""
,,
I" VA
I
I
I
I
I
I

Figure 20.3 Interaction energy curves for two particles in close proximity.

where Rd is the center-to-center interparticle NON-AQUEOUS MEDIA

distance. Equation 20.12 is commonly approxi-
Ceramic particles in non-aqueous media
mated by considering only the maximum in
behave quite differently than in water. There
the interparticle potential, V max (Reerink and
are two general possibilities for surface charge
Overbeek, 1954):
generation in non-aqueous media (Kitahara,
W~-exp 1 (V- -
2KJl
max )
kBT
(20.13)
1984):
1. Preferential adsorption of cation or anion;
The above equations are applicable to dilute 2. Dissociation of any dissociative group on
suspensions. However, it was found that the surface through acid-base interactions.
the equations can be applied to concentrated
suspensions when KJl > 5 (Bensley and Ionic surfactants are judiciously chosen to
Hunter, 1983). This is typically the case for generate surface charge on particles in nOn-
concentrated suspensions of non-oxide par- aqueous media. The surfactants dissociate to
ticles in aqueous media. For non-aqueous a degree, and if the ions are large they will
media, KJl is typically less than 5, and the be stabilized. These ions generate surface
above equations do not apply for concentrated charge by preferentially adsorbing On the
suspensions (Feat and Levine, 1976). particle surface by an acid-base interaction,
510 Solids dispersion in liquids
or by their hydrophilic or oleophilic proper-
ties. If there are no adsorbable ions, the surface
charge generation is dictated by the proton
donor/proton acceptor capability of the sol-
vent. This mechanism of surface dissociation
has been described by Lyklema (1968):
PHI + S- - t PH + SH - t P- + SHI (20.14)
where PH and SH are the surface groups of
the particle and solvent molecule, respec-
tively.
The two main characteristics of non-
aqueous media are the low degree of dis-
sociation of electrolytes (resulting in a low
ion concentration) and the low dielectric
constant. According to equation 20.4, both of
these parameters will affect the Debye
length. Since the effect of the low ion concen-
tration dominates, the thickness of the double
layer will be significantly greater than in
aqueous systems.
The low value for the dielectric constant has
a significant effect on the magnitude of the zeta
potential. Zeta potentials ) for particles in
non-aqueous media are commonly as high as
in water-based systems, even though the sur-
face charge is much less (Fowkes and Pugh,
1984). In addition, ( decays much slower in
non-aqueous media. In other words, the poten-
tial is finite over long distances, and the slope
of (vs interparticle distance curve (dVT/dHd )
is small. Because of the small slope of the
potential energy curve, minor perturbations
(thermal or mechanical) can cause flocculation
in concentrated suspensions. This behavior is
depicted in Figure 20.4.
However, it has been suggested by Fowkes
(1981) that the ionic concentration in non-
aqueous media is higher than previously
thought for concentrated suspensions because
the counter-ions increase the ionic strength of
the system. This acts to compress the double
layer, causing the maximum in the potential
energy curves to move closer to the particle
surface. Electrostatically stabilized non-
aqueous dispersions can therefore behave
similarly to aqueous dispersions.
The presence of water in non-aqueous
suspensions will have a significant effect on
the surface potential of the ceramic particles.
Water typically dissociates and forms protons
and hydroxyl ions, and these may be selec-
tively adsorbed, rendering the particle sur-
faces more basic. Water will therefore make
the particle ( positive in non-aqueous media.
Water has been observed to reverse ( from
negative to positive for ceramic particles in
alcohols (Romo, 1966). Water has also been
observed to increase the positive ( in non-
aqueous systems. However, the positively
charged water layer around the particle has
an affinity for the negative charges in the
media and therefore decreases ( at a certain
concentration (Kitahara, 1984). From this
discussion, it is obvious that water can have
a complicating effect on the dispersion of
non-aqueous ceramic suspensions and the
moisture content should be controlled
carefully.
Although it has recently been shown that
double layer interactions can be used to stabi-
lize concentrated suspensions of particles in
non-aqueous media, inorganic particles are
typically stabilized by steric interactions. The
next section addresses sterlc stabilization as
the primary mechanism for obtaining concen-
trated suspensions in non-aqueous media.
Concentrated suspensions are necessary for
obtaining high spray-drying efficiencies.
STERle STABILIZATION
Typically, particles in non-aqueous media
are commonly sterically stabilized by the
addition of polyelectrolytes, macromolecules,
or adsorbed non-ionic surfactants to obtain
concentrated suspensions (Fowkes et al.,
1982). Adsorption of the aforementioned
species changes the distribution of ions in
the double layer and causes the location of
the shear plane to be shifted a finite distance
from the surface (Tadros, 1980). Steric stabili-
zers are commonly block copolymers, with a
lyophobic part which can anchor onto the
 Steric stabilization 511
Aqueous

VT 0t--t--~----~~~~====~--------

Non-aqueous

VT o+-;-----------~----------------------

Figure 20.4 Comparison of energy barriers to flocculation for two particles in close proximity (aqueous vs
non-aqueous).

particle surface, and a lyophilic part which
extends out in the dispersion medium approxi-
mately 10-20nm (Fowkes, 1981). Commonly
used steric stabilizers are polyisobutenes,
which have basic anchoring groups and
poly(12-hydroxystearic acids) which possess
acidic anchoring groups. Steric stabilization is
favored when the lyophilic moieties are soluble
in the dispersion medium (Napper, 1983).
The change in free energy which occurs
during interpenetration of the lyophilic
chains determines the degree of stability of
sterically stabilized particles. The free energy
change is dependent on the temperature,
pressure and the composition of the solvent
(Shaw, 1983). The condition at which the free
energy change is equal to zero is called the
theta point, B. The change in free energy,
~G, is given by
~G = ~Grn + ~Gel (20.15)
where ~Grn is the change in free energy
associated with mixing of extended chains
on close approach and ~Gel is the free
energy associated with the loss of configura-
tional entropy of the extending chains when
512 Solids dispersion in liquids
the particles approach a distance less than
twice the adsorbed layer thickness. ~Gel is
important only when interpenetration is sig-
nificant, which is rare in practice (Tadros,
1980). For negative ~Gm' the conditions are
worse than (), and attraction prevails. At
conditions better than (), ~Gm is positive and
stability is favored.
The mixing term can be further considered
as being a combination of entropic and enthal-
pic contributions, ~Sm and ~Hm' where
(20.16)
For positive ~Hm and negative ~Sm' the
suspension is expected to be stable at all
temperatures. If ~Hm and ~Sm are both
negative, flocculation is expected below the ()
temperature (entropic stabilization). For posi-
tive values of both ~Hm and ~Sm' flocculation
is favored above the () temperature (enthalpic
stabilization) (Shaw, 1983). Enthalpic stabiliza-
tion is common in aqueous media and can be
important in the processing of non-oxide
ceramic slips. Processing typically requires a
milling operation where the friction between
the moving media generates heat. If enough
heat is generated, enthalpically stabilized
slips can flocculate in the mill and significantly
reduce milling efficiency.
Steric stabilization generates a large positive
interaction energy at short ranges, thus pre-
venting flocculation into a deep primary
minimum (Figure 20.5(a. The use of poly-
electrolytes provides a positive interaction
energy over long ranges by combining the
repulsive forces of electrostatic and steric inter-
actions. The interaction energy is given by
(20.17)
where Vs is the steric contribution to the total
interaction energy. These suspensions are
termed electrosterically stabilized. The inter-
action energy curve for electrosterically stabi-
lized suspensions is shown in Figure 20.5(b). It
can be seen that the secondary minimum is
eliminated.
A distinction between sterlc and semi-steric
stabilizers has been identified (Johnson and

I I
I I
I I
I I
I I
I I
I I
+ I+--- Vs + I
I I
I I
I I
I \

\'\,
I \
\ \
VA+V s \
\ /
VT VT X
I \

0 0
I \ ,
/
~Ha---'
/
I
I Hd - - - .
/ /+-- VR+VA
/
I 4.- VA I
/ I
I I
I I
(a) (b) I

Figure 20.5 Interaction energy diagram: (a) sterically stabilized particles; (b) electrosterically stabilized
particles.

Morrison, 1987). Semi-steric stabilizers adsorb
on particle surfaces similar to steric stabilizers,
but they do not have long enough carbon chains
to produce true steric stabilization. These stabi-
lizers do not create an additional energy barrier
(as electrostatic and steric stabilizers do), rather
they keep particles from coagulating by redu-
cing the attractive forces between particles. In
other words, the van der Waals forces are
reduced because there is a shell around the par-
ticles which has a different Hamaker constant
than either the solvent or the particle (VoId,
1961). This effectively reduces the depth of the
attractive energy well. Combination of semi-
steric and electrostatic stabilization eliminates
the energy well completely, and the potential
energy curves are similar to sterically stabilized
systems. This combined electrostatic/ semi-
steric effect has been found to increase with
increasing particle concentration (Johnson and
Morrison, 1987).
CERAMIC SYSTEMS
The surface chemistry of non-oxide powders
directly influences their dispersion behavior
in suspension (Schwelm et al., 1993; Malghan,
Premachandran and Pei, 1994; Premachan-
dran and Malghan, 1994). An important
factor in determining the dispersion behavior
of ceramic powders is their point of zero
charge (PZC). (The point of zero charge is
also commonly referred to as the isoelectric
point, or IEP. For the purpose of this review,
they will be used interchangeably since
specific ion and/or co-ion adsorption are (is)
ignored.) The point of zero charge for a cer-
amic powder is the pH value at which the sur-
face charge is neutral and flocculation of the
powder is favored. The PZC is closely related
to the relative acid-base nature of the surface
groups. For ceramic powders, this will be very
dependent on the dissociative nature of the
surface, and the size and charge of the cation
in the lattice.
Ceramic surfaces are made up of surface
ROH groups which become protonated
Ceramic systems 513
under acidic conditions, or become negatively
charged under basic conditions. The acid and
base dissociation constants, Ka and Kb , are
given by (Lyklema, 1984)
[ROHi]
Ka = [ROH][H+] (20.18)
K [RO-][H2 0] 1 [RO-][H+] (20.19)
b = [ROH][OH-] Kw [ROH]
where Kw is the water dissociation constant
and R is a surface cation of the surface of a
ceramic such as an oxide (e.g. Si for Si02). At
the PZC, [RO-] = [ROHi] so that
[H+]rzc = (KbKw/Ka)1/2 (20.20)
10g(PZC) = !(pKa - pKb - pKw) (20.21)
The charge and radius of the lattice cation
also have a significant effect on the isoelectric
point of ceramic particles. Parks (1965) has
been able to accurately predict the isoelectric
point (IEP) as a function of the charge-to-
radius ratio (z+/a) of the lattice cation. The
IEP as a function of z+/a is given as
IEP = Aeff - 11.5 (Z; + 0.0029(CFSE))
(20.22)
where CFSE is the crystal field stabilization
energy. The predicted IEP is also dependent
on cation coordination number and the
hydration state of the surface. The predicted
variation of isoelectric point with the charge-
to-radius ratio is shown in Figure 20.6. The
isoelectric point of the metal oxide powders
are also shown. Fairly good agreement is
observed.
The surface of Si3N4 powders is thought to
be made up predominantly of silanol groups
(Si-OH), with a smaller proportion of amino
groups (Si 2-NH) (Busca et al., 1986; Shaw and
Pethica, 1986; Whitman, 1987; Nilsen, Riman
and Danforth, 1988; Bergstrom and Pugh,
1989; Stadelmann, Petzow and Greil, 1989).
The silanol groups are acidic in nature, while
the amino groups are basic. Depending on the
manufacturing route (and impurities), Si3N4
514 Solids dispersion in liquids

14
IEP =18.6-11.5 [i!eff A- Mg II
8 - Fe II
CoCo II
D-Ni II
12 E - Pb II
F - Cd II
G - La III
H - 8e II
10
1- Cu II
J - Zn II
K- Y III
8 L - AI III
a.. M - Th IV
w N - Pu IV
0- Fe III
0::---...
T
6 P- Hg II
Q- Ce IV
' ~ R - Zr IV
S-Cr III
4
o -Hydroxides and Hydrous Oxides T - Ti IV
U- U IV
0- 'Anhydrous' Oxides W - Sn IV
2 - Unflagged, CN = 6 X- Mn IV
b -CN=8 C).-CN=4 Y - Si IV
Z-WVI

o
o 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

z+/a
Figure 20.6 The relationship between IEP and (z+/a)eff' illustrating corrections for crystal field effects,
coordination and hydration. (Parks, G.A., 'The isoelectric points of solid oxides, solid hydroxides, and
aqueous hydroxo complex systems: Chern. Rev., 65(2), 177, 1965. Reproduced by permission of The
American Chemical Society, Washington, DC.)

powders can be produced with different
proportions of silanol and amino groups. The
IEPs of commercial powders will therefore
vary between powders and occasionally from
lot to lot. The IEPs of several commercial
Si3N4 powders are shown in Table 20.1.
Aging and/or washing of the powder can
affect the IEP by removing impurities, or chan-
ging the stoichiometry of the amino / silanol
surface (Whitman, 1987).
The surface chemistry of silicon carbide
(greater than 1 wt% oxygen) is generally
accepted to consist primarily of acidic silanol
groups due to surface oxidation (Crimp et al.,
1986; Whitman, 1987). At lower than 1 wt%
oxygen, it has been proposed that SiC also
consists of more basic carboxylate groups
(COO-). The IEPs of silicon carbide powders
are below pH = 7. Typical IEP values for SiC
powders are from 2.5 to 5pH (see Table 20.1).
Thus, SiC is typically processed in aqueous
systems using higher pH solutions. For SiC
powders with higher IEPs, acidic solutions
have also been used (Adair, Mutsuddy and
Drauglis, 1988). Anionic dispersants have
generally been used for silicon carbide
because of its similarity to silica (Persson,
Hermansson and Carlsson, 1983).
Non-oxide ceramic powders require sinter-
ing aids in order to densify completely by heat
treatment. The IEPs of several oxide ceramic
powders (Al20 31 Ti0 21 Zr021 Si02 and Y203)

Table 20.1 Isoelectric points (IEPs) of some selected ceramics
Ceramic
a-A1 20 3 (Linde A)
'Y-AI203 (Linde B)
a-A1 20 3 (Alcoa A-16 SG)
Ti02 (Rutile)
Monoclinic zr02 (Toyo Soda TZ-10)
Tetragonal zr02 (Toyo Soda TZ 3Y (3 mol% Y20 3
Vitreous Si02
a-Si0 2 (quartz)
Y2 0 3 (Shin-Etsu SU)
a-SiC (Lonza UF-10)
;3-SiC (Starck BDlO)
a-SiC (Showa Denko)
;3-SiC (Showa Denko)
a-Si3N4 (Starck LC-12)
a-Si3N4 (Ube SN E10)
a-Si3N4 (Denka 9S)
a-Si3N4 (Starck LC-lO)
a-Si3N4 (Ube SN E3)
a-Si3N4 (Ube SN E5)
commonly used as sintering aids are included
in Table 20.1. The oxide sintering aids must
therefore be dispersed in suspension along
with the non-oxide powder. Because of the dif-
ferent surface chemistries and isoelectric points
of the starting powders, heterocoagulation of
powders is commonly observed. To disperse
these systems, there are several approaches:
pH adjustment into a regime where all
powders are similarly charged;
specific adsorption of an ionic dispersant
causing the IEP to shift;
surface chemistry manipulation (e.g. react-
ing or encapsulating particles with a differ-
ing phase) (Liden et al., 1991);
prereacting sintering aids to form material
with one IEP (Meenan, Haber and Neisz,
1992).
An active surfactant may also increase the
surface charge potential and consequently the
zeta potential due to preferential adsorption of
co-ions at the particle surface. Frequently, it is
necessary to utilize more than one approach.
Ceramic systems 515
IEP Reference
(pH)
9.1 Yopps and Fuerstenau (1964)
8.9 Wiese and Healy (1975)
8 Hashiba et ai. (1988)
5.8 James, Stiglich and Healy (1981)
5 Hashiba et ai. (1988)
6.5 Hashiba et al. (1988)
2.4 Smit et ai. (1978)
2 Li and de Bruyn (1966)
9.5 Pollinger (1988)
2.5 Crimp et al. (1986)
3.5 Persson, Hermansson and Carlsson (1983)
4 Hashiba et al. (1988)
5.5 Hashiba et ai. (1988)
4.5 Stadelmann, Petzow and Greil (1989)
6.3 Crimp et ai. (1986 )
4 Pollinger (1988)
6 Persson, Hermansson and Carlsson (1983)
5.3 Malghan and Lum (1990)
5.7 Malghan and Lum (1990)
Common oxide sintering aids dissolve
rather easily in water (e.g. MgO, YZ0 3 )
(Greil, 1989). Dissolution generates multi-
valent cations which can preferentially
adsorb on the surface and collapse the
double layer around the non-oxide powder.
Strategies to avoid this problem include:
proper pH selection;
prereacting to form an insoluble compound
(e.g. MgO, Alz0 3 additives prereacted to
form magnesium aluminate spinel);
selection of less soluble forms (magnesium
carbonate vs magnesium hydroxide/ oxide).
Silicon nitride (Si3 N 4 ) is commonly dispersed
in higher pH solutions to avoid dissolution of
the sintering aids and to avoid the downward
shifting of the IEP due to surface hydrolysis.
Silicon carbide (SiC) slips are also commonly
deflocculated in the high pH range to prevent
hydrolysis of the surface.
The use of non-aqueous systems affords the
capability of processing without hydrolysis
and dissolution of the powder additives. In
516 Solids dispersion in liquids
general, the addition of a surfactant which
has two segments, one with better than ()
conditions (where () is theta temperature),
the other with worse than () conditions, will
promote powder dispersion. The segment
with worse than () conditions will prefer-
entially adsorb on the surface, while the
other will extend from the surface. Block
copolymers have been found to be useful in
dispersing ceramic powders in non-aqueous
media (Lee, Pober and Calvert, 1986).
Silicon nitride has been successfully spray
dried in methanol (Peuckert, 1988) and tri-
chloroethane (Kito and Hattori, 1987). Non-
aqueous solvents have also been used
successfully to spray dry silicon carbide
(Yamauchi and Hiramatsu, 1988) and
aluminum nitride (Hirokawa and Taniguchi,
1991).
RHEOLOGY OF NON-OXIDE SLIPS
The degree of dispersion which exists
between ceramic particles in suspension has
a direct effect on the ability to process non-
oxide slip formulations for spray drying.
More specifically, the dispersion characteris-
tics of the ceramic particulate directly control
the rheological behavior of the spray-drying
slip, and therefore control the ability to pro-
cess the slip and form dense, free-flowing
granules in a reproducible manner. Important
secondary properties such as particle size
and shape, particle size distribution and
solids loading also influence slip rheological
behavior. The effect of the aforementioned
properties on the rheological behavior of
non-oxide slips will be addressed in this
section.
The viscosity of a fluid is a measure of its
internal resistance to flow. The Newtonian
concept of viscosity consists of infinitely thin
layers of liquid between two parallel shear
plates. The viscosity is defined as the ratio of
the shear force per unit area (F / A) between
plates to the velocity gradient (dv/dx) within
the fluid (Reiner, 1960):
(F/A) T
(20.23)
I-L = (dv/dx) l'
where T is shear stress and l' is shear rate.
The viscosity of non-oxide slips, however,
will be more complicated because there will
be particles suspended in the liquid. Equa-
tions relating viscosity to particle volume
fraction are extensions of an equation devel-
oped by Einstein (1956). A well-known rela-
tionship for describing viscosity as a function
of solids loading is that derived by Mooney
(1951):
2.5 )
'f/rel = exp ( 1 _ k (20.24)
where is the volume fraction of solids and k
is a constant.
Another frequently used relationship is the
Krieger-Dougherty equation (Barnes, Hutton
and Walters, 1989):
_ ( )-['7lcf>m
'f/rel- l-m (20.25)
where ['f/] is intrinsic viscosity. The maximum
packing fraction, m, is the particle fraction in
which a continuous three-dimensional net-
work is formed and flow becomes impossible.
Its value is strongly dependent on particle size
distribution and particle shape (deviations
from sphericity will increase viscosity and
lower m due to greater interlocking of
particles). Because of this, its value is
typically elucidated by measuring the con-
centration dependence for the system of
interest and applying a nonlinear curve fit
to calculate m. The intrinsic viscosity is the
reduced viscosity as the concentration
approaches zero.
Equations 20.24 and 20.25 are important
relationships for the processing of non-oxide
ceramics because they allow the prediction
of viscosity as a function of slip solids loading.
The variation of viscosity with slip solids
loading becomes extremely important when
 Rheology of non-oxide slips 517
dealing with highly concentrated slips. Slight suspension can be controlled by contouring
changes in solids loading (e.g. suspending the particle size distribution. In addition,
medium evaporation) can lead to large the higher packing densities achieved in the
changes in viscosity, thereby affecting slip slip can lead directly to higher throughput in
transport and drying behavior. Tight control the dryer. For non-oxide systems, there is a
of rheological behavior is necessary for an limitation on how coarse the distribution
efficient spray-drying process. can be while still being sinterable, and how
Thus far, systems with monodisperse par- fine the distribution can be without wide-
ticles have been considered. Suspensions spread flocculation occurring. Within the
which have a distribution of particle sizes two regimes, however, the packing equations
will be rheologically very different. An ideal can be very useful for obtaining high degrees
packing equation for continuous particle size of particle packing and, consequently, low slip
distributions has been conceived by Andrea- viscosities.
sen and Andersen (1930) and has more To this point, Newtonian suspensions have
recently been improved on (Funk, Dinger been considered. Newtonian suspensions
and Funk, 1980). The ideal packing equation is possess a viscosity which is independent
of shear rate. The shear stress-shear rate
(20.26) behavior for Newtonian and non-Newtonian
suspensions is shown in Figure 20.7. Curve 1
where d is the diameter, dmax and dmin the is indicative of Newtonian behavior. Most
maximum and minimum diameters. It has non-oxide slips at high solids loading,
been found that the slip viscosity can be however, will show some degree of non-
greatly reduced when the distribution modu- Newtonian behavior.
lus, n, is close to 0.37. Coarse, well-deflocculated suspensions at
The relevance of the discussion on particle high solids loading will behave similarly to
packing is that the viscosity of a non-oxide curve 2 in Figure 20.7. The viscosity increase

_.-._._.-._._._._;-
4

Bingham ,.,......
_..... -.-. 3
,
I

..
FlOW.," " " , " ' _______ .

........" " I

........
I
I
,'. I
I
,','." I
I
,/ ' Pseudoplastic I

,
"
//Dilatant
,, ,- /
/

,
I
,-
I
,- ,-
,,
I
I I'
I' 2
, I
1'1'

--
1'1'
I
I
...... ......
----
I
I

Shear Rate
Figure 20.7 Flow curves encountered with ceramic suspensions.
518 Solids dispersion in liquids
as a function of shear rate is termed dilatancy,
or 'shear thickening'. The occurrence of dila-
tancy in non-oxide slips is limited, primarily
because the particles must be fine in order to
sinter. However, dilatancy has been observed
in well deflocculated non-oxide slips at
high shear rates. Dilatant flow will cause slip
milling and mixing to become very difficult.
Broadening and/or reduction of the particle
size distribution will lessen the onset of
dilatancy (Collins, Hoffman and Soni, 1979).
As discussed in previous sections, van der
Waals attractive forces between particles
cause flocculation. The flocculation will
cause a portion of the solvent to become
immobilized within the flocs, thereby increas-
ing the effective solids loading of the slip
(Vand, 1948). Increasing the rate of shear
applied to a flocculated slip will promote
the breakdown of the flocs, freeing up the
immobilized fluid (Michaels and Bolger,
1962). The structure of a flocculated slip with
increasing shear is conceptualized in Figure
20.8. The slip viscosity will decrease as a
function of shear rate due to the liberation of
immobilized fluid. This type of behavior is
termed pseudoplastic, or 'shear thinning'
and is illustrated by curve 3 in Figure 20.7.
Continuous
Network
Structure
Increasing Shear Rate
Figure 20.8 Dependence of slip structure on shear rate for a concentrated suspension.
Particle flocculation is also the mechanism
responsible for the Bingham yield shown
by curve 4 in Figure 20.7. When particles
flocculate to an extent that a continuous net-
work is formed, the system will not flow
until a critical stress is exceeded. Once this
stress is exceeded, the flow will typically be
pseudoplastic due to increasing floc break-
down with shear. The Bingham yield will
increase with solids content and decrease
with zeta potential and particle radius (Firth,
1976; Chou and Lee, 1989).
When the shear is removed from pseudo-
plastic slips, Brownian motion will cause the
particles to recombine into flocs. The recombi-
nation of discrete particles into flocs does not
occur instantaneously, but occurs over time.
Therefore, the viscosity of the slip will be
lower upon removal of shear because less
solvent will be immobilized in flocs upon
cessation of shear than when the shear was
applied. This time lag required for flocs to
reform creates a time-dependent rheological
behavior called thixotropy.
As already discussed, the nature of the
surface charge on non-oxide powder surfaces
(i.e. the zeta potential) is influenced by sus-
pension pH. Slip viscosity, thixotropy and
Discrete Primary
Floes or Particles
Aggregates or Floes
of Floes

Bingham yield stress are therefore expected to
vary as a function of suspension pH. At the
particle IEP, there is very little surface charge
available to prevent particle flocculation (i.e.
the zeta potential is low), and non-Newtonian
behavior will result. In this case, the slip
viscosity and yield stress are expected to be
high, and thixotropic behavior is expected.
At pH values where a high surface charge is
expected, flocculation will not be favored
and the flow may become close to Newtonian.
The viscosity will be low and the yield stress
will be very low or completely eliminated. The
effect of the zeta potential and viscosity as a
function of pH is shown in Figure 20.9.
A Bingham yield stress is sometimes
desired because it can prevent sedimentation
at high solids loadings by forming a continu-
ous network structure capable of supporting
coarse slip constituents (Phelps, Silwanowicz
+
Iii
E As previously seen, the rheological behavior
<D
o 0 ~----------~~------------
Cl.
~
N
pH
pH
Figure 20.9 Effect of particle zeta potential on sus-
pension viscosity.
Spray drying 519
and Romig, 1971). At low solids loadings,
however, the flocs may be discrete and
enhance sedimentation by acting as larger
settling units. High degrees of pseudo-
plasticity will create transport problems and
make redispersion of stored slips difficult. In
addition, the high viscosity associated with
pseudoplastic slips during processing (low
shear present) makes evolution of air bubbles
(which can arise during mixing) difficult.
These air bubbles act as defect centers and
will have deleterious effects on the final
mechanical properties of the sintered part.
It can be seen that interparticle forces, as
well as solids loading, particle size distribu-
tion and particle shape, play an important
role in determining non-oxide slip rheology.
Knowledge of these parameters allows the
slip rheology to be manipulated in a logical
manner, providing greater control over slip
processing and spray drying.
SPRAY DRYING
of non-oxide slips is directly influenced by
the dispersion properties of the particulate
constituents. In this section, the effect of rheo-
logical behavior on the processing and spray
drying of non-oxide slips will be examined.
The process of spray drying is reviewed in
Chapter 21.
Slurries are prepared in large mixers or
blungers, or the slip constituents can be
added directly to a mill. Slips are commonly
ball milled or attrition milled to break down
soft agglomerates which form from van der
Waals forces, and/ or to fracture large primary
particles. The milling process also distributes
the sintering aids and binders uniformly.
Binders are best added late in the milling
process to avoid processing problems. Early
binder additions can be detrimental because
of the following (Hoffman, 1972).
1. Severe mechanical action in the mill
degrades binders.
520 Solids dispersion in liquids
2. Binder can cushion media impact and
reduce milling efficiency.
3. Binder dilution can reduce solids content
below optimal value for spray drying.
Milling is typically done on well-defloccu-
lated slips. As discussed, good dispersion
can be maintained by using the proper pro-
cessing pH, using satisfactory surfactants
and avoiding dissolution of constituent
powders. Slip viscosity should be low
enough so that the impact of the milling
media is not cushioned, yet not so low that
the particles move away from the impact
zone (Reed, 1988). Both of these conditions
can be attained by using a highly concen-
trated, well-deflocculated slip.
Once the binder has been thoroughly dis-
tributed in the slip, the slip is pumped to a
holding tank before being spray dried. Slurry
viscosity must be low enough for efficient
pumping. Dilatant slips will not flow well
when pumped. If dilatancy occurs during
milling, the initial solids loading of the slip
should be lowered. Additional powder can
be added sequentially once a significant per-
centage of fines has been generated in the
mill. This effectively contours the particle
size distribution and lessens the onset of dila-
tancy. However, dilatancy is normally not a
problem with non-oxide slip formulations
due to the fine particle size requirements of
the powder.
Industrial holding tanks have a paddle or an
impeller to agitate the slip. This helps prevent
the recombination of the dispersed particles
into flocs. For aqueous systems, this is crucial
since floc formation is not as easily reversible
as with non-aqueous systems. Segregation
effects due to sedimentation must be avoided
to produce reproducible, sinterable granules.
Sedimentation effects increase as the solids
loading is reduced and the particle size
increases. Sedimentation can be avoided
using highly concentrated, fine particle dis-
persions. In addition, agitation during storage
can help prevent particle segregation. Slip
rheology can be manipulated by controlling
the interparticle attractive and repulsive
forces. In this manner, thixotropy can be
engineered into the non-oxide slips. As pre-
viously discussed, this can help minimize
sedimentation in concentrated suspensions.
The viscosity should be low enough, however,
to allow air bubbles to be vented. Occluded air
will lower granule density, which will be
detrimental to final part properties.
Although slip rheology during processing
is very important, it is the viscosity at the
atomizer which has the most direct effect on
the granule character. The shear strain rate at
the nozzle is typically high, regardless of
atomizer type. The high shear rate breaks
down the structure within the slip. To under-
stand the rheological behavior of the slip it is
necessary to measure the viscosity response to
shear over a wide shear rate range. In general,
the atomized droplet size is proportional to
slip viscosity (Masters, 1985). Dilatant slip
behavior will cause improper atomization at
the nozzle, or induce clogging.
Another important aspect of particle dis-
persion is its effect on the microstructure of
the atomized droplets. Drying of the droplets
occurs through capillary flow of the dis-
persion medium from the interior of the
droplet to the droplet surface. The permeabil-
ity to liquid of the particles in a droplet will
therefore significantly affect the drying
rate. The interrelationship of dispersion and
rheology on the structure and permeability
of cakes in filter pressing and slip casting has
been thoroughly investigated. Unfortunately,
very little is known about the role of dis-
persion and rheology on atomized ceramic
droplet structure. A low permeability in the
outer skin of a drying droplet has been identi-
fied as a source of hollow granules (Masters,
1985). It would seem that some investigation
in this area is warranted.
Interparticle dispersion is very important
because it controls the amount of solids
which may be incorporated into a spray-
drying slip. Hollow granules, which reduce

green and sintered densities, have been asso-
ciated with low solids-loading slips (Konsz-
towicz et al., 1992; Uematsu et al., 1990).
Analysis of the process with respect to
drying shows that higher solids loadings will
increase the powder output. It has been found
that increasing the solids from 50% to 75% by
weight can triple powder output (Lukasie-
wicz, 1989). However, tight control of solids
loading is essential at higher solids loadings
because small changes in solids content can
change the character of the granules.
REFERENCES
Adair, J.H., Mutsuddy, B.C and Drauglis, E.J.
(1988) Stabilization of silicon carbide suspen-
sions: I. Influence of surface oxidation in aqueous
suspensions. Adv. Ceram. Mat., 3(3), 23l.
Andreasen, AH.M. and Andersen, J. (1930) Uber
die Beziehung zwischen Kornabstufan und
Swishenraum in Produkten aus losen Korhern
(mit einigen Experimenten). Kolloid Z., 50, 217.
Barnes, H.A., Hutton, J.F. and Walters, K. (1989) An
Introduction to Rheology, Elsevier, New York.
Bensley, CN. and Hunter, RJ. (1983) The coagula-
tion of concentrated colloidal dispersions at low
electrolyte concentrations: I. Rate of coagulation
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SPRAY DRYING
Fred V. Shaw and Michael H. Andrews
INTRODUCTION
Spray drying is a method of blending different
components in a liquid form and processing
in one continuous step into a dry powder.
Its basic principles have been in use for
approximately 100 years. In the past, a liquid
ceramic feed material was filtered, tray dried,
rewetted and then crushed into a workable
particle size. The spray dryer combines these
steps into a single process.
A typical drying system (Figure 21.1) starts
with a heated gas source that is introduced
into a cylindrical chamber. At the same
time, a liquid feed material is also introduced
into this drying chamber. The feed is atom-
ized into a fine spray or mist so that the hot
process gas can evaporate the liquid, leaving
the solid portion of the feed in a dry particu-
late form.
Coarse, dry particles are collected at the
base of the drying chamber. The dried fine
particles and the vapor laden process gas
pass from the drying chamber to the powder
separator. The separator is usually a cyclone, a
baghouse or a combination of both. The dried
particles are discharged from the bottom of
the cyclone while the process gas is pulled
out of the top. This gas now goes to the bag
collector for final cleaning.
An open cycle, which is used with non-
hazardous aqueous feed materials, would
exhaust the process gas to the atmosphere.
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
21
The process gas would be air in this case.
When an organic solvent is used in the feed
material the process gas is an inert gas such
as nitrogen. If large amounts of the process
gas are required, the system is closed and
the process gas is recirculated.
This is the basic system that is used to dry
from several kilograms of product per hour in
the pilot plant (Figure 21.2) to many tonnes
per hour at the production plant (Figure
21.3). The arrangement of equipment, con-
figuration of the drying chamber and the
type of atomization selected will dictate the
properties of the final product.
Many of the ceramic powders that are spray
dried go to a pressing operation to be formed
into small parts for cutting tools or high tem-
perature engine parts. This operation usually
includes the use of an automatic press, as
opposed to a small scale, manually fed
device. The automatic operation calls for uni-
form ceramic powders with good flowability
characteristics. Generally, sufficient flow-
ability can be achieved with powders in the
80-150/-lm range.
In order to produce a ceramic particle in
this size range, it may be necessary to include
additives in the feed to act as binders and
lubricants. Also, for control of powder den-
sity, deflocculents or dispersing agents are
often added to permit a higher percentage of
solids in the feed. These considerations were
discussed in Chapter 20.
526 Spray drying
Figure 21.1 Schematic of a typical open loop aqueous spray-drying system.
The binders are usually organic, and not
more than 3-4 wt%. This is enough to hold
the small particles in the feed together to
form the large particle needed for the pressing
operation. Later in the process the binder will
be burned off.
Ahigh percentage of solids in the feed will
help the economics of the operations and also
promote larger particle sizes in the final prod-
uct (Smith, 1993). The solids can be increased
only to a point where the feed is still workable.
The dispersing agents are added in order to
keep the viscosity down to a workable range
(Chapter 20). If the viscosity is too high, the
feed will not atomize properly or the atomizer
may become plugged, stopping the operation.
The dispersing agents help to insure a contin-
uous flow of powder to the pressing operation
and the most economic running conditions.
Spray drying is also used to produce cer-
amic powders for coatings applied with the
plasma spray process. The powders are
injected into the plasma gun where they are
melted by its high temperature. The melted
powders are sprayed onto a base material
where they rapidly solidify. These coatings
are used for heat resistance, wear resistance,
Exhaust
Product
corrosion control, electrical conductivity or
resistivity, and clearance control (Varacalle
et ai., 1991). Spray-dried powders in the 60-
100 Mm size range work well with the plasma
spray gun. Usually small quantities are
required so that a pilot or small scale produc-
tion dryer can be used. The choice of atomiza-
tion will depend on the size of the dryer and
the average particle size that is desired.
Because spray drying is such a fast transfer
from the liquid stage to a dry particle, the
resulting powder is a homogeneous mixture
of the feed components. Each particle will
contain basically the same ratio of the com-
ponents of the feed material. Where other
drying methods may allow feed components
of different densities to segregate during the
drying process, spray drying does not. This
becomes very important when the electrical
characteristics of a part depend on the precise
distribution of three or four different materials.
BASIC PROCESS - OPEN SYSTEMS
Spray drying incorporates one of several dif-
ferent types of atomizers (Figure 21.4) which
can be located at varying positions in the
 Basic process - open systems 527

Figure 21.2 Pilot plant spray-drying system. (Photo courtesy of Niro, Inc., Columbia, MD.)

drying chamber in order to create a dried
particle with the desired shape and size
(Helsing, 1987).
Rotary atomizers which are located in the
top of the drying chamber work on the
principle of centripetal and tangential accel-
eration (Figure 21.5). A feed is introduced
into a spinning wheel where it is accelerated
to the peripheral velocity of the wheel. As
the liquid leaves the wheel, a shearing force
528 Spray drying

Figure 21.3 Production plant spray-drying system. (Photo courtesy of Niro, Inc., Columbia, MD.)

Figure 21.4 Spray-drying atomizer types. (Photo courtesy of Niro, Inc., Columbia, MD.)
causes it to break up into individual droplets.
The size of these droplets can be varied by
changing the speed of the wheel. In some
cases they can also be varied by changing to
a different size of wheel. Both of these changes
come down to the fact that slower peripheral
velocities produce larger particle sizes.
Another type of atomization is the two-fluid
nozzle atomizer. This type of nozzle uses
high velocity gas as one of the two fluids, to
break the liquid feed stream into individual
particles. This can be accomplished as the
liquid leaves the nozzle, termed 'external
mix nozzles', or within the nozzle cavity,
termed 'internal mix nozzle'.
Basic process - open systems 529
Both arrangements have advantages and
disadvantages. The internal mix nozzle will
produce a narrower particle distribution but
is limited to materials below 1 Pa s (1000 cp)
as a typical viscosity. On the other hand,
the external mix nozzle can handle a higher
viscosity without plugging problems, but
produces a wider particle size distribution.
The particle size of the powder can be
varied when using the two-fluid nozzle by
varying the air-to-liquid feed ratio, on a
weight per weight basis. The higher the
ratio, the finer the particle size. The opposite
is true when lowering the air rate; a coarser
particle can be produced. There is a limit to
530 Spray drying
Figure 21.5 Atomized droplets forming from rotary atomizer stream. (Photo courtesy of Niro, Inc., Colum-
bia, MD.)
this range where the atomization is not uni-
form and plugging takes place in the nozzle
or wall and ceiling deposits form.
A third form of atomization is the pressure
nozzle. This nozzle relies on the pressure that
is produced by the pump to break up the
liquid feed into droplets as it hits the drying
medium. A pressure nozzle can produce
coarse particles in a narrow distribution
range. The size of the particle is controlled
by the pressure of the liquid in conjunction
with the nozzle orifice size and geometry
(spray angle).
The way the spray from the atomizer com-
bines with the hot gas determines the rate
and extent of the drying process. The hot gas
can contact the spray in a co-current or mixed
flow direction. This gas-solids contact is
controlled by the air disperser location and
design, the chamber dimensions and the
atomizer location. Optimum conditions will
leave the chamber walls free of deposits. The
air disperser design is most critical for proper
gas-solids contact.
Air dispersers designed for co-current gas-
solids contact can be roof type air dispersers or
central type dispersers. With the roof type
disperser, the hot gas enters from above the
atomizer. This imparts a rotational gas flow
down around the atomizer.
The central type of air disperser is located
under the atomizer. The hot gas is ducted in
through the drying chamber cone and exits
the insulated duct below the atomizer. The
hot gas is given a rotating motion as it leaves
the air disperser.
Because of this arrangement below the atom-
izer, the process is capable of inlet tempera-
tures as high as 1023-1123 K (750-850C).
This is due to the fact that the atomizer and
drive are not exposed to these temperatures
as they are with the roof air disperser. One

drawback to this system is that the central air
disperser is suited for rotary atomization only
because of the horizontal trajectory.
When the solids contact the gas, they can do
so by rotating in the same direction or in an
opposing direction. If the contact is in the
same direction, the air flow is easier to control
and anticipate. An opposing gas-solids con-
tact gives greater mixing and allows coarser
sprays to be dried per given chamber dimen-
sions.
The co-current gas direction from a roof air
disperser can be used with nozzle atomizers in
either a rotary air flow pattern or a laminar air
flow. The laminar air flow is created by pass-
ing the air through perforated sheets or
straightening vanes. Dryers with a laminar
air flow type of air disperser are tower
dryers which may have a straight side that is
as much as five to six times their diameter.
Another type of air flow pattern used for
gas-solids contact is the mixed flow type of
dryer. In this arrangement, a nozzle atomizer,
either a pressure nozzle or two-fluid nozzle, is
positioned in the cone section and sprays
upward into and against the hot gas that is
introduced into the roof.
This arrangement effectively allows the
drying chamber to be used twice as the
sprayed solids travel upward against the air
flow and then turn and fall back down to the
bottom of the dryer. This creates a longer resi-
dence time and allows coarser sprays to be
dried per given chamber dimensions.
Now that the product is in a dry form, it
must be separated from the exhaust gas and
removed from the spray-drying system. The
first consideration is to use the most economic
means for dry solids recovery. The second
requirement is for the exhaust gas to be free
of airborne particles. The gas must be cleaned
to prevent discharge of fine particles to meet
or exceed local or national clean air standards.
The product can be separated from the
exhaust gas in a simple system by conveying
everything from the drying chamber to a main
cyclone. This system is generally used when
Basic process - open systems 531
the average particle being produced is less
than 75J.tm.
If the average particle size is greater than
75 J.tm, the coarse material is usually collected
at the base of the drying chamber. The fine
material and the exhaust gas are then pulled
from the center of the drying chamber cone
over to a cyclone in order to remove the fines
from the exhaust gas. The degree of separation
in the drying chamber will be approximately
80% depending on particle density and size.
This arrangement is the most common collec-
tion system used for ceramics.
The product that is collected from the
drying chamber should be in a form that is
ready to use, either in a manufacturing
process or for sale. The cyclone material may
contain some usable product that can be
screened out or it all can be re-slurried and
put through the system again.
Two types of secondary dust recovery
systems are in general use. A dry system
such as a bag collector is usually preferable
over a wet scrubber. The wet scrubber is
more economical in terms of capital invest-
ment and maintenance, but it is only 80-96%
efficient. There is also the problem of dispos-
ing of the recirculated liquid after it has
become saturated with fine particles.
The bag collector system will separate the
fines and continually discharge them in a
dry form. It has a high efficiency rating of
95-99.5%, but it also has a high maintenance
cost. The bags that are the main component
of the system will need to be replaced due to
wear. Some of the large drying systems may
have bag collectors containing several hun-
dred bags.
AGGLOMERATE SIZE AND SHAPE
As the liquid feed is atomized and contacts the
hot gas, the temperature of the droplets
increases and evaporation of the liquid takes
place. The size and shape of dried particles
are greatly affected by the drying rate and
atomization.
532 Spray drying
Each droplet consists of many tiny particles
being held together by a liquid. As the particle
dries, the moisture from the center migrates to
the surface (Graef and Seitz, 1991). From the
surface, the moisture is rapidly transferred
into the drying gas. As the evaporation takes
place, the temperature in the drying chamber
is lowered.
The temperature on the particle surface is
approximately the wet-bulb temperature of
the drying air. The surface temperature is
held constant as the internal moisture moves
to the surface at a constant rate to maintain
surface saturation. This is generally termed
first-order drying.
As the evaporation continues, the particle
will get to a point where the surface wetness
can no longer be maintained. The temperature
of the particle will now start to increase. The
lack of moisture on the surface creates the
formation of a dried shell. Now the rate of
evaporation decreases because the moisture
has difficulty penetrating the outer shell.
This causes the shell to thicken. The decrease
in evaporation is the final stage of drying
before the particle leaves the system. This is
known as second-order drying.
When the droplet leaves the atomizer, it
travels from a hot zone in the drying chamber
to a cooler zone. Because the particles do not
rotate, one side of the particle sees a greater
temperature than the other side. This causes
the shell on the hot side to form faster. If a
pressure is created in the center of the particle
by trapped vapors, the weaker side of the
particle may expand to balloon the particle
leaving the center hollow or it may explode to
release the pressure and collapse in on itself.
While this is the generally accepted explana-
tion for particle ballooning, other mechanisms
have been reported (Lukasiewicz, 1989).
The drying rate and the rate at which a shell
is formed can be affected by additives, i.e.
binders and dispersants. Outside of the
formulation, the drying rate is affected by
the inlet temperature. If the inlet temperature
is too high, a dried layer will form almost
immediately. This can cause the particle to
retain moisture, balloon or collapse.
On the other hand, if the inlet temperature
is lowered, the first-order drying is extended.
This has an effect on the particle size and den-
sity. When the moisture leaves the particle at a
steady, slow rate, the particle will shrink and
form a denser, more uniform sphere (Moller,
1980).
SYSTEM DESIGN AND SCALE-UP
Component sizing
There are two basic considerations in the sizing
of a spray-drying system. One is the heat and
mass balance required to achieve the specified
evaporation. The other is the size of the drying
chamber required by the desired particle size of
the spray-dried powder.
A simple mass balance is first performed to
determine the quantity of evaporation needed
to produce the desired amount of dry solids
from the feed slip at the highest available
feed solids concentration (Masters, 1991). Since
the spray-dried product is not always entirely
within the specified particle size range, a feed
rate somewhat greater than theoretical is nor-
mally used to produce the desired production
rate.
Knowing how much liquid must be heated
and evaporated, and allowing for some heat
transmission through the system walls, a
total process heat input is calculated. This
quantity of heat is the product of the mass
flow of air through the system and the tem-
perature difference from inlet to outlet. The
inlet and outlet temperatures which are
appropriate for a given product must be
determined experimentally or known from
experience.
All system components can then be sized,
based on the calculated air flow. The heater
is sized to heat the mass of air from minimum
ambient to inlet temperature. Ducts, air dis-
persers, cyclones and fans are all sized for a
specified pressure drop at the calculated air

flow. Bag collectors are sized by an air-to-cloth
ratio.
Only the drying chamber cannot be sized by
gas flow alone, although it is one important
consideration. Experience with a particular
type of atomization and air disperser com-
bination dictates a gas residence time required
in the drying chamber to permit adequate
control of the drying process and, hence,
final product moisture. Gas residence times
ranging from 12 s to 1 min have been required
for various products. As a rule, the larger the
droplets produced by the atomizer, the longer
the gas residence time required. Therefore, for
a given gas flow, products that demand a
larger particle size will need larger drying
chambers (Figure 21.6).
The other key factor in drying chamber
design is the type of atomization employed
and the configuration of the atomizer in the
drying chamber. Rotary atomizers require
larger diameter but less cylinder height than
nozzle dryers. In the ideal situation, the
volume needed to meet the gas residence
time requirement can be satisfied by the mini-
mum chamber diameter and height required
for the desired particle size distribution. It
Basic process - open systems 533
is important that the final design meets both
minimum criteria, even if it exceeds one of
them.
Once all of the components are sized, it is a
matter of arranging them in suitable fashion
with ease of operation and maintenance
in mind. Most smaller systems are pre-
engineered as 'package plants'. Larger dryers
are usually custom arranged to suit the loca-
tion available and equipment upstream and
downstream from the dryer installation.
Scale-up
Generally speaking, spray-drying systems are
not scaled up directly from pilot or laboratory
tests. Instead, the development work is used
to establish inlet and outlet temperatures and
to get a feel for the type of atomization that
produces the best powder. Engineers can also
learn how fast the material dries and predict a
required gas residence time. The information
gathered during this work is then used to
perform the heat and mass balance which
determines the production equipment size.
This method is far more accurate than direct
scale-up from a test dryer.

7
E
"
....-
(J)
Qi
6

5
E
co
is
....
(J)
4
.0
E 3
co
.r:.
()
Cl 2
c
.~

40 60 80 100 120 140 160 180 200 220

Mean Particle Diameter, dso (j.Lm)

Figure 21.6 Mean particle diameter vs minimum chamber diameter for rotary atomizers.
534 Spray drying
CLOSED CYCLE SYSTEMS
An aspect of non-oxide processing which tends
to complicate spray drying is that non-oxides
are often milled or slurried in an organic
media. Since these liquids are most often flam-
mable organic solvents, both safety and environ-
mental hazards are of concern (Shaw, 1986).
Conventional spray drying uses heated air
to evaporate liquid. The air and resulting
vapor are exhausted to the atmosphere. This
is dangerous when organic solvents are used
because the mixture of air and organic solvent
vapor can easily be within the explosive limits.
Further, release of the vapors to the environ-
ment is illegal, not to mention expensive.
The solution to these concerns is to close the
loop on the spray-drying process (Figure 21.7).
Once the dried powder is separated from the
drying gas the solvent is condensed and the
gas is returned to the heater for reuse. Since
the drying gas is being recirculated, an inert
gas such as nitrogen can be used, eliminating
the possibility of combustion of the solvent
within the drying system.
Because many different solvents, and even
combinations of solvents, are used and
Figure 21.7 Schematic of a typical closed loop solvent-based spray-drying system.
because each spray-dried powder has slightly
different characteristics, closed loop spray-
drying systems are always custom designed
and engineered. There is no standard
equipment sizing which would provide the
necessary evaporative capacity, powder
production and solvent recovery for every
case. As a result, process calculations for a
particular solvent must be performed and
each item in the system must be designed
and sized for that case.
It is quite obvious that an inert gas will have
to be heated indirectly in a heat exchanger.
Steam is the most common source of heat.
Often, if there is no process steam available,
or if the pressure is too low to provide a suffi-
ciently high temperature for the process gas, a
recirculated hot oil system may be used. These
are available as a skid-mounted package and
can be either electrically heated or gas fired.
A shell and tube heat exchanger is usually
selected for the process gas heater. The exchan-
ger must be sized for the particular process
gas and residual solvent vapor on one side
and the heating medium on the other. Besides
providing sufficient heat transfer surface
area, materials of construction, gasketing,
Condensate
Scrubber
Condenser
Recovered
Solvent

connections and expansion joints must all be
properly selected.
From the heater, the process gas passes to
the spray-drying chamber through the inte-
gral gas disperser. These items do not greatly
differ from those used in conventional sys-
tems except that doors, sight ports etc. must
be correctly specified for closed cycle service.
It is important that process gas does not leak
into the operating area around the dryer and
that ambient air does not leak into the system.
As with any spray dryer, the drying chamber
must be properly sized for both gas retention
time and particle size distribution considering
the mode of atomization.
Atomization can be either by pressure
nozzle or rotary atomizer. In the case of the
pressure nozzle, a high pressure, abrasion
resistant, positive displacement pump must
be used. If there are elastomer parts such as
diaphragms, stators or seals, these must be
compatible with the ceramic, the solvent and
any other additives such as dispersants,
binders or lubricants. The pump must have a
suitable pulsation dampening device if it is of
a type which does not produce a smooth flow
of liquid. Pump parts must be consistent with
explosion-proof service and the drive should
have an explosion-proof motor.
When a rotary atomizer is used, the same
principles apply. It must be properly sealed
into the drying system and designed for use
with the solvents in question. Special explo-
sion-proof atomizers are supplied by some
manufacturers.
At any point where powder is being col-
lected, there must be a device for removing
powder from the system while minimizing
any gas flow into or out of the system. In
most cases, removal is directly from the
bottom of the drying chamber. A system of
double butterfly valves, timed so as to prevent
any straight-through opening, is usually
employed. The spent process gas leaves the
dryer through an outlet duct in the cone
portion of the chamber. Fines removal from
this gas stream is accomplished by use of a
Closed cycle systems 535
cyclone, a bag collector or both. If a reverse
pulse bag collector is used, the pulse gas
must be the same inert gas used throughout
the system. Since this creates a regular flow
of nitrogen into the system, there must be an
equal amount of gas vented from the system.
This gas will contain an equilibrium fraction
of solvent. Powder removal from the cyclone
or bag collector must also be done so as to
prevent gas flow into or out of the system.
Since this is ordinarily a small amount, a
sealed collection container is often used at
these points.
The next step in the process is to recover the
solvent which was evaporated in the dryer.
This is accomplished by means of a direct
contact scrubber/condenser. This device is a
cylindrical, vertical vessel containing a series
of sieve trays. Chilled solvent is pumped
continuously onto the top tray and cascades
downward from tray to tray. The gas flow is
counter-current upward through the tray
perforations. Intimate contact is achieved
between the cold liquid and the warm gas,
resulting in cooling of the gas and condensa-
tion of the solvent. When the nitrogen leaves
the top tray, it will be saturated with solvent
vapor at the gas temperature. A suitable mist
eliminator is required to prevent entrainment
of liquid solvent drops or mist. Solvent leav-
ing the bottom tray is collected in a sump
and pumped through a heat exchanger and
back to the top tray. Chilled liquid such as
brine or glycol solution must be supplied to
the heat exchanger.
From the scrubber/condenser, the gas can
pass back to the process gas heater. The only
items in the loop not mentioned so far are two
fans which provide the flow of gas through
the system. These must be equipped with
balancing dampers in order to maintain a
positive pressure throughout the system.
Again, the fans must be supplied with special
bearings and shaft seals to prevent excessive
loss of solvent vapor or inflow of air.
Explosion-proof motors and non-sparking
moving parts are required for safety reasons.
536 Spray drying
Instrumentation and control for a closed loop
system is considerably more rigorous than that
required for open systems. Besides tempera-
ture control for inlet and outlet temperatures,
there are the sump level and system pressure
to control. Oxygen analysis of the gas stream
is required. There must be a pressure relief
vent for pressure which builds up from nitro-
gen purges, thermal expansion and the bag
collector if present. There also must be an
emergency vacuum relief, should rapid cooling
cause a vacuum in the system during an upset
situation. All vents must be equipped with
flame arresters. All wiring for power and light-
ing must be explosion proof and instrument
wiring must be explosion proof or intrinsically
safe. Grounding is crucial and must be
performed per code (see Process Control
section for details).
One inconvenience inherent in a closed
cycle system is cleaning of the system. Cer-
amics which consist of various components
may be produced in several grades having
different additives or varying concentrations
of minor components. As a result, it is desir-
able to clean the system between grade
changes. While it is possible to open the
system, purge with air and follow a safe pro-
cedure for manual cleaning, this is usually
time consuming and troublesome.
A clean-in-place system is often provided to
accomplish thorough cleaning of the system
without opening and purging. Besides short-
ening the time required, a considerable
amount of nitrogen is saved. These systems
employ a rotating cleaning nozzle which is
inserted through the top of the drying cham-
ber. Retractable spray heads can also be
affixed at key areas in the system ductwork
or cyclone. A high pressure pump and clean-
ing solvent storage tank supply solvent to the
system. A drain system, diaphragm pump
and settling tank recover the solvent from
the system. After the solids have settled out,
the solvent is returned to the storage tank.
Solids are removed from the bottom of the
settling tank.
Although the spray-drying system is
usually supplied as a complete package
(Figure 21.8), there are a number of ancillary
components. There must be an ample supply
of nitrogen available at all times. This is
usually provided by a liquid nitrogen storage
tank. Larger facilities often have this as part of
the utility supply service.
PROCESS CONTROL
Control of a spray-drying process is quite
simple, assuming the system is properly
designed and sized. The residual volatile
content of the product is usually specified
and must be controlled within a few tenths
of a percent. Since this variable is a function
of dryer outlet humidity and temperature,
and since humidity remains quite constant,
outlet temperature is the primary control
point. A higher outlet temperature will
produce a drier product. Additional moisture
can be left in the powder by lowering the
outlet temperature. There are two ways to
control this variable.
In the method usually employed with
rotary atomizer plants, the inlet temperature
is controlled to a set-point and the outlet tem-
perature is controlled by modulating the
feed rate (Masters, 1991). The greater the
feed rate, the lower the outlet temperature.
The fact that particle size is relatively insensi-
tive to feed rate through a rotary atomizer
allows feed rate modulation without disrup-
tion of product particle size. There are also
two ways to control feed rate. The most
traditional method uses a constant-head feed
tank and a control valve to provide feed
at a variable flow rate. Recently, with the
widespread availability of variable speed
AC drives, use of a positive displacement
pump with a variable speed drive is more
common. Pump speed setting can be con-
trolled directly from the outlet temperature
controller.
In the case of a pressure nozzle atomization
system, modulation of the feed flow will
 Process control 537

Figure 21.8 Photograph of a closed loop solvent-based spray-drying system. (Photo courtesy of Niro, Inc.,
Columbia, MD.)
538 Spray drying
have a pronounced effect on the particle size
distribution. As a result, feed rate must remain
constant. The only choice here is to allow the
outlet temperature to control the temperature
of the inlet air (Masters, 1991). This is often
done with two controllers in a cascade loop.
In this mode the outlet temperature controller
adjusts the set-point of the inlet temperature
controller. Because the pressure atomization
system almost always requires a positive dis-
placement pump, a constant feed rate is easily
obtained by a manually adjusted variable
speed drive.
Inlet and outlet drying gas temperatures,
along with feed rate, are normally the only
variables which must be controlled for an
open cycle spray-drying system to function
adequately.
Closed cycle systems are somewhat more
complex. Besides temperature control on the
dryer, the condenser outlet temperature
must be controlled. This is done by modu-
lating the chilled liquid to the plate exchanger,
thus modulating the temperature of the
recirculated solvent. An increase in the tem-
perature of the gas from the condenser will
increase the concentration of solvent in the
vapor. This will, in turn, increase the humidity
in the drying chamber and produce a product
higher in residual volatile content.
In addition to all of the monitoring points
on an open cycle dryer, closed cycle units
require some special monitoring points.
There must be at least one oxygen analyzer
in the system. This should be at the location
of lowest pressure in the system. This analyzer
should have both an alarm and an automatic
shutdown capability in case the oxygen
content in the system becomes dangerously
high.
There are also a number of points where
nitrogen pressure must be monitored to
assure that the system is always under inert
atmosphere. To complicate matters a little
more, all field mounted instrumentation
must be explosion proof or intrinsically safe.
All power wiring, switches, lighting and
other electricals must also be explosion
proof. Normal practice is to place the control
panel or computer control outside of the
hazardous area.
CAPITAL INVESTMENT
At present, most non-oxide ceramics are in a
development stage or emerging in new prod-
uct areas. As a result, production capacities
are currently quite small and the associated
equipment is small. Laboratory scale equip-
ment is available at minimal capital invest-
ment. These systems can be portable and
require a 2 m x 2 m (6.6 ft x 6.6 ft) floor area.
It must be remembered, however, that small
scale equipment is not always suitable for
the quality of powder desired, even when
the rate is sufficient. Units designed for use
on the bench are not recommended.
At the other end of the spectrum is the large
pilot plant or small production system. Such a
system will produce 100-200kg/h (",,220-
440 lb /h) of powder depending on the tem-
peratures used and solids concentration in
the feed slip. These drying systems are quite
large by comparison, occupying a 6 m x 6 m
(",,20 ft x 20 ft) floor space and requiring up
to 9 m (29.5 ft) high ceilings. By virtue of the
larger drying chamber, these systems have
greater capability with regard to atomization
type and thus particle size distribution. In
addition, a larger mean particle diameter is
possible, which is important when the
powder is for automatic dry-pressing opera-
tions.
A pilot scale or small production drying
system will cost four to five times as much
as the lab units and can have significant instal-
lation cost. There are numerous options and
ancillary items to consider in specifying a
system and each will have some cost impact.
Drying systems for ceramics are almost
always fabricated from stainless steel sheets.
Mild steel would undoubtedly result in
contamination and higher alloys are normally
not needed.

Closed cycle systems, employed when the
feed slip contains flammable solvents, cost
considerably more, usually two to three
times more. This is not only because there
are more components in the system, but
because each component requires special
care in specification and design. In estimating
the total cost of closed cycle systems, not only
is the equipment expensive, there are more
ancillary items and special requirements.
Although the expense is considerable, the
ability to produce high value-added ceramic
products makes it worthwhile. This is evi-
denced by the fact that these systems have
been employed for several decades in the
manufacture of hard metal carbides.
OPERATING COST
Aside from depreciation of capital, the energy
consumed to evaporate water or solvent, and
the labor required for the system, are the two
primary components of operating cost. As a
rule, the energy requirement for a spray
dryer is less on a kilojoule per kilogram of
evaporation basis. For a dryer operating with
a 423 K (150 DC) temperature difference (~T)
from inlet to outlet, the average consumption
will be 5656 kJ for each kilogram (2426 BTU I
lb) of water evaporated. If a direct-fired
natural gas air heater is used, this equals
0.15m3 of gas per kilogram evaporated
(2.4 ft3 lIb). An electric heater will, on the
other hand, consume 2.2 kW Ikg (1 kW lIb)
for the same evaporation. Electrical usage for
the fans, feed pump and atomizer will average
O.3kW Ikg (O.14kW lIb) of evaporation.
Labor cost is essentially fixed, in that it takes
one person to operate a spray dryer, regard-
less of the system size. Maintenance costs
vary widely depending on plant practice, the
product being dried and the age of the
equipment. In general, a spray dryer should
require less maintenance than particle size
reduction equipment, presses or kilns.
The fact that both equipment size and oper-
ating cost depend on evaporation, points out
Operating cost 539
the importance of dryer feed concentration. At
50% solids, the powder production is equal to
the evaporation. With 65% solids in the feed,
the production is 1.85 times the evaporation
(Figure 21.9).
Economies of scale are also very important.
Operating cost for a system with evaporative
capacity of 1000kg/h (2203Ib/h) can have a
per kilogram cost equal to 10% that of a pilot
scale unit. Not only is there a favorable scale
factor for equipment cost, but the fixed cost of
labor brings the cost per kilogram down quite
a bit for high production rates.
Closed cycle system costs are a little more
difficult to define. Each solvent has a different
latent heat of evaporation and different
specific heats for both vapor and liquid
phases. As a result, it is difficult to estimate
an energy consumption per kilogram of
solvent evaporated, without specifying the
solvent. In most cases, the heat required is
400r-------------------------,
300
~
~
'5
0..
'S 200
0
16
"C
;=
0
Q.
100
OL-----~----~------L-----~
40 50 60 70 80
Weight % Solids
Figure 21.9 Powder output from a spray dryer as a
function of the weight percent solids in the feed
slurry. Dryer evaporative capacity is 100 kg/h of
water and a yield of 100% is assumed. (Lukasie-
wicz, S.J., 'Spray-drying ceramic powders,' J. Am.
Ceram. Soc., 72, 617-24, 1989. Reproduced by
permission of the American Ceramic Society,
Westerville, OH.)
540 Spray drying
much less than for water. Steam-heated and
hot-oil-heated systems can never be as effi-
cient as direct-fired. The solvents also require
lower temperatures to be used, resulting in
more inlet gas recirculation per kilogram eva-
porated.
In addition, every kilogram of solvent
evaporated must, in turn, be condensed. The
condensing is provided by an electrically
driven chilled liquid system. This will ordi-
narily require about the same energy as that
used on the evaporation end of the system.
The nitrogen consumed to maintain the
inert blanket in the system is another cost to
consider in estimating a product cost, if
solvents are used in place of water. Labor,
on the other hand, is still just one person.
EXPERIENCE WITH NON-OXIDE SYSTEMS
Most non-oxides are relatively new develop-
ments with little production history to
report. Further, most producers are reluctant
to provide any information concerning their
production process.
One well documented example of spray
drying the production of a non-oxide material
is in the tungsten carbide (WC) industry.
Cemented carbide grade powders are pro-
duced by milling tungsten carbide in a solvent
with cobalt. Ball mills or attritors are used
and a slurry with well defined grain size is
obtained. A binder, usually paraffin wax, is
\1dded to the slurry which is then spray
dried in a closed cycle spray-drying system.
Most systems employ pressure nozzle
atomization in fountain configuration. Either
a piston-diaphragm positive displacement
pump or an agitated pressure feed tank is
used to force the feed through the nozzle at
a controlled pressure. This permits control of
the mean particle diameter in the powder and,
thus, the pressing characteristics.
Because the paraffin in the powder is often
soft at the temperature required for complete
solvent removal, a powder cooling device is
used at the point the powder is discharged
from the dryer. This allows the wax to
harden and prevents lump formation in the
powder.
Spray dryers for hard metal carbides
usually vary in capacity from 60 kg/h
(132lb /h) to 600 kg/h (1322lb /h) of powder
production. The feed slurry is often between
75% and 80% solids due to the high density
of the powder. Several dozen systems are in
operation worldwide.
Although solvent-based systems predomi-
nate, there is a patented process (Benjamin,
1983) for spray drying tungsten carbide from
a water slurry.
The dispersant and binder system used for
non-oxide ceramics depend on the product
specifications. Dispersants are usually organic
polymers that are attached to the surface of the
particles in the feed slurry (Chapter 20). The
use of a dispersant makes it possible to
increase the feed solids without increasing
the viscosity.
The binder that is added to the feed slurry
will provide green strength to the pressed
part. The binder is usually an organic com-
pound, such as poly(vinyl alcohol), poly(ethyl-
ene glycol) or microcrystalline cellulose. The
amount of binder used has an effect on the
compaction of the powder. Generally 0.5-
4.0 wt% of binder is contained in the feed
slurry (Lukasiewicz, 1989).
Another non-oxide ceramic of increasing
importance is silicon nitride (Si 3N 4 ) (Chapter
15). Due to its grain interlocking property, it
is one of the toughest monolithic ceramics
for use above 1273 K (1000C). Because of its
compatibility with high temperatures and its
wear resistance, applications can include
lightweight engine components. Like tungsten
carbide, silicon nitride can be spray dried
from a solvent or an aqueous-based slurry.
Typical feed formulations can be found in
Tables 21.1 and 21.2.
Aluminum nitride (AlN) and silicon carbide
(SiC) are also found in the formulation tables.
Aluminum nitride (Figure 21.10) is swiftly
becoming a replacement for alumina and
 Experience with non-oxide systems 541
Table 21.1 Aqueous slurry formulations

Powder Solvent Sintering aid Binder Dispersant Solids

(wt%)

Deionized water Al 2 0 3 (5wt%) XUS40303.00 1 wt%) KV 5088 (1 wt%) 50-70

+ Y203 (5wt%) (Dow Chemical) or (Zschimmer
PYA Mowiol and Schwarz)
4-88 1 wt%)
(Hoechst)
Deionized water B 1 wt%) PVAMW Ammonia or 45-60
+ C (2.5wt%) 22000 (Fluka) or ethanolamine
PEGMW
20000 (Merck)

a Herman C. Starck (1992).

b De Angelis et al. (1990).

beryllia for electronics and structural appli-
cations (Janeway, 1991). It has excellent
properties for electrical insulation, thermal
conductivity and specific chemical/tempera-
ture resistivity. These properties lead to
applications for electronic substrates, elec-
tronic packaging, thick film and thin film,
semiconductor heat sinks, laser components
and crucibles. Silicon carbide (SiC) continues
to have increasing application in high wear
parts such as blasting nozzles and seal
rings.
A concern with AIN is its reaction with
water. Contact with water causes hydrolysis
of the powder with release of ammonia
(Sheppard, 1990). Because of this reaction, a
non-aqueous feed must be prepared and
dried in a closed cycle spray dryer, making

Table 21.2 Solvent-based slurry formulations

Powder Solvent Sintering aid Binder Dispersant Solids

(wt%)

Ethanol, Y2 0 3 (>6wt%) or XUS40303.00 (1 wt%) Menhadan fish oil <30

propanol Y2 0 3 (5wt%) (Dow Chemical) O.5wt%)
or hexane + AIN (2.5 wt%)
Ethanol Al2 0 3 + Y2 0 3 PEG (5wt%) 45-60
(6-10vol.%)
Ethanol Y2 0 3 (3wt%) 1:2t02:1 Fish oil 30-50
+CaO(1 wt%) PEG + XUS 40303.00
(4-lOwt%)
(Dow Chemical)
Acetone, Co (6-lOwt%) PVA, PEG or paraffin Stearic acid with 75-80
ethanol, (1.8-2.2 wt%) hexane
hexane or (0.3-0.5 wt%)
methanol

a Herman C. Starck (1992).

b Mulla and Krstic (1991).
C Skeele and Rafaniello (1991).

d Houck (1985).
542 Spray drying
Figure 21.10 Spray-dried aluminum nitride particles. (Courtesy of The Dow Chemical Company, Mid-
land, MI.)
the process more expensive than water-based
systems. Surface modification of AlN powders
has been carried out to allow aqueous
processing (Groat and Mroz, 1994). Both
aqueous and solvent-based systems have
been developed for SiC as shown in Tables
21.1 and 21.2.
REFERENCES
Benjamin, M.L. (1983) Process for producing refrac-
tory powder. US Patent 4,397,889.
De Angelis, B.A., Rizzo, c., Ferretti, E. and Howlett,
S.P. (1990) Sintering of a-SiC: dispersion of the
carbon sintering aid. Paper given at 7th
CIMTEC, 24-30 June 1990, Montecatini Terne,
Italy.
Graef, H.J. and Seitz, G. (1991) Spray drying of
ceramic slurries. Key Eng. Mater., 56-57, 189-203.
Groat, E.A. and Mroz, T.J. (1994) Aqueous slip
casting of stabilized AlN powders. Am. Ceram.
Soc. Bull., 73(11), 75-78.
Helsing, H. (1987) Manufacture of dustfree
chemical and ceramic powders by spray drying.
Paper given at Chemistry '87, September 1987,
Moscow, Russia.
Herman C. Starck (1992) Product sales literature.
Houck, D.L. (1985) Spray drying in the metals
industries. Metal Powder Report, Vol. 40, No. 12.
Janeway, P.A. (1991) Aluminum nitride: making
the grade in demanding electronic applications.
Ceram. Indust., 137, 28-32.
Lukasiewicz, S.J. (1989) Spray-drying ceramic
powders. J. Am. Ceram. Soc., 72,617-24.
Masters, K. (1991) Spray Drying Handbook, 5th edn,
John Wiley & Sons, New York.
Moller, J.T. (1980) Controlling powder properties in
the spray drying process. Paper given at Powtech
1980,4-7 March 1980, Basel, Switzerland.
Mulla, M.A. and Krstic, V.D. (1991) Lab report: low
temperature pressureless sintering of ,B-SiC with
Al 2 0 3 additions. Ceram. Bull., 70, 439-43.
Shaw, F.v. (1986) Closed cycle spray drying for sol-
vent based slurries. Paper given at '87 Advanced
Ceramics, 17-19 February 1986, Cincinnati, Ohio.

Sheppard, L.M. (1990) Aluminum nitride: A versa-
tile but challenging material. Ceram. Bull., 69,
1801-12.
Skeele, F.P. and Rafaniello, W. (1991) Processing of
aluminum nitride ceramics, in Thirty-seventh
Sagamore Army Materials Research Conference Pro-
ceedings.
References 543
Smith, G. (1993) Operating the spray dryer. Ceram.
Indust., 140, 54-56.
Varacalle, Jr, D.F., Kniblow, J.R., Smith-Wackerle,
V.L., Walker, J.A. and Irons, G. (1991) Coatings
applied with the plasma-spray process using
nickel-aluminum powders. Paper given at
ICLAS5-91, July 1991, Gaithersburg, Maryland.
PART EIGHT
COATINGS, FILMS AND
INFILTRATION PROCESSES
OVERALL PROCESS
Chemical vapor deposition (CVD) is a process
whereby gas- or vapor-phase reactants flow
over a heated substrate, react and form a coat-
ing. Typically, the CVD process takes advan-
tage of lowered phase formation energies for
deposition on existing surfaces. Because of
this, high melting point pure materials can
be formed at relatively low temperatures
which are far below the melting point of the
material. Conventional CVD (Chapter 22) is
widely used and provides good quality films
with excellent film uniformity.
In some cases, lower deposition tempera-
tures are needed to prevent damaging the
substrate material. Plasma-assisted chemical
vapor deposition (PACVD) and plasma-
enhanced CVD (PECVD) (Chapter 23) take
advantage of the high energy electrons pres-
ent in glow discharges to dissociate and
ionize gaseous molecules to form chemically
reactive radicals and ions. Because thermal
energy is not needed to break chemical
bonds, reactions can be promoted at lower
temperatures, thereby avoiding substrate
damage.
Chemical vapor infiltration (CVI) (Chapter
22) is simply CVD on the internal surfaces of
a porous preform. Infiltration of continuous
filament preforms is one of the most useful
applications of CVI.
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
The coatings (by CVD, PECVD or CVI) often
provide certain surface properties which
enhance the bulk properties of the substrate
material. Furthermore, on a cost-performance
basis, it is often much cheaper to coat a sub-
strate with a thin layer of a high performance
expensive material than it is to make the bulk
of the part from the expensive material.
The configurations of deposition systems,
their modeling, operation and characteriz-
ation of film properties are discussed in
Chapter 22 for CVD and CVI systems and in
Chapter 23 for PECVD processes, respectively.
SAFETY ISSUES
CVD and CVI systems can be treated as
general high temperature processes with
typical furnace safety considerations. PECVD
systems require special precautions with
regard to plasma generation and handling as
discussed in Part Four.
Additional precautions are often required
for all of these systems based on the precursors
used (see Part Four regarding the handling
of gaseous metal hydrides and liquid or solid
metal halides). Hydrogen (H 2) is a typical
reductant and, thus, fire and explosion
hazards are present. Hydrogen detectors
should be used in ceiling areas of laboratories
and interlocks provided to shut off the H2
flow under off-normal conditions. The exhaust
546 Coatings, films and infiltration processes
systems typically allow for rapid dilution of
the H2 to below the lower explosive limit,
although some practitioners do burn off the H 2
Precursors are often flammable, and in
some cases pyrophoric. Chlorosilanes are
prone to form polymeric deposits on cool
exhaust system surfaces. These deposits can
be pyrophoric, forming an oxide skin when
exposed to air which, if disturbed, can result
in rapid combustion. A number of serious
incidents have been reported due to this prob-
lem. The formation of these pyrophoric
deposits can be prevented by allowing the
chlorosilane reactants to fully react, typically
by providing a large surface area material for
deposition at temperatures of at least 1100 K
(827C). Others have reported using transition
regions to gradually allow the unreacted gases
to cool, thus preventing polymer formation on
cold surfaces.
Precursors tend also to be corrosive and
toxic. Thus, proper ventilation of equipment
spaces is required. In addition, air quality
regulations, as well as protection of ventilation
systems, will require the use of exhaust gas
scrubbers. For small systems, dry scrubbers
that use materials such as sodalime are often
adequate. Larger flow systems, however,
typically require commercially available wet
scrubbers.
CHEMICAL VAPOR DEPOSITION (CVD)
AND INFILTRATION (CVI)
Theodore M. Besmann, David P. Stinton, Richard A. Lowden
and Woo Y. Lee
INTRODUCTION
Chemical vapor deposition (CVD) takes
advantage of gas phase reactants to form
desired phases in situ. CVD reactions are not
unlike those described in Part Four, where
ceramic materials are prepared from vapor
phase precursors. The significant difference
is that in CVD the resultant material is in the
form of a coating deposited on a substrate.
Thus, the CVD process takes advantage of
the lowered energies for phase formation
afforded by nucleation and growth on existing
surfaces.
Chemical vapor infiltration (CVI) is simply
CVD on the internal surfaces of a porous pre-
form and has been used to produce a variety
of developmental materials. The most useful
application of CVI is to infiltrate continuous
filament preforms, taking advantage of the
relatively low stress CVD process.
CHEMICAL VAPOR DEPOSITION (CVD)
In CVD, reactive vapor phase precursors flow
over a heated substrate, react, and form a
single- or multi-element coating. One of the
great attractions of CVD is the ability to form
pure, high melting-point materials at rela-
tively low temperatures. For example, TiB2
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
22
melts at 3598 K (3325 DC), yet can be produced
at 1300 K (1027 DC) or lower via the reaction
TiCl4 + 2BCl3 + 5H2 -+ TiB2 + 10HCI (22.1)
Another advantage of CVD is its throwing
power, which allows hidden surfaces to be
coated, provided diffusion or convection can
transport reactants to the area. Chemical
vapor deposition has also demonstrated
high material deposition rates, which can
reach tens of micrometers per hour or
greater.
HISTORY OF CVD
Chemical vapor deposition is an old tech-
nology, with the first systematic investigation
being reported in the 1920s (von Arkel
and de Boer, 1925). A patent filed in 1890
by de Lodyguine (1893) on preparing tung-
sten by deposition on carbon lamp filaments
from WCl 6 reduced by hydrogen, however,
may be the first literature reference to the
process. Initially, CVD was simply a tool
for preparing highly pure samples of high
melting temperature materials, particularly
metals. As noted above, preparation tem-
peratures can be substantially below a
material's melting point, thus preventing
548 Chemical vapor deposition and infiltration
contaminating reactions or dissolution of con-
tainer material.
More recently there has been a remarkable
increase in the activity in CVD. Initial applica-
tions were largely related to improving the life
and performance of cutting tools. Closer to the
present the greatest growth has been in the
production of semiconductor devices, a sub-
ject which does not fall under the purview of
this book. Currently, there are over a dozen
suppliers of coating consumables and a half-
dozen suppliers of CVD and physical vapor
deposition (PVD) systems. More than 30
companies also offer coating services. The
majority of today's market for CVD coatings,
however, is found in two specific areas:
aircraft engine components and metal cutting
tool inserts. Other markets, such as auto-
motive parts, are very small in comparison
(Abraham, 1988). A listing of the non-oxide,
non-electronic ceramic coatings produced by
CVD is given in Table 22.1.
SYSTEM CONFIGURATIONS
The configuration of CVD systems is largely
tied to whether the system's use is bench
research, development or production scale.
The issues of reactant depletion (particularly
in larger systems), temperature control and
fluid dynamics in CVD reactors have largely
driven their design. Still, much of CVD reactor
design today is largely empirical, although the
use of fluid flow modeling is becoming more
common.
Cold-wall reactors
Cold-wall CVD reactors are so designated
because the substrate is heated directly, leav-
ing the reactor chamber walls relatively cool
(Figure 22.1). The advantage of such systems
is that there is little or no deposition on the
reactor walls which allows for high precursor
efficiency and low reactant depletion. These
systems usually depend on either resistance
or radio-frequency induction heating. For
resistance heating the substrate can be
heated directly or the substrate holder can be
heated. In a similar manner for induction heat-
ing, the substrate can couple directly with the
radio-frequency field or can be placed on a
holder which can act as the susceptor. An
advantages of resistance heating are that the
power supply can be relatively simple. The
advantages of radio-frequency heating are
that no electrical penetrations into the reactor
are required and there is no concern about the
effect of the possibly corrosive reactant gases
on electrical leads. General problems in CVD
are buoyancy rolls and other thermal con-
vective effects which create differential gas
phase species concentrations that result in
non-uniform coatings. Reduced pressure
often mitigates or eliminates this problem.
Hot-wall reactors
Hot-wall reactors are simpler to construct,
generally only requiring the use of a resis-
tance-heated furnace surrounding a reactor
tube (Figure 22.1). All heated surfaces, how-
ever, provide areas for deposition making
control of gas composition difficult. Obtaining
uniform substrate temperature is easy, pro-
vided the substrate is small or the furnace
can maintain a uniform temperature zone
within which the substrate resides. Three-
zone furnaces are often used for CVD because
it is possible to control the outer zones such
that a uniform temperature profile is main-
tained across the central zone.
Bench-scale reactors
Research and development CVD reactors are
relatively easy to construct, requiring flow
meters, a furnace system and an exhaust
system. Two simple, radio-frequency induc-
tion-heated cold-wall systems, one vertical
and the other horizontal, are illustrated in
Figure 22.2. Buoyancy rolls are more likely in
the vertical configuration with downward
flow.
 Chemical vapor deposition (CVD) 549
Table 22.1 Structural or protective ceramic materials produced by
chemical vapor deposition

Coating Precursors Deposition temperature

(K (OC))

Carbides
TiC TiCl4--CHc H 2 1200-1300 (927-1027)
HfC HfClx-CH 4-H 2 1200-1300 (927-1027)
ZrC ZrCl4 --CHc H 2 1200-1300 (927-1027)
ZrBr4--CHc H2 >1200 (>927)
SiC CH3SiClr H 2 1200-1500 (927-1227)
B4C BCl3--CHc H2 1500-1700 0227-1427)
W 2C WF6--CHc H2 700-1000 (427-727)
Cr7C3 CrCI2-CHc H 2 1300-1500 0027-1227)
Cr3C2 Cr(CO)6--CHc H 2 1300-1500 0027-1227)
TaC TaCls--CH4 -H2 1300-1500 0027-1227)
VC VCl2--CHc H 2 1300-1500 0027-1227)
NbC NbCIs--CClc H2 1800-2200 0527-1927)
Nitrides
TiN TiCl c N2-H2 1200-1300 (927-1027)
HfN HfClx-N2-H2 1200-1300 (927-1027)
HflcNH3-H2 >1100 (>827)
Si3N4 SiCI4-NH r H 2 1300-1700 0027-1427)
SiH 4-N 2-H 2 600-700 (327-427)
BN BCl3- NH3-H2 1300-1700 0027-1427)
B3N3H6-Ar 700-1000 (427-727)
BFr NH r H 2 1300-1600 0027-1327)
B2H6-NH3-H2 1300-1600 (1027-1327)
ZrN ZrClc N 2-H 2 1400-15000127-1227)
ZrBr4-NHrH2 >1100 (>827)
TaN TaCIs-N 2-H 2 1100-1800 (827-1527)
AIN AIClr NH r H 2 1100-1500 (827-1227)
AlBrr NH r H 2 1100-1500 (827-1227)
Al(CH 3)rNHr H2 1200-1400 (927-1127)
VN VClc N 2-H2 1200-1500 (927-1227)
NbN NbCIs-N2-H2 1200-1600 (927-1327)
Borides
TiB2 TiClc BClr H 2 1100-1300 (827-1027)
MoB MoCls- BBr3 1700-1900 0427-1627)
WB WCI6-BBr3-H2 1700-1900 0427-1627)
NbB2 NbCls-BCl3-H 2 1200-1500 (927-1227)
TaB 2 TaBrs-BBr3 1500-1900 0227-1627)
ZrB 2 ZrClc BCl r H 2 1300-1800 0027-1527)
Hffi2 HfClx-BCl3-H2 1300-1900 0027-1627)
Silicides
TiSi2 TiClc SiClc H 2 1500-1800 0227-1527)
MoSi2 MoCls-SiClc H2 1200 (927)
Sulfides
MoS2 MO(CO)6-H2S 450-625 077-352)
WS2 W(CO)6-H2S 575 (302)
550 Chemical vapor deposition and infiltration
Heated Substrate

I Exhaust Reactants

Reactants Exhaust

Hot-Wall Reactor Cold-Wall Reactor

Figure 22.1 Schematics of hot-wall and cold-wall CVD systems.

Commercial reactors coat thousands of tool bits (Figure 22.3). Many

Commercial reactors are generally more com-
plex, having to handle larger throughput or
batch size. Continuous reactors are available
for CVD; however, they are exclusively used
in the thin-film device industry. Typically,
commercial-scale CVD reactors for structural
ceramics are large vessels with racks for pla-
cing substrates to be coated. The tool bit coat-
ing industry probably has the largest CVD
reactors, having the ability to simultaneously
of these furnaces are radio-frequency induc-
tion heated for improved energy efficiency.
Unlike the bench-scale systems, however,
these are hot-wall reactors, with a furnace
liner acting as the susceptor.
Larger reactors also face the perennial CVD
system problem of reactant gas depletion.
As the reactants flow the length of a large
furnace system with high surface area (large
number of parts to be coated), significant
depletion occurs. The result is non-uniform

Induction Coil

-I
Substrate

Exhaust


~

I Susceptor

"L" " "
Susceptor

(a) Horizontal (b) Vertical

Figure 22.2 Induction-heated CVD systems: (a) horizontal; (b) vertical.

 Chemical vapor deposition (CVD) 551

(a)

(b) I
Figure 22.3 Commercial CVD system for the coating of tool bits: (a) rack containing a load coated with
TiN; (b) the complete CVD system. (Bhat, D.G. and Rebenne, H., Surface and Coatings Technology, 63, 1-13,
1994. Reprinted with kind permission from Elsevier Science SA, Lausanne, Switzerland.)
552 Chemical vapor deposition and infiltration
Table 22.2 Listings of interrelated CVD parameters, variables and coating properties

Experimental parameters Process variables Coating properties

(direct control) (indirect control) (results)

1. Reactor geometry 1. Gas temperature 1. Morphology

2. Substrate temperature 2. Flow behavior 2. Composition
3. Substrate environment 3. Mean gas velocity 3. Thickness
4. Input gas composition 4. Gas chemistry 4. Density
5. Total flow rate 5. Gas homogeneity 5. Uniformity
6. Total pressure 6. Deposition rate 6. Adhesion
7. Substrate surface 7. Deposition surface 7. Crystallinity
8. Time of deposition 8. Nucleation density 8. Stress
9. Experimental procedure
Source: Spear, K.E. and Dirkx, R.R., 'Prediction of the chemistry in CVD systems,' in Chemical Vapor
Deposition of Metals and Ceramics (eds T.M. Besmann and B.M. Gallois), pp. 19-30, 1990. Repro-
duced by permission of the Materials Research Society, Pittsburgh, PA.

and sometimes inadequate coating of parts in
the downstream areas. Larger systems deal
with this problem by providing multiple
ports for gas injection down the length of the
furnace.
CVD FUNDAMENTALS AND MODELING
CVD is a complex process with a myriad of
variables and possible product properties.
Spear and Dirkx (1990) have concisely listed
the interrelated variables, parameters and
product properties for CVD, and this is repro-
duced in Table 22.2.
The processes involved in CVD include
mass and heat transfer and chemical kinetics.
These processes are indicated schematically in
Figure 22.4:
1. convective flow of reactant species into the
reactor;
2. diffusion/convection of reactant species
to the gas phase-substrate surface inter-
face;
3. adsorption (and unproductive desorption)
of reactant species onto the substrate;
4. surface diffusion/ reactions and inclusion
of coating atoms into the growing surface;

.....
~ -...
- -... Gaseous
Reactant Species

,
~
Bulk Gas

--r
Adsorbed
~ Intermediates

,
~

t t
o Gaseous Product
Species
Boundary
t Layer

Figure 22.4 Processes in chemical vapor deposition.


5. desorption of gas phase product species;
6. diffusion/ convection of gas phase product
species to the bulk gas;
7. convective flow of product species and
unreacted/partially reacted species out of
the reactor.
Despite the complexity of CVD, much can
be learned from the commonly used, simple
thermochemical models. These can indicate
process feasibility and point to appropriate
operating conditions. Recent years have seen
significant efforts on more extensive modeling
which includes chemical kinetics and mass
and heat transport. Although not yet in wide-
spread use, these models are beginning to be
adopted for practical systems (Werner, 1991;
Holstein, 1992).
Thermochemical analysis/assessment
A useful and easy technique for assessing the
practicality of a proposed CVD process is
thermochemical analysis. Thermochemical
calculations allow the elemental reactants to
achieve equilibrium under the CVD condi-
tions of temperature and pressure (Spear,
1979; Besmann, 1988; Bernard and Madar,
1990, 1992). Admittedly, in a typical, dynamic
CVD system in which gases are flowing and
reactants have a limited residence time,
equilibrium is rarely achieved. Yet there are
valuable insights to be gained from a thermo-
chemical analysis, and there are modifications
to the input parameters (pseudo-equilibrium)
which can be made that allow a real system
to be more closely modeled (Spear and
Dirkx, 1990). The information that equilibrium
or pseudo-equilibrium calculations can pro-
vide includes:
1. identification of equilibrium condensed
phases;
2. maximum deposition rates/ efficiencies;
3. partial pressures - homogeneous equili-
brium prior to deposition;
4. partial pressures - heterogeneous equili-
brium with condensed phase(s);
Chemical vapor deposition (CVD) 553
5. sensitivity to CVD parametric changes;
6. suggestion of non-equilibrium mechanisms.
Equilibrium calculations can serve as feasi-
bility tests for proposed CVD processes.
Simple reactant input with likely deposition
temperatures and pressures will yield
whether a particular phase of interest will
form. More extensive calculations can then
be undertaken to develop CVD or equili-
brium diagrams that indicate phases or
partial pressures plotted in CVD parametric
space. An example of such a diagram for
the deposition of TiB2 from halide precursors
(Besmann, 1988) is shown in Figure 22.5.
At moderate boron concentrations in the
reactant gas, single-phase TiB2 will form,
whereas at high concentrations the two-
phase mixture of TiB2 and boron are pre-
dicted to be deposited.
Spear and Dirkx (1990) have provided a
good example of how pseudo-equilibrium
1.0,..---,.---,r---r--,---r---r--,
en
---
."
(!)
c
0 --------
~ 0.6
1 kPa
(])
II:
(])
.;;
(TiB 2 )
.5
c
n~
0
0.4 (C~H) = 0.05
11.
alii
0.2
Temperature (K)
Figure 22.5 CVD diagram for deposition from tita-
nium and boron chloride precursors and hydrogen.
554 Chemical vapor deposition and infiltration
calculations can more realistically model
deposition. They used assumptions about
mass transport to modify the set of reactants
input to the equilibrium calculations. This
allowed explanation of the difference
between predicted and observed deposits.
For example, when the total input quantities
of SiH4 , BCl3 and H2 to a CVD reactor are
used in equilibrium calculations for the
deposition of silicon borides, they predict
the formation of SiB6 Yet at 1400-1500K
(1127-1227C), SiB3 is actually deposited.
Spear and Dirkx (1990) are able to explain
this behavior via the build-up of the SiC12
intermediate at the gas phase-substrate inter-
face (Figure 22.4). Deposition of SiB6, at
equilibrium, results in a high concentration
of SiCl2 in the gas phase. When the calcula-
tions are performed assuming steady-state
conditions in which SiCl2 accumulates at the
interface, causing a shift in the B: Si ratio in
the gas phase near the substrate, then SiB3
is properly indicated to deposit (Figure
22.6). Thus, the formation of SiB3 can be
explained by the initial formation of SiB6
causing higher concentrations of SiC12 near
the substrate, which then drives the system
chemistry to deposit SiB3 .
Chemical kinetics
As noted earlier, CVD is a steady-state, but
rarely an equilibrium process. It can thus be
rate limited by either mass transport or
chemical kinetics, which is the subject of this
subsection. It has been a general assumption
in CVD that the vast majority of rate-limiting
chemical kinetics reactions are heterogeneous
and first order with respect to the major
reactant species. Certainly this is not always
true, but the assumption does offer a starting
point for assessing the chemical kinetics of a
CVD process.
The ideal chemical kinetic relationship for
CVD would be derived via analysis of all
possible sequential and competing reactions.
This is typically not possible, however, due
to the lack of activation or adsorption energies

3.5

0 3.0
0
x
C\I 2.5
C3
i:i5 2.0
SiB6
I/) I/)
I/)J!!
(I) 0
~::ii! 1.5
w
'0
I/)
(I)
(5
! 1.0
::ii!
0.5

0.0
0.60

Gas Composition (BIB + Si)

Figure 22.6 CVD diagram at ISaaK illustrating the effect of a build-up on the surface of excess SiCl2 .
(Spear, K.E. and Dirkx, R.R., 'Prediction of the chemistry in CVD systems,' in Chemical Vapor Deposition
of Metals and Ceramics (eds T.M. Besmann and B.M. Gallais), pp. 19-30, 1990. Reproduced by permission
of the Materials Research Society, Pittsburgh, PA.)

and pre-exponential factors. The most prac-
tical approach is, therefore, to obtain deposi-
tion rate data as a function of deposition
conditions such as temperature, concentration
and flow rate, and fit these to suspected rate-
limiting reactions.
An example of this approach is shown in
Figure 22.7 which contains Arrhenius plots
at different total pressures for the deposition
of B4 C from BCl3 , CH4 and hydrogen
(Naslain, 1992a). The Arrhenius law
kr = ko exp (~:; )
where kr is the kinetic rate constant, indicates
that the reaction rate is exponential in
Chemical vapor deposition (CVD) 555
temperature, such that at lower temperatures
the deposition rate is considerably slowed.
Under those conditions, mass transport (gas
phase diffusion) is rapid compared to
chemical kinetics, and this is reflected in the
lower temperature portion of the Arrhenius
plot.
Mass transport
At higher temperatures chemical kinetic pro-
cesses are rapid compared to mass transport
(22.2) with the resultant change in slope evident in
Figure 22.7. The net deposition rate can thus
be expressed as
J = C1/D) ~ (llk (~
r )) )
(22.3)

where I is the diffusion length and J the flux to

Temperature (OC)
the substrate surface.
1100 1000 900 800
The complex flow patterns of many CVD
reactors can cause significant concentration
and thermal gradients over short distances.
The result can be non-uniform coating thick-
0
2 kPa ness, composition and morphology. These
:c --'"().. problems are, not unexpectedly, significantly
'"E "'0 greater in larger CVD systems, and have

Q',
" \ '' caused a good deal of consternation in efforts
()
Cl \ '
. -1 to scale-up CVD processes. In cold-wall reac-
'\
Q)
til , it tors, for example, in which the reactor envel-
a: \, .0' ope is either unheated or actively cooled, the
c:
0 , '\ large thermal gradients can lead to complex
~
0
-2
a.
,,, '\, buoyancy-driven flows superimposed on the
Q)
, ', bulk flow (Jensen, Einset and Fotiadis, 1991).
0
Cl q, 4I~\ Conditions can be chosen under which flow
0
...J
,, ,'
-3 ,, ... complexities are avoided, such as low pres-
,, .0\
~
sure and uniform temperature. However,
practical considerations of throughput and
deposition rate require the use of systems in
-4~------~-------....I~----~
0.65 0.95 which fluid dynamics are significant.
The value of the Reynolds number, Re, in
CVD systems is generally very low 100)
Figure 22.7 Arrhenius plot of the deposition rate and, therefore, flow is laminar. This allows
of B4 C as a function of reciprocal temperature for
various total pressures. (Naslain, R, 'CVI com- buoyancy-driven convection to interact with
posites,' in Ceramic-Matrix Composites (ed. R forced convection to develop significant
Warren), pp. 199-244, 1992. Reproduced by density gradients. In addition, large mass
permission of Chapman & Hall, London, UK.) differences between the reactants and carrier
556 Chemical vapor deposition and infiltration
gas, combined with concentration gradients,
may also give rise to buoyancy-driven flow
(Jensen, Einset and Fotiadis, 1991).
Increasingly, CVD reactor designers are
utilizing calculational models to understand
mass and heat transport in CVD reactors.
The greater availability of elaborate transport
models has allowed relatively accurate pre-
dictions of flow, thermal and concentration
fields in a complicated CVD system (Carlsson,
1985; Jensen, Einset and Fotiadis, 1991;
Werner, 1991; Gokoglu, 1992).
The CVD reactor models require gas flow
calculations derived from the continuity
equation for energy and momentum. An
example of the results of such calculations
is shown in Figure 22.8, which is a flow
model of a horizontal, cold-wall reactor.
Buoyancy rolls in the cold-wall system are
clearly evident in the system in which

19 ~

Figure 22.8 Schematic of flow patterns ill' a cold-wall CVD reactor with an inductively heated rectangular
substrate in the presence of normal gravitational forces and in the absence of gravity. (Gokoglu, S.A.,
'Chemical vapor deposition modeling for high temperature materials,' in Chemical Vapor Deposition of
Refractory Metals and Ceramics, II (eds T.M. Besmann, B.M. Gallois and J. Warren), pp. 17-28, 1992.
Reproduced by permission of the Materials Research Society, Pittsburgh, P A.)

normal gravitational forces are assumed and
absent in zero gravity.
CVD REACTIONS/MATERIALS
CVD reaction classifications
There are a variety of types of CVD reactions.
The hydrogen reduction of halide precursors
is the most common, of which equation 22.1
is an example. Simple thermal decomposition
is illustrated by SiC deposition from the
methyltrichlorosilane (MTS):
CH3Cl3Si ~ SiC + 3HCI (22.4)
Displacement reactions, such as the forma-
tion of TiN, are more complex:
!
TiCl4 + NH3 + H2 ~ TiN + 4HCI (22.5)
Disproportionation reactions are less com-
monly used since the thermal behavior of the
precursors is often not appropriate. However,
some systems have profitably used dispropor-
tionation, such as
(22.6)
Coupled reactions are used to gain better
control of CVD reactions that tend to occur
too rapidly. Reactions that form precipitates
in the gas phase (powder) are said to cause
homogeneous nucleation (as opposed to
heterogeneous nucleation on substrate sur-
faces). This is a particular problem in oxide
systems where the oxidation reaction has a
high, negative free energy. Coupled reactions
thus allow indirect control of reactant partial
pressures, as seen in this set of reactions:
CO2 +H2 ~ CO + H 20 (22.7)
Al2Cl6 + 3H20 ~ Al20 3 + 6HCl (22.8)
Thus, controlled concentrations of H2 and
CO2 allow fine control of low partial pressures
of water (H20), controlling the deposition of
alumina.
Simultaneous deposition of more than one
phase produces multiphase coatings which
can be desirable for a number of applications.
Chemical vapor deposition (CVD) 557
Such co-deposition relies on relatively
independent reactions occurring in parallel,
such as
SiC4 + CH4 ~ SiC + 4HCI (22.9)
TiCl4 + 2SiCl4 + 6H2 ~ TiSi2 + 12HCI (22.10)
Thus a two-phase SiC-TiSi2 dispersoid coat-
ing can be produced. This coating has been
found to have approximately twice the frac-
ture toughness of SiC alone, and thus resists
cracking and spalling from substrates with
significantly different thermal expansion co-
efficients (Stinton et al., 1984).
Organometallic precursors
Since the 1970s, organometallic precursors
have been successfully used for the epitaxial
growth of compound semiconductors such
as GaAs and InP. Currently, more than two
dozen compound semiconductors are pro-
duced by organometallic CVD (OMCVD) for
various electronic, laser and solar cell appli-
cations (Dapkus, 1982; Morton, 1992; Aylett,
1994; Jones, Rushworth and Ault, 1995).
More recently, OMCVD has also received
much attention as a means of depositing a
variety of metal and dielectric films at low
deposition temperatures in the microelec-
tronic industry.
OMCVD offers several distinct advantages
over halide-based CVD processes. First,
the halides of many elements are not suffi-
ciently volatile to be used as CVD precursors.
As an example, the vapor pressure of
YCl3 is about 100Pa (0.75 torr) at 1400K
(1127 DC) while the boiling point of an yttrium
complex containing ,B-diketonate ligands,
Y{(CH3hCC(O)CHC(O)C(CH3hb, is about
563 K (290 DC). Because of their relatively
high vapor pressures, the diketonate com-
plexes of Y, Cu and Ba have been widely
used to deposit superconducting YBa2Cu30x
thin films (Lackey et al., 1990). The second
major advantage of using OMCVD is that
temperatures required to activate deposition
558 Chemical vapor deposition and infiltration
reactions for many materials can be lowered
because the energy between a metal atom
and an organic ligand is generally lower
than that between the same metal atom and
a halogen atom. In the microelectronic indus-
try, reducing processing temperatures is of
critical importance for fabricating smaller
devices and achieving higher integration
density. A major drawback associated with
OMCVD is the difficulty in controlling the
incorporation of undesired carbon and hydro-
gen in films. On the other hand, the possibility
of film contamination with halogens which
may cause corrosion is eliminated.
Research on the OMCVD of Al (Levy, Green
and Gallagher, 1984), Cu (Kaloyeros and Fury,
1993) and TiN (Prybyla, Chiang and Dubois,
1993) has been actively pursued for metal-
lization applications. Also, the OMCVD of
advanced dielectric films such as TazOs (Lo
et al., 1993) has been extensively studied.
Prior work on the OMCVD of borides,
carbides, silicides, nitrides, oxides and sul-
fides was reviewed by Girolami and Gozum
(1990).
OMCVD has yet to see widespread use in
high temperature structural applications. For
these applications, coatings are usually
needed to be highly crystalline. In general,
relatively high deposition temperatures are
required to nucleate and grow crystalline
materials. Organometallic precursors are
not particularly desirable for use in high tem-
perature reactive environments because they
would prematurely decompose and deplete
in the entrance region of the reactors, causing
diminished throwing power. In addition, at
these temperatures, carbon contamination
might become significant and would be
problematic for applications in oxidative
environments. In some applications, the
development of low temperature crystalline
or nanocrystalline ceramic coatings via
OMCVD routes is encouraged. For example,
it has been recognized that polyimide
materials developed for aerospace applica-
tions for use at temperatures up to 600 K
(327C) are susceptible to oxidation and ero-
sion. Thus, it is technologically important to
develop protective coatings such as SiOz and
SiN x which can be applied to the polymers
below 600 K (327C) (Harding and Sutter,
1993; Miller and Gulino, 1993). Also, there is
a considerable interest in coating plastic
bottles and containers used in the food and
pharmaceutical industries with an oxygen
impermeable coating. In the cutting tool and
process tooling industries, the development
of a non-line-of-sight OMCVD process which
would allow the deposition of high quality
TiN at temperatures below 700K (427C),
is needed for coating iron-based materials
without metallurgical tempering (Oguri,
Fujita and Arai, 1991).
CVD of ceramics
There is an extensive list of ceramic materials
that have been fabricated by CVD (Table 22.1).
CVD coatings are typically prepared from
group IIIB to transition metals and group
lIlA to VIA non-metals. They are largely
deposited to prevent or control wear or to
protect against oxidation and corrosion, not
surprisingly applications common to bulk
ceramics as well.
A major advantage of CVD processes for
producing coatings is the ability to control
the microstructure, which can vary widely
depending on the deposition conditions
(Kim, Park and Lee, 1995). The fairly well-
known classification of microstructures of
Movchan and Demchishin (Thornton, 1977)
for vacuum-deposited films is equally applic-
able to CVD coatings (Figure 22.9). Micro-
structural control is, of course, necessary to
optimize the mechanical properties of a
material. Epitaxial deposits result from
conditions of low supersaturation (low reac-
tant concentrations) and sufficiently rapid
surface diffusion. Deposits consisting of ran-
domly oriented fine grains near the substrate
surface that grow into large columnar grains
of preferred orientation are due to higher
 Chemical vapor deposition (CVD) 559

Columnar grains
Recrystallized
grain structure
Porous structure

Figure 22.9 Modification of Thornton structural zone diagram as suggested by Gokoglu (1992). (Gokoglu,
S.A., 'Chemical vapor deposition modeling for high temperature materials,' in Chemical Vapor Deposition of
Refractory Metals and Ceramics, II (eds T.M. Besmann, B.M. Gallois and J. Warren), pp. 17-28, 1992.
Reproduced by permission of the Materials Research Society, Pittsburgh, PA.)

supersaturation and more limited diffusion.
The most desirable coatings for mechanical
strength and fracture toughness consist of
very fine, equiaxed grains. This microstructure
is typically produced at still higher supersat-
urations and conditions under which surface
diffusion is limited. The supply of reactants
must be sufficient to rapidly renucleate new
grains while the movement of atoms to pre-
ferred crystal lattice sites is restrained. Addi-
tion of trace quantities of impurities or
catalysts may promote renucleation.
Examples of the wide range of coating
morphologies which can be produced from
even the same chemical system are shown
in Figure 22.10. The boron carbide coatings
were deposited on graphite from BCl3 ,
CH4 and Hz and the structures modified
by simply adjusting temperature and
reactant concentrations (Lowden, Riester and
Akerman, 1992).
Coating adherence is a critical problem that
must be addressed in every coating appli-
cation. A coating's coefficient of thermal
expansion must be closely matched with that
of the substrate to prevent cracking or
spalling. Compliant intermediate coatings
are often necessary to minimize the residual
560 Chemical vapor deposition and infiltration
Figure 22.10 Varying CVD conditions can create a variety of microstructures/morphologies in the same
chemical system.
stresses created at the interfaces. Surface
pretreatments are often used to improve
adhesion, typically by roughening the sub-
strate surface to enhance mechanical inter-
locking of coating and substrate. These
treatments can include chemical etching and
grit blasting.
More recently, coatings have been produced
in which the composition of the interlayer
gradually varies from that of the substrate
to that of the coating (Sasaki and Hirai,
1991; Kowbel, Bruce and Withers, 1995). This
variation not only reduces the residual
stresses but also avoids the effects of abrupt
interfaces. Coating compositions must also be
selected that avoid significant reaction at the
coating-substrate interface. Reaction layers
frequently create large residual stresses that
result in cracking or spalling.
Another method for increasing adherence is
to increase the fracture toughness of the coat-
ing. As noted above, tough coatings can be
produced by co-deposition of more than one
phase (Stinton et al., 1984; Moss, Lackey and
Freeman, 1995). Composite coatings exhibit
increased toughness because cracks that
propagate in the coating interact with the
included second phase and are blunted or
deflected. The example of the co-deposition
of an SiC- TiSi2 layer noted earlier increased
the fracture toughness of the coating by a
factor of two over SiC (Figure 22.11) (Stinton
et al., 1984).
PRACTICAL CVD SYSTEMS
CVD reactors can be considered to be made up
of three sections in series. The first is the reac-
tant feed system, or manifold, which serves to
meter reactant species into the CVD system.
The second is the CVD reactor itself, which
can be as simple as a tube furnace. The final
section contains the vacuum pump (if less
than atmospheric pressure is used), the
pressure control system (again, if necessary),
and the exhaust gas clean-up or scrubber. A
schematic of a typical CVD system is shown
in Figure 22.12.
Flow control
Conventional mass flow controllers are cur-
rently available to accurately meter precursor
gases, including highly corrosive gases, at
either atmospheric or reduced pressure.
These instruments allow for close control of
inlet species partial pressures, regardless of
ambient conditions.
The metering of vapor sources that are
liquids or solids at room temperature is
 Chemical vapor deposition (CVD) 561

SiC

Dispersed
phase

Substrate

100fLm
I I

Figure 22.11 Optical metallograph of SiC coating with TiSi 2 dispersed phase. (Stinton, D.P., Lackey, W.J.,
Lauf, R.J. and Besmann, T.M., 'Fabrication of ceramic-ceramic composites by chemical vapor deposition,'
Cer. Eng. Sci. Proc., 5(7-8), 668-76, 1984. Reproduced by permission of the American Ceramic Society,
Westerville,OH.)

more problematical. Liquids with significant
vapor pressures are more easily controlled.
Variants on conventional mass flow control-
lers are available for use with low pressure
CVD systems. The precursor reservoir is
kept at a pressure above that of the reactor,
which can require warming of the reservoir,
such that there is flow to the reactor. The
mass flow controllers used in such systems
take advantage of the pressure drop and

Control
Valve
Inert Gas
for Pressure
Control

Scrubber
Column

MTS
Vaporizer

Vacuum Pump

Figure 22.12 Schematic of a typical CVD system for the deposition of SiC from methyltrichlorosilane and
hydrogen. (Stinton, D.P., Besmann, T.M. and Lowden, RA., 'Advanced ceramics by chemical vapor
deposition techniques,' Am. Ceram. Soc. Bull., 67(2), 350-55, 1988. Reproduced by permission of the
American Ceramic Society, Westerville, OH.)
562 Chemical vapor deposition and infiltration
are usually designed to handle greater than
ambient temperature.
Providing vapor species from a liquid
source to an atmospheric pressure reactor is
a more difficult problem. Typically, a carrier
gas is bubbled into the precursor reservoir
with the hope that the gas would be saturated
with vapor. Thus, close control of reservoir
temperature together with a knowledge of
the dew point of the liquid allows fairly
accurate metering of the precursor. In recent
years, vapor source controllers have become
available for a few precursor liquids. These
controllers monitor and control the flow of
carrier gas into the bubbler and measure the
mixture of precursor and carrier exiting the
bubbler. The instrumentation then controls
the carrier gas control valve on the inlet side
of the bubbler to maintain the proper concen-
tration. These systems obviate the need for
controlling reservoir temperature. Finally, if
liquid metering systems are available that
can be adequately sealed against air leaks,
that have the necessary corrosion resistance,
and that can accurately pump at a continuous
rate, the simple pumping of liquid precursor
into a heated vaporization vessel can provide
metered flow.
Providing precursor species from solid
sources is more difficult still. A carrier gas
saturation method is again possible, but
difficult to control. In addition, the vapor
pressures are typically so low as to make all
but the lowest CVD growth rates impossible.
In-situ halination is a method whereby the
halide precursor is produced within the CVD
reactor, upstream of the substrate. A pre-
reactor chamber containing a metal to
be halinated is heated by the CVD furnace or
a separate furnace. The halogen is then
allowed to flow through the prereactor
chamber, converting the metal to halide and
then sweeping it to the substrate. Finally,
Lackey et al. (1990) have developed a tech-
nique for directly metering powder precur-
sors into a CVD furnace such that they
evaporate at the high temperature of the
CVD reactor. This was successfully used to
produce high deposition rates of the ceramic
superconductors.
Pressure
Many, if not most, CVD systems operate
under reduced pressure so as to drive the
rate-limiting steps to be surface reaction
rather than gas phase mass transport limited.
Controlling reduced pressure can be accom-
plished in two ways: either by a throttle
valve or by a gas ballast technique. Throttle
valves can be placed upstream of the
vacuum pump and thus control the resultant
orifice size. Given the continuous flow of the
reactant gas, adjustment of the valve results in
control of the pressure. Automatic throttle
valves can be slaved to a controller which
acts on a signal from a pressure transducer
placed upstream in the system.
Gas ballast control removes the need for a
throttle valve, which can often have difficulty
controlling moderate vacuum systems. Gas
ballast depends on injection of inert gas into
the inlet of the vacuum pump to control
pressure (Clark and Sullivan, 1982). The
signal from a controller, driven by a pressure
transducer on the furnace, appropriately
opens a control valve to flow gas into the
pump. The pump is operating at a constant
pumping speed, thus the inert gas makes
up the difference between the exhaust gas
flow from the reactor and throughput
capability of the pump at the setpoint
pressure.
Temperature
Temperature control in CVD systems can
be accomplished with conventional thermo-
couples and a controller which drives the
furnace power supply. Thermocouples in
CVD systems generally have to be protected
from the corrosive CVD gases, and are often
located outside of the reactor. More accurate
control can often be achieved using optical

pyrometry, with the pyrometer linked to a
power supply controller.
CHEMICAL VAPOR INFIL TRA TION (CVI)
Chemical vapor infiltration (CVI) originated
in efforts to densify porous graphite bodies
by infiltration with carbon (Bickerdike et al.,
1962). The technique has developed com-
mercially such that half of the carbon-carbon
composites currently produced are made by
CVI (the remainder are fabricated by curing
polymer-impregnated fiber layups). The
earliest report of CVI for ceramics was a
1964 patent for infiltrating fibrous alumina
with chromium carbides (Jenkin, 1964).
In CVI, reactants are introduced in the
porous preform via either diffusion or forced
convection, and the CVD precursors deposit
the appropriate phase(s). As infiltration pro-
ceeds, the deposit on the internal surfaces
becomes thicker. Thus after some length of
time the growing surfaces meet, bonding the
preform and filling much of the free volume
with deposited matrix.
t tHott t
t tott t
Type III Isothermal-forced Type IV Thermal gradient-
flow: reagents flow
through preform
Figure 22.13 The five different types of CVI processes classified as to method transport of reactant species
into the preform and the presence of a thermal gradient.
Chemical vapor infiltration (CVI) 563
The greatest commercial interest is in con-
tinuous filament fibrous preforms, in which
the high strength fibers can be aligned with
the high stress directions (Haug, Knabe and
Ehrmann, 1994). The major advantage CVI
has over competing densification processes is
the low thermal and mechanical stress to
which the relatively sensitive fibers are sub-
jected. As noted above, CVD can occur at
temperatures much more modest than the
melting point of the deposit, and therefore
usually well below the sintering temperature.
In addition, the process imparts little mechan-
ical stress to the preform as compared to more
traditional techniques such as hot pressing.
CVI TECHNIQUES
There are five general types of CVI techniques
and they are classified as to whether they
utilize diffusion or forced flow for transport
of gaseous species, and whether thermal
gradients are imposed (Figure 22.13). The
most widely used commercial process is
isothermal-isobaric CVI (lCVI) (Rossignol,
Hot
----Cold--
Type II Thermal gradient:
Reagents contact
cold surface of preform
and enter via diffusion
t
Type V Pulsed flow: reagents
forced flow: flow into and out of
reagents flow preform because of
through preform cyclical evaluation
from cold to hot and back filling
surface
(forced CVI:FCVI)
564 Chemical vapor deposition and infiltration
Langlais and Naslain, 1984; Fitzer and Gadow,
1986; Naslain and Langlais, 1990; Naslain,
1992b), which depends only on diffusion for
species transport. These generally operate at
reduced pressure 0-10 kPa; 7.5-75 torr) for
deposition rate control. Fixturing of the
fibrous preforms is needed before initial den-
sification to maintain the proper shape. Den-
sity gradients are minimized by a low
reaction temperature, although in order to
get economical densification rates, deposition
is often sufficiently rapid to overcoat the outer
surface before infiltration is complete. Inter-
ruption of the CVI process for periodic
machining of parts is thus necessary for all
but the thinnest parts, to open diffusion
paths from the surface. Regardless, this diffu-
sion-dependent process is still slow, requiring
several-week-Iong infiltration times. It is com-
mercially attractive, however, because large
numbers of parts of varying dimensions are
easily accommodated in a single reactor.
The thermal gradient process (Figure 22.13)
appears to be little used but may have advan-
tages under certain circumstances. In a new
development for this technique, there have
been some exploratory efforts in using micro-
wave heating to produce the thermal gradient
(Devlin et al., 1992, 1993; Morell, Economou and
Amundson, 1992a; Spotz et al., 1993; Day et al.,
1994). The outer regions of a relatively low ther-
mal conductivity preform will cool radiatively,
while the central volume rises to temperatures
at least several hundred degrees centigrade
higher. This may still be a slow process, how-
ever, due to the dependency on diffusion.
The potentially more rapid isothermal-
forced flow process (Figure 22.13), which
uses forced convection, has begun to be used
commercially for very thin-walled material
(typically one cloth layer in thickness). Thicker
materials suffer from density gradients and
loss of permeability at the entrance surface
also seen in the isothermal-isobaric process
(Roman et al., 1993).
The forced-flow-thermal gradient tech-
nique (FCV!) (Figure 22.13) overcomes the
problems of slow diffusion and restricted
permeability, and has demonstrated a capabil-
ity to produce thick-walled, simple-shaped
components in times on the order of hours
(Besmann, Stinton and Lowden, 1988; Stinton,
Besmann and Lowden, 1988). These tech-
niques all require individual fixturing of
each part to maintain the required shape,
and pressure and thermal gradients.
Pulsed-flow CVI (Figure 22.13) utilizes
alternate introduction of reactant gases and
evacuation of the CVI reactor to rapidly trans-
port reactant species into, and product gases
out of, the preform (Beatty and Kiplinger,
1970; Sugiyama and Yamamoto, 1989; Itoh
et al., 1992; Sotirchos, 1993; Sugiyama and
Yoshida, 1993). The technique has not been
widely investigated, although some modeling
calculations indicate it can significantly
improve infiltration rates over those experi-
enced in isothermal CVI (Sotirchos, 1993).
HISTORY OF CVI AND ITS MARKET
During the last two decades much of the
development of CVI techniques has taken
place at the University of Karlsruhe (Fitzer,
Kehr and Sahebkar, 1973; Fitzer, Hegen and
Strohmeier, 1980; Fitzer and Gadow, 1986),
the University of Bordeaux (Lamicq et al.,
1986; Naslain and Langlais, 1986, 1990) and
Oak Ridge National Laboratory (Besmann,
Stinton and Lowden, 1988; Stinton, Besmann
and Lowden, 1988; Besmann et al., 1991).
Markets for CVI-produced ceramic com-
posite materials are just emerging with the
recent establishment in the US of a moderately
large scale production facility at E.I. Dupont
de Nemours and Company and B.F.
Goodrich. Based on similar facilities operated
by Societe Europeenne Propulsion (SEP) in
France, these are currently the major world
suppliers of ceramic matrix CVI materials.
Some products have already found them-
selves in regular commercial use, yet the
considerable output of the US and French
producers is being used largely for material

testing and component evaluation. Many of
the likely applications of CVI material will
be in aerospace systems, with thrust deflectors
already being used routinely in Rafel aircraft.
Potential other areas are in high temperature
heat exchangers and hot gas filtration. By far,
the most common ceramic matrix produced is
SiC, although matrices of TiC, B4 C, BN, Si3 N 4 ,
TiN and TiB2 have been fabricated (Roman
and Stinton, 1995).
CVI FUNDAMENTALS AND MODELING
During CVI, the primary objective is to
maximize the rate of matrix deposition and
minimize density gradients. Unfortunately,
there is an inherent competition between the
deposition reaction and the mass transport of
the gaseous reactant and product species.
Deposition reactions which are too rapid
usually result in severe density gradients,
where there is essentially complete densifi-
cation near the external surfaces and much
lower densities in the interior regions.
Alternatively, exceptionally slow deposition
reactions require an uneconomically long
time to densify a part.
General relationships
Describing the deposition of matrix material in
a porous structure is, in principle, a simple
matter. The process is accurately represented
by the well-known partial differential equa-
tions that describe mass and heat transfer, in
conjunction with relationships that accurately
describe the chemical kinetics and the evolu-
tion of the microstructure during infiltration.
Because of the practicalities involved with
obtaining these specific relationships, the
development of fully predictive models has
been elusive. For an isothermal-isobaric CVI
system, diffusion and a first order reaction
are described by
8(cp c)
-at = V' . [V'(De c)] - cpSvkrc (22.11)
Chemical vapor infiltration (CVI) 565
where cp is the void fraction and Sv is the
surface to volume ratio of the porosity. The
final term is easily modified to describe more
complex reaction kinetics. Since the porosity
changes as infiltration proceeds, cp ' Sv and
De are not constants. Therefore, the model
must also contain additional equations that
describe these changes. The complete set of
equations can then be solved for appropriate
boundary conditions. If mass transport to the
outside of the preform is important, then the
boundary condition for c at the external sur-
faces must include a description of this
mechanism. The time derivative is usually
set to zero, in accordance with the pseudo-
steady-state approximation (Luss, 1968).
The simplest CVI models treat the process
as a pore diffusion problem, using cylindrical
pores and a first order deposition reaction
(van den Brekel et al., 1981; Fedou, Langlais
and Naslain, 1990; Fitzer, Fritz and Schoch,
1991). This treatment illustrates the formation
of undesirable density gradients during
infiltration. It is convenient to compare the
relative rates in this process with a dimension-
less number called the Thiele modulus, <P,
which represents the ratio between the
chemical kinetic deposition rate and the gas
phase mass transport rate. The primary diffi-
culty with applying the Thiele modulus to
infiltration processes is that its value changes
during the process due to changes in pore
size. It is therefore convenient to characterize
isothermal CVI with the initial value of the
Thiele modulus, <Po (Sheldon and Besmann,
1991). For a first order deposition reaction in
a cylindrical pore:
<P6 = 2kr l2 (22.12)
RoDo
where Ro and Do are the pore radius and the
gas diffusivity in the initial preform, respec-
tively, and I is the length of the pore (i.e. the
characteristic thickness of the preform).
The two limiting cases during isothermal-
isobaric CVI are illustrated in Figure 22.14.
Under reaction rate-controlling conditions
 ......
566 Chemical vapor deposition and infiltration

Filaments'
~
~ro
/
Filament Bundle

Deposited
Matrix

"",,141--- ro --~
Pore
--
Reactant Concentration C

Figure 22.14 Depending on whether mass transport or chemical kinetics is rate-limiting determines
uniform infiltration. (Besmann, T.M., Sheldon, B.W., Lowden, R.A. and Stinton, D.P., 'Vapor-phase fabri-
cation and properties of continuous-filament ceramic composites,' Science, 253,1104-09, 1991. Reprinted
by permission of the American Association for the Advancement of Science, Washington, DC.)

(<1>6 ~ 1) gas transport is rapid, and the initial
reactant concentration is essentially uniform
throughout the pore volume. As a result,
uniform deposition takes place down the
length of the pore causing no gradient in com-
posite density. For diffusion rate-controlling
conditions (<1>6 1), however, the deposition
reaction is fast causing a decreasing con-
centration of reactants down the pore length
with a proportional decrease in the formation
of matrix material and a significant composite
density gradient. Mixed control occurs when
the two rates are comparable (<1>6 : : : : 1).
Describing CVI with cylindrical pores
does not accurately reflect the often complex
microstructures that are present in real pre-
forms. The most common reinforcements in
composites formed by CVI are fibers with a
relatively small diameter (",10 p,m). Bundles
of these are woven into cloth layers, which
are then stacked to form a preform. In some
cases, three-dimensional weaves are also
used. All of these preforms have multimodal
porosity distributions, which range from
micrometer scale within fiber bundles, to
hundreds of micrometers between bundles
and cloth layers. The porosity and fiber archi-
tecture, which are typically anisotropic,
govern the gas permeability and the thermal
properties. As densification proceeds, the
dimensions and distribution of the porosity
changes non-uniformly with attendant
changes in the preform's physical properties.
For CVI to be successful, the reactant gases

must initially reach the finest porosity (i.e. the
interfilament volume), react, and fill those
pores. When this volume is relatively well
infiltrated, the larger interbundle and interply
porosity should then be filled. The series of
photos in Figure 22.15 illustrates this pro-
gression during the infiltration of Nicalon
fibers within an SiC matrix.
Chemical vapor infiltration (CVI) 567
Modeling
Several CVI models have used descriptions of
the porosity that are based on the actual near
cylindrical shape of fibers used in CVI (Starr,
1988; Currier, 1990; Tai and Chou, 1990;
Sheldon and Besmann, 1991; Chang, Morse
and Sheldon, 1994; Kawase et al., 1994).

INFILTRATION
TIME

(!)
z
en
<l
w
a::
u
z

Figure 22.15 Evolution of microstructure in CVI of SiC-Nicalon. (Besmann, T.M., Sheldon, B.W.,
Lowden, RA. and Stinton, D.P., 'Vapor-phase fabrication and properties of continuous-filament ceramic
composites,' Science, 253, 1104-09, 1991. Reprinted by permission of the American Association for the
Advancement of Science, Washington, DC.)
568 Chemical vapor deposition and infiltration
Recent efforts to describe the evolving poros-
ity in fibrous preforms are based on a model
for phase transformations (Currier, 1990;
Sheldon and Besmann, 1991). Models have
also been developed for reacting porous
solids which undergo pore closure in systems
other than CVI, which more accurately
describe the inevitable formation of trapped
porosity using percolation theory (Yortsos
and Sharma, 1986; Reyes and Jensen, 1987;
Yu and Sotirchos, 1987). These approaches
describe mass transport with percolation in a
Bethe lattice (Sahimi, Gavalas and Tsotsis,
1990) and can easily be modified to describe
CVI (Sheldon and Besmann, 1991). The pri-
mary shortcoming of all of these continuum-
and percolation-based models is that they
fail to describe the multimodal nature of the
porosity in real preforms. However, very
recent modeling efforts that are currently
under way are employing multimodal descrip-
tions of the porosity (Chung et al., 1992; Starr,
1992; Chang, Morse and Sheldon, 1994).
Although work is continuing at a number of
laboratories to develop more extensive CVI
models, most of these have not been compared
to experimental results. Thermogravimetric
experiments of the reaction-controlled infiltra-
tion of fiber bundles with carbon (Devlin, Bar-
bero and Currier, 1990) agree generally with
Currier's (1990) model. Sheldon and Besmann
(1991) compared isothermal data for the infil-
tration of individual fiber bundles with SiC
from methyltrichlorosilane, to modeling results
that were based on a first order reaction and a
wide variety of different descriptions of diffu-
sion. The results of this comparison imply that
a multistep reaction leads to poor infiltration
compared to the predictions for a first order
reaction. It is theoretically possible that other
complex reaction kinetics can lead to infiltra-
tion which is more uniform than the first
order predictions. A relatively simple descrip-
tion of isothermal CVI with a sequence of two
first order reactions has been used to demon-
strate this possibility (Middleman, 1989; Shel-
don, 1990). These experimental and calculated
results suggest that a greater understanding of
complex reaction sequences can lead to
significant improvements in existing CVI
techniques. Lin (1990) has used a continuous
model to describe isothermal-forced-flow CVI.
Several CVI modeling efforts have described
non-isothermal processes (Starr, 1988, 1992; Tai
and Chou, 1989, 1990; Melkote and Jensen,
1990; Starr et al., 1993). In these systems, there
are additional complexities associated with
heat transfer and forced convection as infiltra-
tion proceeds and the structure of the material
changes. For models such as these to accurately
describe infiltration behavior, accurate descrip-
tions of the complexities associated with these
transport processes will have to be combined
with the complex microstructure evolution
and chemical kinetics that have already been
discussed in connection with isothermal CVI.
Compounding these issues are those associated
with microwave heating, including the
coupling of the field to the component and the
resulting thermal behavior (Gupta and Evans,
1991; Morell, Economou and Amundson,
1992b,1993).
Regardless of these complexities and the
current inability to fully describe them, under-
standing the general relationships between
the relevant kinetic processes has led to the
practical solution of many CVI problems.
Control of temperature is critical because
chemical reactions exhibit Arrhenius behavior
such that the rates increase exponentially
with temperature. Therefore, relatively low
temperatures slow the deposition rate
substantially more than does diffusion, thus
reducing <P. Simple reactant gas depletion
within the CVI reactor or poisoning of the
deposition process by reaction by-products
(e.g. HCl in the CVI of SiC from methyl-
trichlorosilane) also reduces the deposition
rate (Besmann et al., 1992). In thermal gradient
processes, controlling the temperature differ-
ence prevents the gas entrance surfaces from
becoming sealed until after the interior of the
component has reached an acceptable density
(Stinton, Besmann and Lowden, 1988).

FIBROUS PREFORMS
Fibers
The properties of the fibers are fundamental
to a composite's properties. Like the matrix,
ceramic fibers have high strength and high
elastic modulus. Although an advantage of
CVI processing is prevention of damage
to ceramic fibers, they must still be able to
withstand the CVI environment. This gener-
ally entails elevated temperatures of the
order of 1300 K (1027 0c) and corrosive
matrix precursors.
A number of carbide and nitride fibers
(Chapter 17) have become available in recent
years which offer a variety of properties to
the material designer (Table 22.3), although
almost all have been restricted to developmen-
tal activities. Silicon carbide fibers are attractive
for use in high temperature, oxidative environ-
ments, and these are being established in
potential commercial products (Stinton et al.,
1995). A chemical-vapor-deposited, large
diameter (",,150 mm) SiC fiber produced by
Textron Specialty Materials has been used in
Table 22.3 Developmental and commercially available non-oxide ceramic fibers (adapted from Hong,
Rigdon and Fortenberry, 1990)
Chemical vapor infiltration (CVI) 569
CVI, although such a large fiber is difficult to
form into other than very simple shapes. The
most commonly used SiC fiber is Nicalon,
which is a polymer-derived microcrystalline/
amorphous material containing significant
amounts of silica. Recent development of Hi-
Nicalon and Hi-Nicalon types offer
higher temperature, low silica content alterna-
tives. Other similar fibers, Tyranno and
LOX-TyrannoTM, are produced by Ube Indus-
tries. A silicon-nitrogen fiber (HPZTM) and a
new, high strength SiC fiber have been
developed by Dow Corning.
In general, however, the polymer-derived,
amorphous fibers, while having the advantage
of lower cost and easier handling, typically
lose strength at elevated temperatures and
under CVI atmospheres (Simon and Bunsell,
1984; Lamicq et al., 1986; Bunsell et al., 1988).
Preforms
Preform geometries can be tailored to the
application in order to maximize strength
and toughness in the direction of maximum

Source Trade name Commercially Type Process Diameter

available (/-Lm)

Textron SCS-2 No SiC on C CVD 140

SCS-6 No SiC on C CVD 143
SCS-8 No SiC on C CVD ~140
No SiC-Si3N4 Polymer precursor 6-10
Dow Corning MPDZ Yes SiC Polymer precursor 10-15
HPZ Yes Si3N4 Polymer precursor 10
MPS No SiC Polymer precursor 10-15
Carborundum No SiC Extruded and sintered 30-50
No BN (fiber) nitridation
Nippon Carboni Nicalon Yes SiC Polymer precursor 10-20
Dow Corning Hi-Nicalon Yes
Hi-Nicalon type S No
Ube (Textron) Tyranno Yes SiC-TiC Polymer precursor 8-10
LOX-Tyranno Yes
BP Sigma No SiC on W CVD 100
Electroceramics Yes BN (fiber) Polymer precursor 2-6
Toa Nenryo No Si3N4 (fiber) Polymer precursor 10
Kogyo (Tonen)
 570 Chemical vapor deposition and infiltration
stresses. The general types of preforms
include felts, which are randomly oriented,
continuous fiber lengths that maintain shape
by entanglement. A common preform is
made by stacking layers of tape or cloth plies
(for reinforcement within the plane of the
cloth). The most sophisticated preforms are
three-dimensional weaves or braids, which
can offer multidimensional reinforcement,
bordering on isotropy.
FIBER-MATRIX INTERFACE
Interfacial shear stresses playa key role in deter-
mining the mechanical properties of a fiber-
reinforced ceramic composite. In single-phase
materials, the energy absorbed during fracture
is determined by the applied forces and the
strain and surface energies of that material. In
composites, however, there are the additional
phenomena of strain energy of the fibers and
the work done in debonding the fibers from
the matrix. These additional factors will contri-
bute to increasing the stress at which the matrix
in a composite will begin to crack.
Fiber coatings have been used to modify
fiber-matrix interfacial forces and thus control
mechanical properties of continuous fiber cer-
amic composites. It has been shown that the
properties and thickness of the interlayer

3OO r-------~------~--------~------~------~--------,

250

200

LOAD 150
(N)

too

50

OL---~--~------~~L-----~------~--------~------~
o 0.01 0.02 0.03 0.04 0.06 0.07
DISPLACEMENT (em)
Figure 22.16 Load-displacement curves for four-point flexure tests of CVI SiC-Nicalon composites
produced with differing thicknesses of carbon precoats on the fibers. Associated with each curve is an
SEM image of the fracture surface indicating the relationship to fiber pullout. (Besmann, T.M., Sheldon,
B.W., Lowden, R.A. and Stinton, D.P., 'Vapor-phase fabrication and properties of continuous-filament
ceramic composites,' Science, 253, 1104-09, 1991. Reprinted by permission of the American Association
for the Advancement of Science, Washington, DC.)
 Chemical vapor infiltration (CVI) 571

(a)

(b)
Figure 22.17 (a) Commercial isothermal-isobaric CVI system and (b) products fabricated in these reactors.
(Photo courtesy of DuPont Lanxide Composites Inc., Newark, DE.)
572 Chemical vapor deposition and infiltration

Figure 22.18 Developmental forced CVI system at Oak Ridge National Laboratory.

influence composite properties such as matrix Experience has shown that NicalonTM, and
cracking and ultimate strength, toughness and most other fibers, require precoating before
interlaminar shear (Miller, Lowden and Liaw, infiltration to avoid strong interfacial bonding
1995). and, thus, brittle fracture (Figure 22.16).

Composites with uncoated fibers exhibit frac-
ture surfaces which are flat and smooth with
no evidence of fiber pullout and result in little
toughening. To tailor the mechanical proper-
ties of Nicalon-SiC composites, a thin pyro-
lytic carbon layer is deposited on fibrous
preforms prior to densification to provide a
controlled and uniform interface with the
matrix. The carbon deposition conditions are
chosen to produce a graphitic coating with a
laminar structure that generally lies parallel
to the fibers. The coating has been found to
prevent chemical damage of the fibers
during processing, as well as weakening the
fiber-matrix interface, enhancing fiber
debonding and slip (Lowden and More,
1989; Lowden et al., 1993). Thus, the coating
results in an increase in the toughness and
the ultimate strength of the composite
materials. Recent work on alternative, more
oxidation-resistant coatings has indicated
that EN may usefully replace carbon.
PRACTICAL CVI SYSTEMS
As noted earlier, the largest production
facility for CVI ceramic materials are those
of DuPont and B.F. Goodrich in the US and
SEP in France. These organizations employ
the isothermal-isobaric CVI process to pro-
duce components, largely SiC matrix and
using either Nicalon or carbon fibers. The
CVI reactors are essentially vacuum vessels
with graphite internals. The process is per-
formed at reduced pressure with CH3 SiCl3
as the reactant for SiC infiltration. Preforms
are placed on graphite shelving and the reac-
tants flow through the system. The hot zones
of these reactors measure 3 m (9.8 ft) or larger,
accommodating hundreds of parts (Figure
22.17). The slow infiltration rate required of
isothermal-isobaric systems causes these
reactors to operate up to weeks at a time.
Depending on the component, intermediate
machining may be required for shaping and
to open passages for reactants, which may
have sealed during infiltration, to diffuse
References 573
into the part. Typically, a final CVD seal
coat is applied to the parts to prevent
oxidation of the carbon interface during
service. Details of commercial systems are
highly proprietary and thus more informa-
tion is not available.
There are currently no commercial-scale
forced-flow-thermal gradient CVI systems.
General Atomics Corp. and Amercom have
developmental capabilities to produce disks
of the order of 0.3 m (11.8 in) in diameter and
several centimeters in thickness. A develop-
mental system is illustrated in Figure 22.18.
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pulse CVI of SiC J. Mater. Sci., 24, 3756--62.
Sugiyama, K and Yoshida, K (1993) Pressure-
pulsed CVI of silicon carbide into 2D-Tyranno/
carbon preforms, in Proceedings of the 12th Interna-
tional Conference on CVD (eds KF. Jensen and
G.W. Cullen), The Electrochemical Society, Pen-
nington, NJ, pp. 371-77.
Tai, N.-H. and Chou, T.-W. (1989) Effects of manu-
facturing parameters on the chemical vapor
infiltration of ceramic/ceramic composites. Proc.
Am. Soc. Compos., Technomic, Lancaster, PA,
pp.317-22.
Tai, N.-H. and Chou, T.-W. (1990) Analytical
simulation of an improved CVI process for form-
ing highly densified ceramic composites, in
Chemical Vapor Deposition of Refractory Metals and
Ceramics (eds T.M. Besmann and B.M. Gallois),
Materials Research Society, Pittsburgh, PA,
pp.61-66.
Thornton, J.A (1977) High rate thick film growth.
Annu. Rev. Mater. Sci., 7, 239-60.
Werner, C (1991) Numerical modelling of CVD
processes and equipment. ,. Physique, 1(C2),
3-18.
Yortsos, Y.C and Sharma, M. (1986) Application of
percolation theory to noncatalytic gas-solid
reactions. AIChE J., 32(1), 46-55.
Yu, H.-C and Sotirchos, S.V. (1987) A generalized
pore model for gas-solid reactions exhibiting
pore closure. AIChE J., 33(3), 382-93.
PLASMA-ENHANCED CHEMICAL
VAPOR DEPOSITION (PECVD)
Steven R. Droes, Toivo T. Kodas and Mark J. Hampden-Smith
INTRODUCTION
This chapter presents a short review of
plasma-enhanced chemical vapor deposition
(PECVD) of non-oxide ceramics. A brief
discussion of glow discharge plasmas as
used in PECVD is presented first. This dis-
cussion provides a practical understanding
of the processes and characteristic chemistry
involved in PECVD. Next, the deposition of
specific ceramic films is discussed in terms
of precursors, types of plasmas and film
properties. Although PECVD has been used
extensively in microelectronics, these applica-
tions are not reviewed here. The focus of this
chapter is on non-oxide ceramics used mainly
as hard coatings, with the discussion confined
to nitrides and carbides. Although TiB 2, MoB,
TaB2 and other borides are used as hard cer-
amic coatings, their deposition via plasma-
enhanced CVD has not been reported. This
chapter concludes with a discussion of the
advantages and limitations of PECVD-
prepared coatings.
High performance tools and machine parts
demand specific bulk properties such as hard-
ness, high thermal conductivity and both high
compressive and bending strength. Since
these materials are subjected to heavy wear,
their surface properties are also of vital impor-
tance. For an extensive list of these properties
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
23
for nitrides, carbides, borides and other
ceramics, the reader is referred to the work
of Galasso (1991). A high surface hardness
(e.g. Si3N 4; Hy = 20-40 GPa: SiC, Hy = 230-
350 GPa) and a low coefficient of friction are
required to reduce wear. These properties
are exhibited by hard materials and not
necessarily the material from which the tool
is composed.
There are two ways to achieve the required
combination of surface and bulk properties.
First, composites consisting of a hard material
and a metallic phase can be formed. The hard
material provides the required wear resistance
and the metal phase provides ductility. The
formation of the composite, however, results
in a compromise of both the surface properties
of the hard material and the bulk properties of
the metal phase. Second, properties of the
surface can be separated from bulk properties
by depositing a hard coating on a ductile sub-
strate. This second method has the advantage
that there is little loss of the required inherent
properties of both the surface and bulk phases
provided good adhesion exists between the
coating and the substrate (Laimer, 1990).
Options available for deposition of hard
coatings include using gaseous, liquid and
solid species as sources of the deposition
material (Figure 23.1). Deposition from the
gas or vapor phase is the most important for
580 Plasma-enhanced chemical vapor deposition
I Therm. CVD I
Figure 23.1 Systematic of deposition techniques.
hard coatings. Among the techniques avail-
able, conventional chemical vapor deposition
(CVD) (as discussed in Chapter 22) is most
widely used and provides good quality films
with excellent film uniformity. However, most
CVD processes for hard materials require
deposition temperatures of about 1273 K
(1000C). For many applications, damage to
the metal phase occurs at this high tempera-
ture (Arai, Fujita and Oguri, 1988).
Plasma-assisted CVD (PACVD) and plasma-
enhanced CVD (PECVD) take advantage of the
high energy electrons present in glow dis-
charges to dissociate and ionize gaseous
molecules to form chemically reactive radicals
and ions. Because thermal energy is not needed
to break chemical bonds, reactions can be pro-
moted at lower temperatures (Petrich, 1989)
thereby avoiding substrate damage. Thermally
sensitive materials, such as tool steels, can be
coated with a hard coating of TiN, improving
the wear performance immensely.
Although the chemistry and physics of a
glow discharge are extraordinarily complex,
the plasma performs only two basic functions.
First, reactive chemical species are generated
by electron-impact collisions; this overcomes
kinetic limitations that may exist in thermally
Plasma-
Polymerization
activated processes. Second, the discharge
supplies 'energetic radiation' (generally in
the form of positive ions, neutral species,
metastable species, electrons and photons)
that bombard surfaces immersed in the
plasma and thus alter the surface chemistry
during deposition. The combination of these
physical processes with the strictly chemical
reactions due primarily to atoms, radicals or
molecules yields material properties unattain-
able with either process individually (Laimer,
1990).
In order to provide a basis for discussion of
the various applications of PECVD, a brief
outline of the physical and chemical character-
istics of plasmas is presented first. This outline
provides a mechanistic understanding of the
processes involved in plasma processing and
PECVD. For a more detailed discussion of the
chemical and physical processes involved in
plasma processing the reader is referred to
the works by Boenig (1988) and Hess and
Graves (1989).
GLOW DISCHARGE PLASMAS
One of the earliest and most important
developments in plasma studies was the

Positive
Sealed Glass Tube
Electrode
Electrons
Figure 23.2 Crookes glow discharge tube. (Boenig, H.V., Fundamentals of Plasma Chemistry and Technology,
1988. Reproduced by permission of Technomic Publishing Company, Inc., Lancaster, PA.)
work of Sir William Crookes who, in 1879,
developed the 'glow discharge tube'. The
apparatus consisted of a tube evacuated to a
low pressure and filled with a gas. Under
these conditions an electrical current could
be forced through the gas, and when excited
by the electrical energy the rarefied gas
showed a glow the color of which depended
on the nature of the gas being used. This
glow was caused by the electrical current
flowing between two electrodes which disso-
ciated the gas molecules into positively
charged ions and electrons (Figure 23.2).
Glow discharges or low temperature plas-
mas are, by definition, plasmas that exhibit
no net charge, i.e. the number of negatively
charged and positively charged species are
equal. The plasma, a partially ionized gas, is
composed of ions, electrons and a host of
neutral species in both ground and excited
vibrational states.
PLASMA CHARACTERIZATION
Within the classification of low temperature
plasmas there are many types of plasmas.
They are characterized by the electron concen-
tration, ne, and average electron energy, kBTe,
Joules/ electron, where kB is the Boltzmann
constant and Te is electron temperature. The
electron densities (n e ) and positive ion densi-
ties (ni) range from 108 to 1012 / cm3 . These
Plasma characterization 581
Negative
Electrode
Positively Charged Ions
types of plasmas are termed non-equilibrium
plasmas, because the average electron energy
(kBTe) is considerably higher than the ion
energy (kBTi, where Ti is ion temperature).
Therefore, the discharge cannot be described
adequately by a single temperature, but is
described by electron (Te ), ion (Ti ) and neutral
particle (Tn) temperatures.
Since the plasma is electrically neutral,
the number of negatively charged particles
(electrons) equals that of the positively
charged species. Therefore, the electron den-
sity (negative charge) and the positive ion
density (positive charge) must balance. How-
ever, the ratio of the neutral species density to
the electron density is usually greater than 103 ,
so that these plasmas are only weakly ionized.
Radicals and molecules are not inherently
more reactive than ions, but they are present
in significantly higher concentrations. As a
result, free radicals and molecules in the
discharge are primarily responsible for
deposition reactions.
Free atoms or larger fragments of molecules
which contain one or more unpaired electrons
are called free radicals. Although some free
radicals are relatively inert, they are generally
highly reactive with respect to rearrangement,
radical-radical recombination or reactions
with other species. A large number of free
radicals are known to exist in glow discharge
plasmas. In common discharges, a free radical
582 Plasma-enhanced chemical vapor deposition
such as cr is most often formed from gas
molecules by the abstraction of an atom,
although in some discharges low-molecular-
weight radical species such as CF3 ' may be
prevalent.
The energies required for free radical for-
mation lie well within the electron volt
ranges normally encountered in glow dis-
charges. For simple radicals, the collision
efficiency is close to unity, i.e. nearly every
collision will result in recombination.
PHYSICAL AND ELECTRICAL
CHARACTERISTICS
The voltage applied to the electrodes for the
glow discharge may be either DC or radio-
frequency (RF) or sometimes even microwave
frequency. Since plasma deposition usually
requires RF voltage, the characteristics of
such plasmas will be described. There are
two routes by which electrons, ions, neutral
molecules, neutral fragments and free radicals
may leave the plasma: first by diffusion out of
the plasma, or second because of additional
velocity imparted to them either by impact
with other particles or by the applied RF
field. Since an electron is much smaller than
the ions in the plasma, it will be accelerated
to a greater extent and thus has a much
higher effective temperature than the
molecules and ions.
The important potentials in the RF glow dis-
charge systems are the potential of the glow
region (the plasma potential), the potential
assumed by a surface within the plasma that
is not externally biased or grounded and thus
draws no net current (the floating potential)
and the potential of the powered or externally
biased electrode. When the plasma contacts a
surface, even if that surface is grounded, the
surface is usually at a negative potential with
respect to the plasma. Therefore, positive ion
bombardment occurs, the energy of which
depends on the varying potential throughout
the plasma. The energy is determined by the
potential difference between the plasma and
the surface the ion strikes, the RF frequency
and the gas pressure. The RF frequency
influences the energy because of mobility
considerations of the electron and the gas
pressure due to collisions.
The cause for the different potentials
throughout the plasma becomes clearer when
one considers the electron and ion mobilities.
Consider applying an RF field within a low
pressure gas. On the first half-cycle of the
field, one electrode is negative and attracts
positive ions, the other is positive and attracts
electrons. Since the mobility of electrons is
greater than that of positive ions, the flux (cur-
rent) of electrons is much larger than that of
positive ions. This situation causes a depletion
of electrons in the plasma and results in a
positive plasma potential.
On the second half-cycle, a large flux of elec-
trons flows to the electrode that previously
had received the small flux of ions. In most
RF discharges no direct current can be
passed and, thus, on each subsequent half-
cycle, a negative charge continues to build
on the electrodes and on other surfaces in con-
tact with the plasma. Consequently, electrons
are repelled and positive ions are attracted to
the surface. This transient situation ceases
when a sufficient negative bias is achieved
on the electrodes such that the fluxes of
electrons and positive ions striking these
surfaces are equal. At this point, time-average
(positive) plasma and (negative) electrode
potentials are established.
Between the glow and the electrode (and
other surfaces in the plasma chamber) is a
narrow region, its size depending on pressure,
power and frequency, where a change from
the plasma potential to the electrode potential
occurs. This region is called a sheath or dark
space and is where most of the voltage drop
across the plasma-electrode interface occurs.
Positive ions within the plasma drift to the
sheath edge where they encounter the strong
field. The ions are then accelerated across the
potential drop and strike the electrode or
substrate surface (Figure 23.3).
 Plasma characterization 583
Cathode
Layer(s) Negative Anode
Glow Glow
(a) Positive
/ Column

( 11/ ~
\. u ~~ \
\ Faraday
Aston \ Anode
Cathode Region
(Crooke Hittorf)
Dark
Spaces:

~/
I
(b) Luminous
Intensity V
1\

~
V
(c) Potential
de

Ej
(d) Field
"'-
~
(e) Space- r-
charge
"\
Density
""'\
\../'n F+t
(f) Current
Density
ex r
t

Figure 23.3 Regions in a glow discharge plasma. (Boenig, H.V., Fundamentals of Plasma Chemistry and
Technology, 1988. Reproduced by permission of Technomic Publishing Company, Inc., Lancaster, PA.)

CHEMICAL CHARACTERISTICS etching, the creation of these products is

The overall process of deposition via PECVD
can be broken down into six primary steps:
1. generation of reactive species;
2. transport of the reactive species to the
surface;
3. adsorption;
4. reaction;
5. desorption of volatile products;
6. transport of volatile products away from
the surface.
While the consideration of volatile products
seems more important for processes such as
extremely important for deposition processes
as welL Secondary (e.g. hydrogen, halide or
carbide species) must react to form volatile
products which can desorb to avoid incor-
poration into, and thus contamination of, the
growing film. Also, the low temperatures of
both the gas and the substrate reduce the
mobility of species that impinge on the
substrate surface. Hence, plasma-deposited
layers are usually amorphous and contain
higher percentages of extraneous reaction
components compared to the same material
deposited by high temperature CVD.
584 Plasma-enhanced chemical vapor deposition
The chemical reactions of a glow discharge
are extremely complex and, as a result,
modeling of these processes is limited (Rhee
and Szekely, 1986; Yoo and Dixon, 1989; Sato
et al., 1992). Further understanding and char-
acterization of the plasma deposition process
can be gained, however, by categorizing the
reactions into two general types: homoge-
neous gas phase collisions and heterogeneous
surface interactions.
Homogeneous gas phase collisions generate
reactive free radicals, metastable species and
ions. As already noted, chemical dissociation
and ionization are therefore independent of
the thermodynamic temperature. Electron
impact can result in a number of different
reactions depending upon the electron
energy. The following reactions are listed in
order of increasing energy requirements,
where the notation '*' denotes an electronic
excited state:
1. excitation (rotational, vibrational or elec-
tronic)
e- +X2 ----> Xi +e-
2. heterolytic dissociation
e- + X2 ----> x- + X+ + e-
3. homolytic dissociation
e- +X2 ----> 2X' +e-
4. ionization
e- +X2 ----> xi +2e-
5. dissociative ionization
e- +X2 ----> X+ +X' +2e-
Excitation and dissociation processes can
occur with mean electron energies below a
few electron volts. Thus, the discharge is
extremely effective in producing large quan-
tities of free radicals.
The heterogeneous processes of interest
that can occur at solid surfaces exposed to a
glow discharge are summarized below.
These interactions result from the bombard-
ment of surfaces by particles.
1. Ion-surface interactions:
(a) neutralization and secondary electron
emission;
(b) sputtering;
(c) ion-induced chemistry.
2. electron-surface interactions:
(a) secondary electron emission;
(b) electron-induced chemistry.
3. radical- or atom-surface interactions:
(a) surface etching;
(b) film deposition.
The formation of the coating is likely to take
place on the substrate and on the film surface
by adsorption of radicals, reaction with neigh-
boring atoms on the surface and chemical
reaction to deposit a film with desorption of
volatile by-products. The alteration and
enhancement of film properties due to particle
bombardment can be understood by referring
to the process steps 3 to 5 listed previously.
These are heterogeneous processes whose
kinetics are temperature dependent. Tempera-
ture, however, is only one method of increas-
(23.1 ) ing the surface energy. Particle bombardment
can break surface bonds which cannot only
create adsorption sites, but can also assist
(23.2) in product desorption. Further chemical
reactions at the surface can be promoted by
the bombardment.
(23.3)
EFFECT OF PLASMA PROCESS PARAMETERS
(23.4) ON FILM PROPERTIES
Although desirable for producing films with
specified and reproducible properties, a fun-
(23.5)
damental understanding of the complex
chemical and physical processes occurring in
PECVD is not yet established. A representa-
tion of these interactions is given in Figure
23.4. Although more specific descriptions of
the effect of these processes on particular
films will be presented, a few general points
will be presented here.
Control of the basic or microscopic plasma
parameters (neutral-species, ion and electron
densities; electron energy distribution; and
 Effect of plasma process parameters on film properties 585
Kinetics Parameters Electrical Parameters
-Gas Flow -Power
-Nature of Gas -Frequency
-Pumping Speed -Geometrical Factors

Basic Plasma Parameters

-Electron Ion Densities and Fluxes
-Neutral Density
-Residence

Growth Kinetics
Ion Energy

Nature of
Chemical Species

and Mechanism

Surface Parameters
-Nature of Surface
-Material
-Surface Potential

Figure 23.4 Interaction of homogeneous and heterogeneous plasma processes that determine film
properties. (Hess, D. and Graves, D., 'Plasma-enhanced etching and deposition,' in Microelectronics
Processing: Chemical Engineering Aspects. Advances in Chemistry Series 221 (eds. D.W. Hess and
K.F. Jensen), pp. 377-440, 1989. Reproduced by permission of the American Chemical Society,
Washington, DC.)

residence time) would allow for control of
the gas phase chemistry. Many of the macro-
scopic plasma variables (gas flow, discharge
gas, pumping speed, RF power, frequency
etc.) can be changed to alter the basic
plasma conditions. However, the precise
manner in which a change in anyone of
these variables affects basic plasma par-
ameters is unknown.
Variations in a macroscopic variable usually
result in a change in two or more basic gas
phase parameters as well as surface potential,
particle flux and surface temperature. For
instance, RF power determines the current
and voltage between the electrodes in a
parallel-plate plasma reactor. Varying the
frequency changes the number and energy of
ions that can follow the alternating field.
The temperature dependence of deposition
rate for most ceramic materials follows an
Arrhenius rate expression, when feed-rate
and transport-rate limitations are not impor-
tant (Kodas and Hampden-Smith, 1994). As a
result, the temperature of the reactant gases
and the surface temperature are critical pro-
cess parameters. The configuration of the
glow discharge (DC, DC pulsed, RF, micro-
wave), the gas inlet and distribution system
affect not only deposition rates of films, but
also the ultimate properties of the film itself
such as compositional homogeneity, density
and microhardness.
586 Plasma-enhanced chemical vapor deposition
The pressure can also influence the deposi-
tion process and in a steady-state flow system
is determined by:
rate of gas feed into the reactor;
rate at which the gaseous products from the
reaction are removed;
rate of adsorption by surfaces within the
reactor;
rate and extent of fragmentation of species
in the gas phase;
rate of transport from surfaces including the
growing film.
Pressure effects are easily understood for a
system in which there is a single source of
gas or monomer and the object is to polymer-
ize the monomer at the surface. However, for
production of ceramic materials such as TiN,
Si3N 4, AlN, TiC etc., the process requires a
number of reactive species. Therefore, the
pressure of the system is a function of
the numerous reactions occurring between
the process gases in the plasma and the sur-
face reactions. However, for the case of most
ceramic materials, the effects of gas flow rate
and the ratio of flow rates of the reactive
species are more important.
FILM DEPOSITION
Thin films of ceramic materials can be produced
by CVD, molecular beam epitaxy and ion beam/
sputter techniques. However, the high temp-
eratures in CVD and the high energy surface
bombardment in ion beam/sputter techniques
can make these approaches inappropriate for
material-sensitive applications. The use of
PECVD offers a low temperature route
compared to conventional CVD, though the
substrate is still bombarded by high energy
particles. Remote PECVD can be used for
applications where this bombardment is of
concern. In this case, the substrate is removed
from the plasma and placed downstream
where reactions with activated species occur.
The low temperatures of the gas and the
substrate in PECVD processes reduce the
mobility of the reactants impinging the sub-
strate surface. Therefore PECVD layers are
often amorphous and often contain higher
concentrations of extraneous reaction com-
ponents than would be expected from high
temperature CVD. The next sections discuss
some specific examples of the deposition
of nitride and carbide films by PECVD
techniques.
NITRIDES
Aluminum nitride (AIN)
Aluminum nitride has a wurtzite structure,
a coefficient of thermal expansion (AlN
a = 3.5 x 10-6 jK at room temperature) near
that of Si (Mohammed and Corbett, 1985), a
thermal conductivity of k = 319W /m K
(theoretical at room temperature) (Slack
et al., 1987), an electrical resistivity of
p > 1013 ohm. cm (at room temperature) and
a low dielectric constant, K' = 8.9 (at 1 MHz
and room temperature) (Mohammed and
Corbett, 1985). Applications include protec-
tive coatings and substrates for integrated
circuit chips.
The earliest work on PECVD of aluminum
nitride films utilized halides such as AlBr3 as
aluminum sources. Work with the AlBrrNz-
Hz-Ar system showed that AlN films with
highly preferred (001) orientation could be
obtained at a total pressure of 2 kPa (15 torr)
(Itoh, Kato and Sugiyama, 1987). Graphite
substrate temperatures above 773 K (500C)
were required to obtain single-phase AlN
without NH4Br contamination. Similar results
were obtained by later researchers using the
AlBr3-Hz-Nz system. The growth rate and c-
axis orientation were dependent on tempera-
ture with the best orientation factor occurring
at a temperature of 823 K (550C) (Someno,
Makoto and Hirai, 1987). Further, the micro-
wave plasma technique produced smoother
films at lower temperatures (823 K (550C) vs
973 K (700C than RF-based techniques
using AlBr3 sources. Another advantage for
 Film deposition 587
Table 23.1 Crystallinity and preparation methods of AlN films

Method Gas system Pressure Tsub Deposition rate Crystallinity

(Pa) (K) (nmjmin) of films

RF plasma CVIY AlBr3-Hr Nr Ar 1330-5300 973 330 (001) preferred

orientationC
RF plasma CVDb TMA-H2-N2-NH3 133-266 573 200 Amorphous d
Reactive sputteringb Al target, N2 13-2665 673 10 (001) preferred
orientation
RF plasma CVDb TMA-NH3 13 1123 Epitaxial
Microwave plasma AIBrrH2-N2 180 823 60 (001) preferred
CVDb orientation
a Itoh, Kato and Sugiyama (1987).
b Sameno, Makato and Hirai (1990).
C Graphite substrate.

d (100) silicon wafer.

the microwave-based system is the excellent crystallinity and preferred orientation. In

crystallinity obtained compared to techniques
such as RF plasmas and reactive sputtering
(Table 23.1).
Alternatives to halide precursors that have
been used are trimethylaluminum (TMA) and
triisobutylaluminum (TIBA). The AlN films
were deposited using a parallel plate electrode
RF plasma unit with TMA, NH3 and H2 or N2
carrier gases (Hasegawa et al., 1987). In con-
trast to the AlBr3 studies, the films deposited
from TMA were amorphous rather than crys-
talline. Consistent with the AlBr3 results was
the requirement of a hydrogen source such as
H2 or NH3 (David, Babu and Rasmussen,
1990). This suggests that an abundance of
(NH x ) species is required for deposition of
AlN. It was proposed that this was the result
of the higher dissociation energy of N2
compared to (NH x ) species (David, Babu and
Rasmussen, 1990). Hence, in a nitrogen
plasma, the concentration of (NH x ) species
is likely to be significantly lower than in
ammonia- or hydrogen-based plasmas. The
better quality of films obtained with H2 com-
pared with N2 (Hasegawa et al., 1987) as the
carrier gas is consistent with this idea.
Excitation frequency also plays a significant
role, not only in the depOSition rate of AlN
films, but also in film characteristics such as
investigating the effects of substrate material
and excitation frequency, AlN could be depos-
ited from TMA-NH3 at 603 K (330 C) on a
variety of substrates (Azema et al., 1991). The
deposition rate decreased with increasing
excitation frequency (Figure 23.5). The crys-
tallinity of the films also varied with both
temperature and frequency, with lower tem-
peratures and lower frequencies favoring
amorphous films and higher frequencies and
higher temperatures favoring crystalline
phases.
Remote plasma-enhanced CVD (RPECVD)
is a process that can be utilized for situations
where substrate damage due to ionic particle
showering is a concern. In RPECVD, the
substrate is removed from the plasma so that
surface damage is absent. The radicals formed
in the plasma, however, are still able to par-
ticipate in the reactions.
Utilizing RPECVD with a microwave
system and TMA (Figure 23.6), AlN films
could be deposited, but they suffered from
carbon contamination (Matsumoto et al.,
1992). Attributing this contamination to the
high reactivity of methyl groups in TMA,
TIBA was investigated as an alternative.
Since the radicals derived from the isobutyl
groups of TIBA are more stable and more
588 Plasma-enhanced chemical vapor deposition
2.5 r - - - - - - - - - - - - - - - - - - - - ' - - - ,

2.0
35kHz

-5
::i.
'-"
1.5 440kHz
III
~ 1.0
c:
~

:aEo-<
c.J

0.5

20 40 60 80 100 120 140

Time (min)
Figure 23.5 Deposition kinetics for various frequencies. (Azema, N., Durand, J., Berjoan, R, Balladore, J.L.
and Cot, L., 'Influence of excitation frequency on oriented (l00) growth of aluminum nitride thin films by
PECVD,' J. Physique IV, 1, C2405-12, 1991. Reproduced by permission from Editions de Physique,
Cedex, France.)

easily formed (due to the higher degree of
substitution of the carbon-bearing radical)
than the methyl groups, the researchers
hoped that use of TIBA would reduce the
carbon contamination. Furthermore, it is
well known that isobutyl radicals rearrange
to form isobutylene and H radical, although
,8-methyl migration can complicate this
process. Auger electron spectroscopy (AES)
analysis of the films, however, indicated
several percent carbon in the deposited AlN
films. While carbon incorporation is detri-
mental in electronic device applications, for
coating applications, the process affords an
alternative route for low temperature deposi-
tion of AlN films.
The lowest temperature at which deposition
of AlN films occurred was at 523 K (250 DC)
using TMA-NH3 with an RF plasma discharge.
The deposition rate at this temperature, how-
ever, was only 4nm/min (David, Babu and
Rasmussen, 1990). The highest deposition
rate, 500 nml min, was achieved at a higher
temperature of 973 K (700 DC) using an RF
plasma source with AlBrr H 2-N2 (Itoh, Kato
and Sugiyama, 1987). An intermediate deposi-
tion rate of 28 nm/min was achieved at 603K
(330 DC) using an RF plasma at 35 kHz with
TMA-NH3 (Azema et al., 1991). A list of
relevant references on PECVD is given in
Table 23.2. It includes precursors used,
temperatures, plasma type and parameters
investigated.
Comparison of PECVD with conventional
CVD of AIN shows that deposition rates for
PECVD are generally lower than for CVD.
Although deposition rates of 3000nm/min
have been achieved with conventional CVD
(Lee, Lackey and Agrawal, 1991), the
maximum deposition rates achieved with
PECVD are only 500nm/min. However, the
substrate temperature in PECVD experiments
 Film deposition 589
MFC MFC PG

Substrate
TIBA
Ar Bubbler

Heater

VVaveguide ~
,
I

Thermo-
with couple
Microwave

~
Generator Pyrex Glass Tube
Pump
--------- 57cm --------

Figure 23.6 Microwave RPECVD apparatus for AlN deposition. (Matsumoto, K., Meikle, S., Nakanishi, T.
and Hatanaka, Y., 'Deposition of aluminum nitride by remote plasma enhanced chemical vapor deposition
using triisobutyl aluminum,' Jap. J. Appl. Phys., 31, 1423-25, 1992. Reproduced with permission.)

is significantly lower (923 K (650C) vs 1273 K
(1000C than those used in CVD. The
crystallinity of deposits formed with PECVD
compares well with that of CVD. Aluminum
nitride (AlN) deposited from a microwave
plasma shows preferred (001) orientation at
low temperatures of 823 K (550C) compared
with the 1073 K (800 DC) required for CVD.
Films deposited via CVD at 973 K (700 DC) to
1073 K (800 DC) flaked and cracked as soon as
they were removed from the CVD furnace
(Lee, Lackey and Agrawal, 1991).
Boron nitride (BN)
Cubic boron nitride (cBN) has almost the same
hardness and thermal conductivity (6.27W /
m . K and 1.0 W / m . K, respectively, in a,
band c directions) as diamond. Although
boron nitride commonly crystallizes in a hex-
agonal form (hBN) it transforms into a wurt-
zite (wBN) or cubic structure (cBN) under
conditions of high temperature and pressure.
Recent successes in synthesizing films of cBN
have created opportunities for its use not only
as a hard coating, but as a semiconductor
device material as well. Boron nitride has sev-
eral other applications as crucible materials,
electrical insulators, heat shields, high tem-
perature capacitors, furnace components, opti-
cal windows at 5.5 mm, 12 mm and 15 mm
where it can be used as an IR polarizer, and
in microwave applications.
Boron nitride prepared by CVD exhibits
increasing anisotropy as the deposition tem-
perature is increased. The hexagonal planes
of BN become preferentially oriented parallel
to the deposition surface. This highly aniso-
tropic material called pyrolytic BN is obtained
at temperatures of 2173 K (1900 DC) from the
BClr NH3 reagent system.
The crystallinity of PECVD boron nitride dif-
fers significantly from pyrolytic CVD material.
Whereas CVD films are analogous to highly
oriented pyrolytic graphite, PECVD produces
cBN films analogous to the diamond structure.
The first experimental work on PECVD of cBN
was performed using a reactive pulsed plasma
590 Plasma-enhanced chemical vapor deposition
Table 23.2 Experimental conditions and variables studied for AlN films

Method Gas system Pressure Tsub Parameters Reference

(Pa) (K)
RF plasma AlBr3-H2- <1330-5320 473-1073 Reaction time; pressure; Itoh, Kato and
N2-Ar temperature; gas velocity; Sugiyama
AlBr3 concentration; (1987)
graphite substrate
Microwave AlBrr H2-N2 180 693-883 Deposition rate; orientation; Someno, Makato
plasma crystallinity; (100) Si and Hirai
substrate (1990)
RFplasma TMA-H2- 133-266 573 Power; TMA supply; NH3 Hasegawa et al.
N2-NH3 flow rate; RF power; film (1987)
characteristics; quartz
substrate
RF plasma TMA-NHr 39 523 NH3/TMA ratio; film David, Babu and
N2 properties; temperature; Rasmussen
(100) silicon single crystal (1990)
RF plasma TMA-NH3- 6 603 RF frequency; substrate Azema et al.
N2 (100) Si, graphite, (1991)
polycrystalline SiC and
glass); film properties;
deposition rate;
crystallinity
Remote RF TMA-NH3- 10.3-39 773 Plasma characterization; Nomura et al.
plasma N2 carbon contamination; (1991)
N2:H2 silicon and quartz
substrates
Remote RF TMA-N2 39 473--673 Plasma reactions; film Meikle et al.
plasma characteristics; silicon (1990)
and quartz substrates
Remote TIBA-N2-Ar 573-773 Plasma characteristics; Matsumoto et al.
microwave carbon impurities; film (1992)
plasma characteristics; silicon
and quartz substrates

crystallization method in a special reactor deposition rate. By applying a magnetic field

(Sokolowski, 1979). Since this pioneering
work, there have been various attempts to
deposit cBN from vapor by both CVD and
physical vapor deposition (PVD) methods.
However, in many of these cases, the films
obtained have contained mixtures of cBN and
hexagonal or wurtzite phases (Ikeda, Kawate
and Hirai, 1990). These types of multiphase
films have also been deposited using PECVD
techniques (Komatsu et al., 1991a,b).
Early work on the deposition of BN investi-
gated the effects of a magnetic field on the
to a parallel plate RF plasma discharge, the
deposition rate could be affected significantly.
Using B2 H 6, NH3 and H 2, the deposition rate
was greater with the applied magnetic field at
pressures below 55Pa (400mtorr), while at
pressures above this value the deposition
rate was higher without magnetic field
enhancement (Figure 23.7). These results
were explained by noting that at lower pres-
sures there was a decrease in electron mobility
leading to an increase in electron density
(Yuzuriha, Mlynko and Hess, 1985).

3.0
2.5
C the deposition of boron nitride films, Maya
'E
E 2.0
.s
~ films at significantly lower temperatures than
a: 1.5
c:
0
:;:::>
'iii 1.0
0
C.
Ql
0 o Without Magnet
0.5 With Magnet
0
600 800
Pressure (mtorr)
Figure 23.7 Boron nitride deposition rate as a func-
tion of total pressure. (Yuzuriha, T.H., Mlynko,
W.E. and Hess, D.W., 'Magnetic field effects in the
plasma enhanced chemical vapor deposition of
boron nitride,' J. Vac. Sci. Technol., A3(6), 2135-40,
1985. Reproduced by permission of the
American Institute of Physics, Woodbury, NY.)
Related work on improving PECVD of cBN
focused on means of exciting the deposition
surface with laser irradiation (Komatsu et al.,
1991a,b). The PECVD of cBN films from
BCI3 + NH3 + H2 + Ar using an RF plasma
along with UV laser irradiation produced
multiphase films of boron nitride. These
films were composed of three phases: (1) a
thin film of 10 nm crystallites; (2) polycrystal-
line phases with cBN or wBN structure
embedded in the thin film layer; and (3) crys-
tallites grown much larger than the thin film
thickness. Later, work by the same researchers
focused on producing crystallites of cBN
(Komatsu et al., 1991b).
Films of BN were deposited and character-
ized in an alternative system using a micro-
wave plasma with solid NaBH4 and NH3
and H2 gases as reagents. The ratio of cBN
to hBN or wBN was dependent on the total
pressure used. Although the film deposited
at 8 kPa (60 torr) had a Raman spectrum that
indicated the presence of cBN, no x-ray
Film deposition 591
diffraction pattern was observed (Saitoh and
Yarbrough,1991).
In examining lower temperature routes for
(1992) used polymeric cyanoborane (CNBHz)n
as a boron source. The PECVD route produced
the thermal CVD route (573 K (300C) as
compared to 1273 K (1000C. The deposition
rate of 1.5 /-lm/h was significantly higher
than the 0.18 /-lm/h achieved with a microwave
plasma, yet considerably less than the 21 /-lm/h
achieved with thermal CVD at 1273 K (1000 DC)
(Lee, Lackey and Agrawal, 1991). In contrast to
the above studies, the films produced in this
work were hexagonal graphitic BN. However,
the films also contained up to 20 wt% poly-
meric cyanogen as a contaminant.
In discussing the PECVD of BN, attention
should be drawn to the work of Komatsu and
co-workers on the PECVD of boron. This work
provides a thorough investigation of the
mechanisms, kinetics and morphology of
PECVD boron. Since many of the plasma and
surface reactions that occur in deposition of
BN are similar to those that occur in boron
deposition, this reference provides a useful
source of further information for BN (Komatsu
and Moriyoshi, 1988a,b, 1989a,b, 1990).
In summary, the PECVD of boron nitride
films is primarily concerned with producing
cBN films. However, to date most of the
films produced have been multiphase films
with hBN and wBN as contaminants.
Silicon nitride (Si 3 N 4 )
Silicon nitride is used for wear-resistant and
anti-corrosive coatings due to its relatively
high hardness and its chemical and oxidation
resistance. Both amorphous and crystalline
films have been prepared by CVD. Silicon
nitride (Si3N 4) can be deposited from a
wide variety of precursors including SiCI4,
SiF4, SiH2CI2 and SiH4 (Kingon, Lutz and
Davis, 1983; Lee, Strife and Veltri, 1992).
Ammonia (NH3) is the most widely used
592 Plasma-enhanced chemical vapor deposition
nitrogen-containing precursor, although
N2H4 and N2 have been used. The CVD of
crystalline a-Si3N 4 has been achieved at tem-
peratures above rv 1573 K (1300C) using
SiClc NH 3 and SiFcNH3 precursor mixtures.
Silicon nitride has also been deposited via
CVD at lower temperatures (1273 K to
1973 K; 1000C to 1700C) using SiHc NH 3,
SiClc NH 3 and SiFcNH3.
The high temperatures required by CVD
(2::873 K; 2::600C) cause interactions of the
Si3N4 with components of the metal substrate,
often resulting in formation of silicides.
Hence, PECVD has been explored to enable
deposition of coatings below 1273 K
(1000C). Despite its potential significance as
an industrial material, there have been few
papers presented on plasma CVD of silicon
nitride that are concerned with the mechanical
properties of the films.
In integrated circuit technology, insulating
films of silicon nitride are used in many
ways. These films exhibit wide ranges of elec-
trical, optical and mechanical properties such
as band gap, refractive index and dielectric
constant, depending on the chemical composi-
tion and method of preparation. Because of
the growing interest in thin film dielectrics
deposited at low temperatures (200-500C),
PECVD of Si3N4 has gained increasing impor-
tance in microelectronic applications. While
not unrelated to the mechanical properties, a
discussion of the optical and electrical proper-
ties of PECVD films is not within the scope of
this chapter. For a review of the preparation
and characterization of Si3N4 films for
integrated circuit applications, the reader is
referred to Gupta et al. (1991).
Studies of mechanical properties of PECVD
Si3N4 have concentrated primarily on the
micro hardness, internal stress and adhesion
characteristics. The micro hardness of PECVD
Si3N4 is comparable to, or even slightly super-
ior to, values obtained using a conventional
CVD process (Endler et al., 1991; Moriyama,
Kamata and Tanabe, 1991). The principal
factor affecting the hardness of Si3N4 coatings
appears to be the NISi ratio in the film. This
can be understood by noting that the crystal
structure of Si3N4 consists of an SiN4 tetra-
hedron shared by three other SiN4 tetrahedra
forming a three-dimensional network. The
Si-N bond, formed by overlapping Sp3 orbi-
tals of Si and Sp2 orbitals of nitrogen is further
stabilized by additional 1r-bonding from the
nitrogen lone pair into an empty silicon 3d
orbital providing some partial multiple bond-
ing character. This exceptionally strong bond
creates a very rigid structure (Taylor, 1991). It
is not surprising that a defect in the structure
such as Si-H bonds would affect the rigidity
and hardness. Hence, as the NISi ratio
approaches the stoichiometric value, the
hardness of the films increases with maxi-
mum hardness occurring at stoichiometric
ratios (Figure 23.8) (Moriyama, Kamata and
Tanabe, 1991; Taylor, 1991).
The internal stress of the films is also a func-
tion of the N lSi ratio. This stress, sometimes
reported as total stress, varies from increas-
ingly compressive with increasing hydrogen
incorporation to increasingly tensile with
increasing amounts of N-Si bonding (Figure
23.9) (Endler et al., 1991; Lee, Sooriakumar
and Dange, 1991; Moriyama, Kamata and
Tanabe, 1991). Compared to the stress induced
by pyrolytic CVD, the stress in PECVD films is
considerably lower (about three times).
Factors such as the NISi ratio and the
hydrogen content of Si3N4 films are critical
to the mechanical properties of these coatings.
However, the effects of various process par-
ameters of PECVD such as RF power, gas
flow rates, frequency, reactor design and feed-
stock have received little attention. In contrast,
the relationships between the electrical and
optical properties of Si3N4 films and the
plasma environment have received much
more attention (Petrich, 1989; Gupta et al.,
1991; Landheer et al., 1991; Lee, Sooriakumar
and Dange, 1991). There is therefore a need
for a systematic evaluation of the effects of
the plasma variables on such properties as
microhardness, internal stress and adhesion.

30 r - - - - - - r - - - - - , - - - - - - , - - - - - - ,
'2
c.. 20
S ~
o L-_ _ --L._ _ _--'--_ _ _. l . -_ _----'
o 0.5 1.0 1.5 2.0
Atomic ratio of N/Si or C/Si
Figure 23.8 Vickers micro hardness vs atomic ratio
of NISi for plasma CVD SiNx and SiCy . (Moriyama,
M., Kamata, K. and Tanabe, 1., 'Mechanical proper-
ties of SiNxC y ceramic films prepared by plasma
CVD,' J. Mater. Sci., 26, 1287-94, 1991. Repro-
duced by permission of Chapman & Hall,
London, UK.)
Titanium nitride (TiN)
One of the most widely used ceramic coatings
for improving the wear resistance and per-
formance of materials is titanium nitride
(TiN). Although conventional CVD using
TiCl4 , H2 and N2 provides excellent unifor-
mity, it requires a deposition temperature of
about 1273 K (1000 C). Since this high tempera-
ture would anneal high speed steel and, thus,
destroy its hardness, the use of CVD for
deposition of TiN is mostly confined to cemen-
ted carbide materials. While physical vapor
deposition (PVD) offers a lower-temperature
route, rotation of the workpieces is required
in order to obtain uniform coatings. PECVD
offers a combination of both CVD and PVD
techniques in that lower temperatures are
achievable and good uniform coverage can be
obtained.
Film deposition 593
2000
"
Jt
~
.~ t
~
b 0-
S -2000
C/l 0
u
~
"
1;;
S0 -4000
E-
-6000 oL---,:-':---....",..,,---.,-',:-----,,....,.--'
Atomic ratio of N/Si or C/Si
Figure 23.9 Total stress vs atomic ratio for plasma
CVD of SiN x and SiCy . (Moriyama, M., Kamata, K.
and Tanabe, 1., 'Mechanical properties of SiNxC y
ceramic films prepared by plasma CVD,' J. Mater.
Sci., 26, 1287-94, 1991. Reproduced by permis-
sion of Chapman & Hall, London, UK.)
Early work on PECVD of TiN focused on
demonstrating the ability of the process to
produce TiN films at lower temperatures
than CVD, while retaining the hardness,
color and adhesion properties of CVD films
(Konuma, Kanzaki and Matsumoto, 1980;
Archer, 1981). In investigating the deposition
of both TiC and TiN using a DC plasma,
Archer (1981) found that TiN could be depos-
ited at temperatures as low as 673 K (400C),
with properties similar to those obtained by
conventional CVD processes. Shizhi et al.
(1984) were some of the first to study the
effects of various process parameters on the
deposition rate, morphology and film proper-
ties of PECVD TiN. In addition to noting the
linear relationship between the TiCl4 content
of the feedstock and the deposition rate, gas
pressure played a significant role in the
microstructure of the deposited films. Films
deposited at 133.3 Pa (1 torr) were smooth
and pinhole free and the deposition rate
was high (8 JIm/h), while at a pressure of
33 Pa (0.25 torr) the deposition rate was low
(3 JIm/h) and the film contained many
nodules and pinholes. These early studies
utilized both DC CArcher, 1981; Shizhi et al.,
594 Plasma-enhanced chemical vapor deposition
1984) and RF plasma sources (Konuma, 3000
Kanzaki and Matsumoto, 1980).
With regard to precursors and plasma gases,
the majority of earlier work and present-day
research has focused on use of the TiClc N 2-
-
0
0
2000 0

>
H2 system. Ammonia (NH3) has been used as ::r:
an alternative to N2 and H2 as the plasma gas 1000
(Hilton et al., 1986, 1987; Hilton, Salmeron and
Somorjai, 1988). However, the adhesion of TiN
films deposited with Nz-H 2 systems was o 40
much better. Although the adhesion proper-
ties are inferior, the deposition rate using Cl Content (wt%)
NH3 is higher than that using Nz-H 2 (Hilton
Figure 23.10 Vickers microhardness of TiN coat-
et al., 1987). An alternative that has yet to be ings as a function of CI content. (Arai, T., Fujita,
studied is a sequential deposition that utilizes H. and Oguri, K., 'Plasma assisted chemical vapor
an N2-H2 system to deposit an adherent layer, deposition of TiN and TiC on steel: properties of
followed by an NH3 system for increased coatings,' Thin Solid Films, 165, 148-49, 1988.
growth rate (Hilton, Salmeron and Somorjai, Reprinted with kind permission from Elsevier
1988). Science SA, Lausanne, Switzerland.)
One of the concerns with using TiC4 as a
reactant is the incorporation of chlorine into TiC14 and NH2 reveals the cause of this
the TiN film. In investigating the effect of chlor- behavior. Reactions 23.6-23.8 are the main
ine on PECVD of TiN, it was proposed that reactions of interest in the deposition, with
chlorine atoms produce lattice defects in TiN, similar behavior shown by the N 2-H2
thereby deteriorating crystallinity (Jang, Chun systems. Reaction 23.6 is favored at low
and Kim, 1989). Hence an increase in chlorine
content will produce strain in the deposited
layers. Support for this view is derived from Temperature CC)
measurements of Vickers microhardness of 400 450 500 550 600
30~----~----~r---~~----~
PECVD-deposited TiN films from a DC
plasma which varied as a function of the chlor-
ine content (Figure 23.10, Arai, Fujita and Oguri, ;9:
1988). The Vickers microhardness decreased 20
~
from Hv = 19.6GPa (2.8 x 106 psi), 0.01 kg at a C
!!
chlorine content of <5 wt% to a low of only d
u0 10
Hv = 2.9GPa (4.2 x 105 psi), 0.01 kg at 30wt% 0
chlorine. (The first number in the hardness
notation is the hardness measured using the
O~ ____~____~____~____~
load indicated in the second number.) 673 723 773 823 873
The major factor affecting the chlorine Temperature (K)
content in the deposited film is the deposition
temperature. As shown in Figure 23.11 the Figure 23.11 Chlorine content in TiN Films as a
chlorine content of the film is inversely related function of temperature. (Arai, T., Fujita, H. and
Oguri, K., 'Plasma assisted chemical vapor deposi-
to the substrate deposition temperature tion of TiN and TiC on steel: properties of coatings,'
(Hilton et al., 1986, 1987; Sanders and Verspui, Thin Solid Films, 165, 148-49, 1988. Reprinted
1988; Jang, Chun and Kim, 1989). Examination with kind permission from Elsevier Science SA,
of the thermodynamics for deposition from Lausanne, Switzerland.)

temperatures and produces a solid NH4Cl
product. As the temperature is increased the
equilibrium shifts toward reactions 23.7 and
23.8 where the gaseous HCl product is favored
(Hilton et al., 1986):
TiCl4 + 6NH3 ---. TiN + 4NH4Cl
+H2 +!N2 (23.6)
TiCl4 + 2NH3 ---. TiN + 4HCl
+H2 +!N2 (23.7)
TiCl4 + 6NH3 ---. TiN + 4HCl
+7H2 +~N2 (23.8)
This explanation is consistent with the
decrease of deposition rate with increasing
temperature as shown in Figure 23.12 (Shizhi
et al., 1984; Jang, Chun and Kim, 1988; Sanders
and Verspui, 1988). As the HCl content in the
gas increases, film growth becomes a function
Deposition Temperature eC)
400
200 300
1.5
Steel
OWC-Co
o 473 673
Deposition Temperature (K)
Figure 23.12 Dependence of deposition rate on
deposition temperature. (Jang, D.H., Chun, J. and
Kim, J.G., 'The deposition rate and properties of
the deposit in plasma enhanced chemical vapor
deposition of TiN: J. Vac. Sci. Technol., A7(1), 31-
35, 1989. Reproduced by permission of the
American Institute of Physics, Woodbury, NY.)
Film deposition 595
of a competitive erosion and deposition
mechanism with the chlorine atoms playing
a role in the erosion process (Shizhi, 1984).
A further consideration with the use of
TiCl4 is the corrosion problems inherent with
TiCl4 itself. Thus, there have been efforts to
find alternative precursors such as organo-
metallic titanium compounds. However, the
choice of compounds is restricted mainly to
titanium alkoxides, since these are available
in sufficient quantities at moderate prices
(Mayr and Stock, 1986). By using high partial
pressures of nitrogen and low partial pres-
sures of titanium isopropoxide (Ti(OC 3H 7 )4),
it was possible to deposit Ti(O,C,N) layers at
temperatures between 773 and 973 K (500-
700C) (Mayr and Stock, 1986). The hardness
of the films, however, was less than that of
stoichiometric TiN. In an alternative route,
titanium tetrakis(dimethylamide) was used
to deposit Ti(C,N) films at temperatures
below 673 K (400C). Decomposition of tita-
nium dimethylamide to carbonitride powder
occurred when used with an RF plasma
(Hilton et al., 1987). However, when a pulsed
plasma CVD system was used, adherent films
of TiN could be produced at 553 K (280C),
with growth rates of 1-2J,tm/h (Rie, Wahle
and Gebauer, 1991).
The mechanical properties of PECVD TiN
and related compounds (Ti(C,N), Ti(O,C,N),
Ti-Si-N) are comparable to CVD- or PVD-
deposited films (Arai, Fujita and Oguri, 1988;
Sanders and Verspui, 1988; Jang, Chun and
Kim, 1989; Laimer, St6ri and R6dhammer,
1990; Shizhi, Yulong and Hongrui, 1992). In
general, the hardness of PECVD TiN coatings
increases with increasing temperature and
decreasing chlorine content (Arai, Fujita and
Oguri, 1988; Sanders and Verspui, 1988). The
crystallinity of the films also increases with
increasing temperature and increasing RF
power (Hilton et al., 1986; Sanders and
Verspui, 1988; Jang, Chun and Kim, 1989).
Also of importance, not only in the PECVD
of TiN, but also of other films as well, is
the design of the gas inlet and distribution
596 Plasma-enhanced chemical vapor deposition
systems. The design of the gas distribution
system was of critical importance in determin-
ing the morphology of deposited nitride
layers (Laimer, 1990). In the case of a central
gas inlet system, the deposition coatings
have typically three different zones with
the composition varying radially outward.
Converting the distribution system to a two-
stage gas shower system, as shown in Figure
23.13, improved the uniformity immensely
(Laimer, Stori and Rodhammer, 1990). Related
to effects of the gas distribution system is
the effect of various regions of the plasma
reactor: the cathode, substrates isolated from
cathode and anode, and the anode. The
region where TiN is crystallized chiefly deter-
mines the growth kinetics of the TiN layers
and, to a smaller degree, the morphology
and chemical composition (Michalski and
Wierzchon, 1991).
A collection of recent work on PECVD of
TiN is presented in Table 23.3. For a more
thorough review of earlier work containing
experimental details, Laimer, Stori and
Rodhammer (1990) should be consulted.
Table 23.3 Recent work on PECVD of TiN
Plasma discharge Feed gas
RF
TiCl4-H 2-N 2 /TMTa
TiClc NH 3
DC
TiClc Hz-N2
[Ti(OC 3H 7)4]
TiCl c SiCl4 -H 2 -N2
TMTa /TETa /N2-H 2 -Ar
a TMT = tetrakis(dialkylamido)titanium - THNR214 (R= Me (TMT) or Et (TET.
..............................
"""##"#_#I_":I#".I"''''~
Figure 23.13 Two stage gas shower system for TiN
deposition. (Laimer, J., St6ri, H. and R6dhammer,
P., 'Titanium nitride deposited by plasma assisted
chemical vapor deposition', Thin Solid Films, 191,
77-89, 1990. Reprinted with kind permission
from Elsevier Science SA, Lausanne, Switzerland.)
CARBIDES
Silicon carbide (SiC)
Silicon carbide has excellent strength, heat
stability, electrical properties, wear and corro-
sion resistance. Despite the high strength and
wear resistance of these films, few papers
have dealt with deposition of SiC via
PECVD. In addition to high strength and
Reference
Laimer, St6ri and R6dhammer (1990)
Jang, Chun and Kim (1989)
Konuma, Kanzaki and Matsumoto (1980)
Sanders and Verspui (1988)
Bull et al. (1991)
Laimer, St6ri and R6dhammer (1989)
Hilton, Salmeron and Somorjai (1988)
Hilton et al. (1987)
Hilton et al. (1986)
Archer (1981)
Michalski and Wierzchon (1991)
Arai, Fujita and Oguri (1988)
Shizhi et al. (1984)
Mayr and Stock (1986)
Shizhi, Yulong and Hongrui (1992)
Rie, W6hle and Gebauer (1991)
 Film deposition 597
wear resistance, SiC exhibits exceptional 30r--------------------.
electronic and optical properties. Because of
its high thermal conductivity and good
electrical insulation, it has applications in
l
!.
large scale integrated circuits. When alloyed :t 20
II)
with H as amorphous SiC (a-SiC:H), it makes Q)
II)

c:
an attractive material for use in solar cells, "E
til
photoreceptors and graphic devices because
e
~

the optical gap can be continuously con- 0

~ 10
trolled by changing the composition of the t!!
Q)
alloy. 0
~

Silicon carbide has been prepared by CVD :>

at temperatures exceeding 1473 K (1200 DC),
using SiCl4-C3H s, Si2H 6-C2H 4 and Si2H 6- 0.4 0.6 0.8 2.0
C2H 2 as precursors. At these high tempera- (SiC)
Rx
tures, the substrates are restricted to such
materials as graphite, thermally stable Figure 23.14 Vickers microhardness vs composi-
ceramics and refractory metals. tion for SiNxCy films. (Kamata, K., Aizawa, N.
Work on PECVD of SiC has focused on and Moriyama, M., 'Microhardness and internal
preparation of polycrystalline films and stress of Si3 N c SiC films prepared by plasma
evaluation of the various parameters affecting CVD,' J. Mater. Sci. Lett., 5, lOSS-57, 1986. Repro-
the hardness. Work on a-SiC:H, however, duced by permission of Chapman & Hall, London,
UK.)
has focused on preparation of amorphous
materials and the evaluation of how various
experimental parameters affect the optical Later work (Moriyama, Kamata and Tanabe,
and electrical properties. While the focus of 1991) examined the relationship between
this review is on SiC films, relevant work on microhardness and the C/Si ratio. Films with
the deposition of a-SiC: H films will be dis- stoichiometric ratios of C/Si exhibited maxi-
cussed as well. mum hardness (Figure 23.8). The internal
Although previously discussed under silicon stress varied as a function of C/Si, becoming
nitride, the work of Kamata, Aizawa and Mor- increasingly compressive with decreasing
iyama (1986) examined microhardness, inter- ratio of C/Si (Figure 23.9).
nal stress and the adhesive strength of hybrid The crystal structure of SiC films deposited
films of Si3N4 and SiC. Using SiH4, NH3, CH4 via RF plasma CVD using SiH4, C~ and H2 is
and H 2, films of SiNxCy were deposited onto a function of the C/Si ratio. For the general for-
glass and stainless steel substrates at 673 K mula Si1_xCX/ films are basically amorphous for
(400 DC) (Kamata, Maeda and Moriyama, 0.300 ::; x ::; 0.500, hexagonal and/or rhombo-
1986). The microhardness of stoichiometric hedral SiC crystallites for 0.500::; x ::; 0.525,
SiC was Hv = 12 GPa (1.74 x 106 psi), while polycrystalline cubic SiC for 0.525 ::; x ::; 0.550
the hardness of mixed compositions of Si3N4 and randomly oriented hexagonal and/ or
was equal to or lower than this value (Figure rhombohedral for 0.550 ::; x ::; 0.600 (Takeshita
23.14). Compared to the hardness of films pro- et al., 1991).
duced by conventional CVD, this value is con- Although most PECVD of SiC has used
siderably lower (Hv = 12 GPa (1.74 x 106 psi), RF plasmas and SiH4 + CH4, an electron
0.05 kg vs Hv = 33GPa (4.79 x 106 psi), 0.05 kg cyclotron resonance plasma has been success-
for CVD). The lower value was attributed to the fully used to deposit films at 873 K (600 DC)
lower deposition temperature. (Chayahara et al., 1986).
598 Plasma-enhanced chemical vapor deposition
Using SiH4 and CH4 in PECVD of SiC Silicon Content (%)
90 80 70 60 50 40 30 20 10
involves a high safety hazard because of the 11 J

explosive and toxic nature of SiH4. In order

lI-
to decrease these hazards, liquid sources
with the formula R3 SiX (where R = CH3 , S 10
C2HS or C4H 9 and X = H, CI, or CH3 ) have 9-
been investigated (Bielan and Arendt, 1992). 0::
0 8-
Although process parameters need to be 0
Z
more fully investigated, preliminary results ~ 7 -
showed that, by using liquid compounds, '"'"<1.l 6-
c:
SiC films with a Knoop hardness up to ]
::z:: 5-
29.4 GPa (4.2 x 106 psi) could be produced.
.!
c:
An alternative route that allows for lower
0
4-
deposition temperatures (",523 K, 250C) is c 3
the use of fluorine-containing gases for the ~
tf 2
preparation of SiC crystallites. Using a mix- S
ture of SiF4-CFcH2 gases and a low power
density (80mW /cm 2), polycrystalline films
10 20 30 40 50 60 70 80 90
of Q-SiC were grown on glass substrates
Carbon Content (AT. %)
(Ganguly et al., 1991).
An interesting use of PECVD technology Figure 23.15 a-SiC: H microhardness vs composi-
has been the production of SiC whiskers tion. (Bayne, M.A., Kurokawa, Z., Okorie, N.V.,
from thin films. By using a conventional RF- Johnson, B.D. and Moss, RW., 'Microhardness
based SiH4-CH4 system to deposit thin films and other properties of hydrogenated amorphous
silicon carbide thin films formed by plasma
of SiC, then using reactive ion etching, high enhanced chemical vapor deposition,' Thin Solid
strength microfibers of SiC can be produced Films, 107, 201-06, 1983. Reprinted with kind
(Koskinen, Soave and Johnson, 1990). permission from Elsevier Science SA, Lausanne,
Although the primary concerns with PECVD Switzerland.)
films of a-SiC:H are the electrical and optical
properties, the hardness of these films is a
Titanium carbide (TiC)
function of carbon and hydrogen content
(Bayne et al., 1983). Generally, hardness in Titanium carbide films have been deposited by
amorphous SiC increases with increasing various methods such as sputtering and ion
carbon content and decreasing hydrogen con- plating. However, substrates with complicated
centration (Figure 23.15). Investigation of the shapes are difficult to coat with these tech-
optical and electrical performance of PECVD niques. Chemical vapor deposition of TiC
films of a-SiC: H and the effect of various most often utilizes TiCl4, C~ and H2 to pro-
process parameters has received continued duce coatings at temperatures of 1073-1273K
attention (Keski-Kuhan et al., 1988; Derst et al., (800--1000C) and pressures of P = 1 Pa
1992; Nakano et al., 1992). (0.008 torr).
In summary, the preparation of hard coat- Titanium carbide films produced by PECVD
ings of SiC via PECVD has focused on the utilize TiCl4, the same titanium source used in
production of polycrystalline films via RF- plasma deposition of TiN films. It is not sur-
based plasmas and SiH4 and CH4 gases. In prising then that films of TiC show similar
contrast, the production of a-SiC: H films has functional behaviors with regard to chlorine
concentrated on producing amorphous films content as TiN films. Below a substrate tem-
with optimal electrical and optical properties. perature of 723 K (450C), the chlorine content
 Advantages and limitations of PECVD-prepared coatings
of TiC films increases rapidly and results in
films with low hardness, increased flaking
and lower adhesion strength (Archer, 1981;
Arai, Fujita and Oguri, 1988).
The carbon content of these films also affects
the mechanical behavior (Figure 23.16).
Stoichiometric films of TiC exhibit the high-
est hardness, Hv = 29.4GPa (4.2 x 106 psi),
0.025 kg, while films with hyperstoichiometric
amounts of carbon have lower hardness, even
though the chlorine content is less than 5 wt%
(Arai, Fujita and Oguri, 1988). The structure
of TiC is tolerant of large deviations from
stoichiometry.
Boron carbide (B 4 C)
Boron carbide has applications as a tool bit
coating and for filaments. Deposition of
boron carbide films via PECVD has received
little attention. However, the effects of sub-
strate bias upon electron cyclotron resonance
plasma deposition of amorphous boron car-
bide have been studied. Rather than focusing
599
on the specific properties of amorphous boron
carbide films, the study was concerned mostly
with how general properties of plasmas such
as sheath and plasma potential are affected by
substrate bias and how these effects influence
film properties (Shirai and Gonda, 1990).
Veprek (1992) has examined the use of
PECVD to produce large-area boron carbide
coatings for controlled thermonuclear research.
Various modes of plasma excitation, 80MHz,
DC current and HF JDC current discharge
were used to deposit BxC films from B2 H 6 ,
C~ and Ar, He or H 2 . The films were depos-
ited on the toroidal geometry of a Tokamak
reactor and resulted in improved operation.
However, sections of the films that were
exposed to high heat loads and energetic
particles had relatively short lifetimes.
ADVANTAGES AND LIMITATIONS OF
PECVD-PREPARED COATINGS
PECVD is an effective means for preparing
hard coatings of ceramic materials at lower

60 ~--------------------------------,

~
~
'-'
40
.".Q.
~

~\
~
Hv2000
0
u ~-~!t"'../
~_ Hv 1000
U
20 -----~Q~
J ... - - - - - . g l
Hv 2500

o 10 20 30
40
CIContent

Figure 23.16 Effects of chlorine and carbon content on Vickers hardness of PECVD TiC coatings. (Arai, T.,
Fujita, H. and Oguri, K., 'Plasma assisted chemical vapor deposition of TiN and TiC on steel: properties of
coatings,' Thin Solid Films, 165, 148-49, 1988. Reprinted with kind permission from Elsevier Science SA,
Lausanne, Switzerland.)
600 Plasma-enhanced chemical vapor deposition
temperatures than CVD. The resulting film
quality is also comparable, if not better than
conventional CVD films in terms of mechani-
cal properties. However, the application of
this technique has been confined mainly to
nitrides and carbides. A major obstacle to
more effective use of PECVD for ceramic
materials is a lack of understanding of the
relationships between gas phase and surface
chemistry, and film properties that occur in
plasma deposition. Thus, there is a need for
research efforts that focus on the effects of
various parameters on conditions within the
plasma and surface reaction chemistry. The
majority of PECVD work has used halide
precursors as metal sources (AlBr3, TiC14
etc.) and either RF or DC plasmas. These
precursors, however, often result in the
formation of halide-containing contaminated
films. When TiCl4 is used for deposition of
TiN and TiC, chlorine contamination of the
film occurs, causing reduced hardness and
adhesive strength. The use of toxic and
explosive SiH4 for silicon carbide films also
is of concern. These concerns have initiated
investigations into alternative organic precur-
sors in order to minimize contamination and
toxicity, e.g. TMA and TIBA for deposition
of TiN and (CNBH 2 )n for BN. The use of
organic precursors, however, often results in
increased carbon incorporation in the film.
The current advantages of PECVD over
CVD for producing non-oxide ceramic coat-
ings reflect the lack of rational design of
CVD precursors. By designing CVD precur-
sors appropriately, it should be possible to
solve the problem of the high substrate
temperature associated with current CVD
techniques. For example, traditional routes of
TiN CVD generally require substrate tem-
peratures in excess of 873 K (600C). How-
ever, Fix, Gordon and Hoffman (1991), have
shown that TiN and other metal nitride films
can be deposited at much lower temperatures
by CVD of metal dialkylamido compounds
such as Ti(NR2 )4 species in the presence of
NH3. These conditions rival those of PECVD
processes. Another important issue that can
be addressed by precursor design for CVD is
control over stoichiometry of the final film.
Stoichiometry plays a crucial role in influen-
cing the physical properties of the final
materials as described in this chapter and
there are a number of examples of stoichio-
metric control over thin film composition
based on the precursor stoichiometry. Finally,
CVD may offer some advantages of selective
deposition over PECVD under some circum-
stances. However, one possible disadvantage
of CVD techniques is the incorporation of
impurities and the difficulty in formation of
dense films under these mild deposition
conditions. The PECVD and CVD of non-
oxide ceramics for applications as protective
coatings are likely to continue to be areas of
active research.
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PART NINE
HIGH TEMPERATURE FURNACE ENGINEERING
TYPES OF HIGH TEMPERATURE FURNACES
Furnaces (or reactors, calciners or kilns) are
either of the batch type or continuous type.
In general, cost-effective large scale operations
have tended toward the development of con-
tinuous processes. Hence, continuous-type
furnaces are of the most interest. Applications
of some of the most common types of contin-
uous furnace configurations (Figure 1) have
already been discussed in previous chapters.
Pusher furnace reactors (Chapters 6 and 10)
offer a semi-continuous type of operation in
which reactant powder precursors (as
powder mixtures or as formed aggregates)
are loaded into crucibles (or 'boats') and are
pushed through a 'tunnel kiln' which is
heated according to the desired temperature
schedule. A pusher furnace system can be
designed to mimic the heating in a batch-
type furnace (identical heat-up, soak and
cool-down conditions), but on a continuous
basis. This is a simple process with respect to
the physical handling of powders and is well
suited to processes requiring extended reac-
tion times (hours). The process challenges
and limitations associated with pusher fur-
naces are related to the ability to flow gas
and transfer heat uniformly through the
powder bed and the heat losses associated
with the heating and subsequent cooling of
crucibles. Often, the powder mass is less than
10% of the total mass (powder and crucible)
being heated. Nonetheless, pusher furnaces
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
are used extensively throughout the ceramics
industry for synthesizing powders. The cruci-
bles (or trays) can be moved either horizontally
or vertically through the heating zone.
In moving bed reactors (Chapter 6), precur-
sor powder aggregates are fed into the top of
the reactor and flow downward through the
vertical hot zone. A primary advantage of
the moving bed over the pusher furnace is
the elimination of the trays (or crucibles)
and, hence, a more energy efficient process
since only the aggregates are heated. In addi-
tion, gas-solid contacting is improved since
gas can flow easily around the aggregates as
they move through the vertical furnace.
Again, long reaction times (hours) can be
accommodated with this process. The primary
challenges associated with moving bed fur-
naces are the requirements to keep the aggre-
gates from disintegrating and to keep them
flowing through the hot zone in a pseudo-
plug flow manner. The primary limitation of
moving beds is heat transfer from the wall to
the centerline of the hot zone as discussed in
Chapter 6.
Rotary tube reactors (Chapters 7 and 25)
have the advantage that precursor powder or
aggregates are continuously replaced at the
furnace tube wall, thus providing superior
and more uniform heat transfer characteristics
relative to moving bed reactors. Residence
times are typically shorter (typically 30 min
to a few hours) than in moving beds. The
primary challenge associated with rotary tube
606 High temperature furnace engineering
Pusher Kiln
-..
Solids
"'-
Gas
Transport Flow
Solids I J
-----.. :; ,:.,_.:, ~_. ' ~ ' .~; ',~ ". :.1 .. , I:.':".:";":'.~'
Gas I I
Figure 1 Common types of continuous furnace configuration.
reactors is related to the flow of powder or
aggregates through the process. Reactor vol-
umes are typically limited to a 10-15 vol. %
loading. The primary limitations of rotary
tube reactors for high temperature applica-
tions (requiring refractory tubes) are the
limited availability of any large refractory
tubes and the complications associated with
mechanically rotating them and processing
powders at high temperatures. The economy
of scale may be severely limited by the
requirement that parallel furnaces are
needed due to size limitations on stock.
Fluidized bed reactors (Chapters 8 and 10)
can be operated batchwise or continuously.
They provide excellent heat transfer and
gas-solid contacting and the ability to flow
powders into and out of the furnace easily.
They are best suited for carrying out highly
endothermic or highly exothermic reactions
in which large volumes of solids are pro-
cessed. For batch operations, it is particularly
important that solids are not easily friable
since they are typically maintained in the
Moving Bed
Solids
Fluidized
Bed
t
Gas
Gas
bed for many minutes to hours. For continu-
ous operations, reaction times should be
short, in the order of seconds to several
minutes. The reason for this is the continuous
stirred tank residence time distribution in the
bed due to the rapid mixing. Many variations
of fluidized bed reactors are possible, includ-
ing staged furnace designs and baffled fur-
naces to impose a more plug flow contacting
pattern in the bed. The primary challenges
associated with fluidized beds are the integ-
rity of the solids including the subsequent
containment of any fines which might be gen-
erated and how the perfectly mixed contacting
pattern is managed relative to the reaction
residence time requirements.
Dilute phase flow reactors (aerosol, trans-
port or entrained flow) are discussed in
Chapters 10 and 12 and are most suitable for
synthesis processes requiring short reaction
times. Often gases or vapors are reacted
together to produce powders while flowing
through tubes. In some instances, solids are
reacted with gases or other solids. Heat

transfer rates are fast with radiation dominat-
ing the process. Limited reaction times require
fast kinetics for reactions which can only be
completed in several seconds. The primary
challenge associated with dilute phase flow
reactors is the elimination of plugging prob-
lems which typically exist near the entry and
exit of the reactor.
Design considerations for high temperature
batch- and continuous-type furnaces are des-
cribed in Chapter 24. Design considerations
for lower temperature rotary calciners are
considered in Chapter 25.
SAFETY ISSUES
Safety must be considered a priority in the
design, operation and maintenance of indus-
trial furnaces. Due to the temperatures, atmo-
spheres and cooling water that may be
involved in high temperature furnace opera-
tions, there are several aspects of furnace
safety that are especially important.
TEMPERATURE SAFETY
Occupational Safety and Health Administra-
tion (OSHA) and common sense both dictate
that furnaces subject to possible contact by
operating personnel should not be hot
enough to cause burns. OSHA specifies that
this temperature must not exceed 344 K
(71C). Operators should wear proper protec-
tive clothing when working in furnace areas.
Since damage to the retina of the eye can
result almost instantly when exposed to the
high intensity light emitted by high tempera-
ture sources, visual access to internal heating
chambers must be limited and provided with
protective guards and warning signs.
Furnaces must be allowed to cool to near
room ambient temperature before attempting
to gain access to their interiors for servicing.
Components should always be considered
to be hot unless proven otherwise. On those
pieces of equipment where it is difficult
or impossible to gauge internal insulation
Safety issues 607
temperatures, provisions may be included to
install low level thermocouples through the
outer furnace shell into the insulation. Depth
of thermocouple penetration is dependent
upon furnace temperature, type of insulation
and the type of thermocouple.
ATMOSPHERE SAFETY
There are three types of atmospheres that may
be encountered in association with high tem-
perature furnaces. They are the atmospheres
required by the process, those produced by
reaction upon heating and those needed to
protect furnace components. Furnace safety
must take each of them into account.
First, a flammable gas system must always
be thoroughly purged with a non-flammable
atmosphere such as nitrogen before intro-
ducing any flammable gas into the system.
Therefore, the atmosphere system should
include provisions for neutral gas purging.
When using flammable atmospheres, combus-
tion gas monitors in the furnace area are also a
valuable safety device.
Depending upon circumstances, it may also
be advisable to install oxygen monitoring
devices near the furnace to detect conditions
that could aggravate breathing problems or
cause asphyxiation. This is particularly
advised when large amounts of inert gases
such as nitrogen or argon are used.
Use of flammable furnace atmospheres
poses special safety considerations. To burn at
a violent or explosive rate, flammable atmo-
spheres within an enclosed furnace require a
strong infusion of air (oxygen) directly into
the furnace cavity, and sufficient temperature
or a spark to ignite the mixture. Therefore, a
'tight' furnace with all gaskets, seals and
glands maintained in top condition is the first
step toward safe operation.
There are two common ways of introducing
flammable gas into a furnace. First, the fur-
nace may be thoroughly purged with a non-
flammable gas such as nitrogen. The quality
of this purge can be verified with an oxygen
608 High temperature furnace engineering
analyzer sampling effluent gases from the
furnace. Alternatively, an unpurged furnace
may be raised to a temperature above approxi-
mately 1033 K (760C) at the precise point
where the flammable gas first enters the
furnace, before the flammable gas is intro-
duced into the furnace. This temperature in
combination with the air inside the furnace
insures immediate safe controlled ignition of
the flammable gas. Flammable gas must not
be injected into an unpurged furnace that is
at a temperature below approximately 1033 K
(760C). Doing so creates a potentially serious
explosive condition.
Before a furnace using flammable gas
atmospheres is opened for service or main-
tenance, the furnace must be thoroughly
purged with a non-flammable gas to eliminate
any explosive potential.
All flammable gases flowing out of a fur-
nace through doors, vents and purge pipes
should be ignited, and the combustion
products exhausted from the area.
Many processes release gaseous by-
products during thermal cycling. These gases
may be flammable, corrosive, toxic etc. There-
fore, provision must be made to safely remove
them from the furnace, to allow for safe and
proper disposal. Such furnaces must also be
thoroughly purged to remove all possible
traces of these gases before maintenance or
service personnel attempt to open or enter
them. In some cases, special protective cloth-
ing and/or air packs may be necessary to
insure personnel safety.
Possible explosive conditions can result with
the formation of CO. If NH3 is used, special
precautions must be made for handling any
produced HCN as well as the NH3. The HCN
product gas is extremely toxic and must be
properly handled. Proper selection of the
system off-gas components, as well as effective
atmospheric control of the furnace by use of
seals, gaskets, airlocks and inert purge gases
for start-up, operation and shutdown is
required for safe equipment operation.
COOLING WATER SAFETY
Some high temperature furnaces and some
types of heating elements require a flow of
cooling water to maintain safe temperatures.
Since the combination of high temperatures
and water create a potential for high tempera-
ture steam that could easily lead to a steam
explosion, a system engineered for safety as
well as to meet furnace requirements is essen-
tial. In the case of graphite furnaces, the steam
could react directly with the graphite, produ-
cing large volumes of CO and H 2 Properly
designed relief devices need to be installed on
furnaces to handle worst-case scenarios.
Due to the potential for serious conse-
quences if cooling water is lost or becomes
inadequate to meet the needs of the furnace,
a reliable source of water and an equally reli-
able alternate emergency source or back-up
circulating system is essential. The latter can
be any type of fuel-powered engine and
pump combination.
EMERGENCY SYSTEMS
High temperature furnaces using special
atmospheres and/or cooling water must be
equipped with a manual or automatic transfer
mechanism to an emergency back-up system
for these services. Both the transfer mechan-
ism and the emergency back-up system must
be fully tested for proper operation on a
regularly scheduled basis, preferably under
simulated conditions.
DESIGN CONSIDERATIONS FOR
HIGH TEMPERATURE FURNACES
Ellis W. Delahoy
INTRODUCTION
From the days when primitive man squatted
beside a mound of glowing coals, fire-harden-
ing the tips of wooden spears, to the tightly
controlled, high temperature furnaces and
kilns of today, heat has been and will continue
to be a significant part of many manufacturing
processes. However, the open fire used to
make a wooden spear point harder and more
durable, or to bake a clay pot, has evolved
over millennia into a sophisticated piece of
high technology equipment. Today's products
demand ever more of the industrial heating
equipment used to process them.
Higher temperatures and/ or tighter tem-
perature uniformities, precise control over
process temperatures throughout a heat-cool
cycle, special atmospheres and/or multiple
sequential atmospheres; automated material
handling etc., are all part of today' s equipment
specifications. Furthermore, in a world grow-
ing increasingly more conscious of energy
costs and dwindling natural resources, opera-
tional efficiency is essential. To meet these
demands, an understanding of the specific
application requirements has never been
more important.
Traditionally, ceramicists have called their
heating equipment 'kilns', while metallurgists
referred to theirs as 'furnaces'. Kilns provide a
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
24
slow heat-up, a soak and a slow cool-down, to
minimize thermal shock to vulnerable ceramic
materials. Furnaces used to process metallic
materials that had only minimal susceptibility
to thermal shock, featured comparatively
rapid heating and cooling cycles. Today, the
distinctions between the terms 'furnace' and
'kiln' are becoming blurred as some modern
ceramics display characteristics that are
approaching those of some traditional
metals, including greater resistance to thermal
shock. As a result, the words 'furnace' and
'kiln' are often used interchangeably.
As the focus of this chapter is high tem-
perature furnace engineering, discussions of
comparatively low temperature equipment
such as ovens, alloy mesh belt furnaces etc.,
are not included.
PROCESS AND PRODUCT
CONSIDERATIONS
Furnaces are used for powder synthesis (Van
Dijen, Metselaar and Siskens, 1985) and for
part fabrication (greenware densification)
(Wittmer and Miller, 1991; Wittmer, Paulson
and Miller, 1992; Wittmer et al., 1993). The
ability to engineer the best piece of heating
equipment to meet the specific needs of either
process is directly proportional to the amount
of essential process information known. This
610 Design considerations for high temperature furnaces
applies equally to stock 'off-the-shelf' furnaces
as well as to special custom-designed equip-
ment. Ideally, every engineering evalu-
ation, selection process or design needs to
consider:
1. the heating requirements of the batch or
continuous 'charge';
2. the handling of any by-product gases or
condensables;
3. the need for any special atmospheres
during processing.
The heating requirements include the need
to heat the batch or continuous 'charge' (pro-
cess material including gases and any saggers,
trays or crucibles etc.) at the desired rate to the
desired temperature, to maintain temperature
at the desired set point for the required
amount of time and then to reverse this
process with subsequent cooling. There may
be several levels of heating and cooling
according to the desired heating cycle for the
process. Of critical importance is the heat loss
to cooling water or atmosphere through the
walls of the furnace and the energy require-
ments of any reaction (endothermic or
exothermic) which may be taking place.
Often, by-product gases or condensables
associated with the removal of organic binders
or the synthesis of powders must be continu-
ously removed and properly handled outside
of the furnace. In order for the condensables to
be collected outside of the furnace, internal
furnace temperatures must be greater than
the temperature of condensation. Gases (or
vapors) are usually directed to a single exit
port and properly disposed of in suitable
burners which mayor may not be an integral
part of the furnace itself. In addition to health
and environmental concerns, the by-products
may have a significant detrimental effect on
the inside walls, insulation, heating elements
or furnace shell.
Special process atmospheres are usually an
integral part of the process. Typical require-
ments include the need for a minimum or
maximum oxygen content or dew point and
a particular process or protective atmosphere
such as argon (Ar), nitrogen (N 2) or hydrogen
(H 2). The most common and inexpensive inert
atmosphere used to protect the process is N 2.
When N2 is unacceptable due to reactivity
concerns, Ar is usually a second choice as it
is more expensive. When reducing atmo-
spheres are desired, H2 is usually used.
Some atmospheres are required as part of
the process such as N2 atmosphere when
nitrides are synthesized. Argon is often
preferred for the manufacture of carbide
and boride powders in order to prevent the
formation of nitrides which may be more
thermodynamically favored than the desired
carbide or boride product (Chapter 3) in the
presence of N 2.
Argon has one characteristic that sets it
apart from most other common process
atmospheres. Under certain high temperature
conditions in the presence of a relatively low
electrical potential (approximately >20 V), Ar
ionizes, becoming an electrical conductor. The
exact conditions under which ionization
occurs vary with temperature, pressure and
voltage. Ionization occurs more readily at
higher temperatures (approaching 2773 K
(2500C)). The thermal effect of ionization
can be retarded by the addition of a low per-
centage of N2 or helium (He) to the Ar base.
The ultimate temperature, heating cycle
and atmosphere required for the process
determine the optimum design configuration,
size, type of heating element(s), amount and
distribution of heat (power) and type of
insulation required. Additional considera-
tions include the level of material handling
and control sophistication.
FURNACE CONFIGURATIONS
Furnaces are generally of the batch type or
continuous type. When considering possible
configurations, it is essential that the furnace
selected be compatible with the needs of the
process, production requirements and any
space limitations.

BATCH FURNACES
The furnaces in this category (sometimes
called periodic type) are charged or loaded
with the furnace at or near room temperature.
Then, with the charge remaining stationary,
the furnace is cycled up and down through a
predetermined time-temperature cycle. When
it returns to near room temperature, the
furnace is unloaded and prepared for the
next cycle.
Due to this cyclic mode of operation, batch
furnaces are generally characterized by flex-
ibility. This feature allows their operating
parameters to be changed from cycle to cycle
with relative ease, to meet the requirements of
multiple more-or-Iess similar processes or
materials. On the down side, a cyclic opera-
tion tends to consume greater amounts of
energy due to the necessity of reheating the
furnace itself with each cycle. The characteris-
tics of various batch furnaces are compared in
Table 24.1.
Box (front loading)
Front loading box furnaces are generally of
smaller size and manually loaded, which is
labor intensive and time consuming. Since
Furnace configurations 611
their hearth areas are usually raised above
heating chamber floor level, they can
accommodate a variety of heating element
arrangements and achieve varying degrees
of temperature uniformity.
Elevator (bottom loading)
Elevator furnaces (Figures 24.1 and 24.2)
feature a hearth resting upon an insulated
plug. After loading, the hearth and insulated
plug are raised up into the furnace by an
elevator mechanism. If the insulated plug
and its hearth are incorporated in a car, the
car can be rolled to one side from beneath
the furnace where increased clearances offer
easier loading and unloading. The addition
of a second car and hearth permits one car to
be unloaded and then reloaded while the first
one is being thermally cycled within the heat-
ing chamber. This capability allows faster
recycling (shorter tum-around time) and,
therefore, greater utilization of the furnace.
Pit (top loading)
Pit furnaces are top loaders, similar to
inverted elevator furnaces without an elevator

Table 24.1 Characteristics of batch furnace configurations

Furnace configuration Charge Temperature Turn-around Limitations or comments

capacity uniformity time

Box (front loading) Small to Mediocre to good Poor Frequently used for R&D
moderate and pilot applications
Elevator (bottom Large Excellent Minimal High overhead clearances
loading) are usually required
Pit (top loading) Large Excellent Poor Loading charges into a deep
chamber is difficult
Bell (movable Large Excellent Minimal High overhead clearances
heating chamber) are usually required.
Long power and service
cables
Car (roll-in hearth) Largest Moderate Minimal Not recommended for
tightly controlled or
flammable atmospheres
612 Design considerations for high temperature furnaces
MULTIPLE VERTICAL
ZONES OF HEATING
ELEMENTS ON 2 OR
4 SIDES
2nd LOAD
CAR
Figure 24.1 Elevator furnace schematic.
mechanism. As such, they can theoretically
offer equivalent internal capacities and
temperature uniformities. Unfortunately,
depending upon size and chamber depth,
loading and unloading ceramic materials
through a top opening can be a difficult
procedure, manually or mechanically.
Bell (movable heating chamber)
Borrowing their name from a laboratory bell
jar, these furnaces feature one or more fixed
hearths in combination with a movable
heating chamber that is raised or lowered
over the hearth by an overhead hoist. Multiple
hearths permit faster recycling and maximum
utilization of the furnace.
On the other hand, heating chambers are
encumbered with long flexible power cables.
Depending upon temperature capabilities
and the type of heating elements employed,
PRODUCT LOAD
CENTERED
WITHIN
HEATING
CHAMBER
they may also be burdened with multiple
cooling water supply and drain lines. In
addition, moving the heating chamber sub-
jects refractories and heating elements to the
high probability of repeated physical shock.
As many refractories and the majority of
heating elements are quite sensitive to physi-
cal shock, this raises the likelihood of frequent
replacement.
Car (roll-in hearth)
These furnaces feature an insulated car sup-
porting the hearth, generally with a system
of tracks to guide the car into place within
the heating chamber. The wall through
which the car passes is closed by either an
integral insulated vertical wall at the outer
end of the car or by an insulated vertical slid-
ing door that lowers into place after the car is
in position inside the heating chamber.

Figure 24.2 Elevator furnace. (Courtesy of Harper International Corporation, Lancaster, NY.)
Due to the difficulty of sealing this furnace
in two planes (end wall or door and around
the base perimeter of the car), this furnace is
not generally recommended for tightly con-
trolled or flammable atmosphere applications.
CONTINUOUS FURNACES
A continuous furnace is one that is heated
to a series of preset temperatures over its
length to obtain a specific unchanging tem-
perature profile from one end of the furnace
to the other. The charge, consisting of the pro-
cess material plus any required support
refractories and furniture, is passed through
the furnace at a predetermined speed, cycling
each charge through an identical heating and
cooling program. The speed of the charge
moving through the furnace and the lengths
of the various furnace sections are selected
to allow the charge to be heated and cooled
Furnace configurations 613
at a rate that will achieve the desired overall
time-temperature profile.
Material processed through a continuous
furnace generally has the most consistently
uniform characteristics. Uniformity is further
enhanced when automated material handling
is employed to minimize the variables of
human handling. Automated continuous
furnaces are ideally suited for 24 h per day
operations. Compared to batch furnaces,
continuous furnaces generally consume less
energy per unit of output, by not having to
reheat the furnace with each charge cycled.
On the other hand, continuous furnaces
do not have the same flexibility as batch
furnaces. Changing operating parameters
usually consumes significant time due to
the need to remove existing in-process
rna terial from the furnace before making
any radical changes. The characteristics of
various continuous furnaces are compared
in Table 24.2.
614 Design considerations for high temperature furnaces
Table 24.2 Characteristics of continuous furnace configurations

Furnace Charge Temperature Energy Service Limitations or comments

configuration capacity uniformity efficiency accessibility

Car Excellent Moderate Low Good Not recommended for

tightly controlled or
flammable
atmospheres
Pusher Excellent Excellent Very good Good Charge weight and
pusher plate friction on
hearth limit furnace
length
Walking beam Excellent Very good Excellent Fair Mechanical walking
beam linkages are
beneath heating
chamber, limiting
service access
Roller hearth Variable Excellent Very good Good Temperature limited by
charge weight and
chamber width
Carpet Hearth Variable Good Very good Good Not recommended for
tightly controlled or
flammable
atmospheres.
Restricted load height
Rotary tube Good Superior Superior Good Charge material limited
to no more than 15%
moisture by weight
Vertical tube Variable Superior Excellent Good High overhead clearances
or multifloor
installation may be
required
Note: Carpet Hearth is a Registered Trademark of Harper International Corporation.

Car
Car furnaces are horizontal furnaces with
multiple insulated cars forming a portion of
the bottom of the heating chamber. The cars
with their hearths and their charges are
pushed slowly along a track, in a continuous
line through the furnace. Each car pushes the
ones in line ahead of it. Heating elements are
generally limited to sidewall locations. These
furnaces are not recommended for tightly con-
trolled or flammable atmosphere applications
due to the problems encountered in sealing or
controlling atmosphere movement around
and between the moving cars.
Pusher
Pusher furnaces (Figures 24.3 and 24.4) are
horizontal units that use ceramic, metal
(such as Mo) or graphite pusher plates upon
which the charge material is placed. These
plates and their cargo are pushed slowly
through the furnace in a continuous line at a
constant speed, each plate pushing those
plates in line ahead of it. The pushable
length is dependent upon the weight of each
pusher plate and its charge and the friction of
the plate against the hearth material. Pusher
plates must also have flat parallel edges to
insure evenly distributed pressure against
 ENTRANCE
I HEATINC SECTIONS COOUNC SECTIONS
CONTINUOUS PRODUCT LINE
HEARlH
I
Furnace configurations 615

EXIT
DOOR DOOR
rA7~777T~~~~~

PUSHER--~

Figure 24.3 Pusher furnace schematic.

the pushing surfaces. Excessive length or Walking beam

uneven plate edges can cause the plates to
buckle upward or 'hump' where they push
against one another, causing a production
stoppage. Heating elements may be located
on chamber sidewalls and/ or over and
under the hearth and charge space. Powder
synthesis processes using pusher furnaces
are reviewed in Chapter 6.
Walking beam furnaces (Figures 24.5 and 24.6)
use a fixed refractory support in combination
with a reciprocating refractory hearth to
transport charge materials through the
length of the furnace. Since each charge is
slowly lifted and moved forward without
contacting any other charge, this permits

Figure 24.4 Pusher furnace. (Courtesy of Harper International Corporation, Lancaster, NY.)
 I
616 Design considerations for high temperature furnaces
HEATING SECTIONS COOUNC SECTIONS ~

SUPPORT RAILS I
Ar~~77+r.~~~

HEARTH '" PRODUCT MOVING FORWARD

HEAATH CYCLING BACKWARD, PRODUCT AT REST

Figure 24.5 Walking beam furnace schematic.

lighter charge configurations and eliminates
the problem of pusher plate 'humping'. It
also allows much greater furnace length. On
the other hand, reciprocating hearths require
extensive mechanical linkages that are
mostly beneath the furnace and sealed
within any atmosphere-tight furnace shell.
This arrangement complicates servicing these
mechanisms. Heating elements are generally
located on the chamber sidewalls.
along the length of the furnace to provide
greater time-temperature flexibility. Furnace
capacity is dependent upon a combination of
the weight of the charge and its support tile,
the width of the chamber, the chamber tem-
perature and, of course, the size and strength
of the roller material. Heating elements may
be located on the chamber sidewalls and/or
over and under the roller hearth and charge
space.

Roller hearth Carpet Hearth

In a roller hearth furnace, the charge is placed
on relatively thin setter plates or tile and
carried through the furnace on multiple cer-
amic rolls driven from outside the heating
chamber. Each charge is moved indepen-
dently without contacting any other charge.
Furthermore, roller drives may be designed
to permit faster speeds as the charge travels
A Carpet Hearth furnace uses a continuous
belt of low thermal mass, insulating fiber
modules to carry a charge through the
furnace. Since the moving modular belt
forms the insulated floor of the heating
chamber, heating elements are restricted to
locations above the belt and charge space.
Consequently, this configuration is not

Figure 24.6 Walking beam furnace. (Courtesy of BTU Engineering Corporation, North Billerica, MA.)
recommended for thick or tall charge config-
urations. The use of the fiber module belt as
the chamber floor also prevents tight atmo-
sphere control and limits atmosphere use to
inert and non-flammable gases.
Rotary tube
Rotary tube or rotary reactor furnaces (Figures
24.7 and 24.8) are limited to the processing of
powders, grain, granules or pellets with low
moisture content (approximately 15% or less
by weight). Since the process material is fed
continuously into the upper end of an
externally heated rotating tube, and tumbles
down the inclined length of that tube to the
discharge end, no trays, saggers or crucibles
are required. This provides exceptionally
good energy efficiency. In addition, every
particle of the process material is exposed to
Furnace configurations 617
the same temperatures and the same atmo-
spheres, insuring the highest possible product
uniformity. Heating elements may be placed
on the sidewalls and/ or over and under the
tube. At temperatures above the capabilities
of alloy metals, furnace production capacities
are limited by the smaller sizes of available
ceramic or graphite tubes. Powder synthesis
processes using rotary tube-type reactors are
reviewed in Chapter 7. Lower temperature
rotary calciners are reviewed in Chapter 25.
Vertkal tube
A vertical tube furnace is simply a vertical
refractory tube within a vertically oriented
heating chamber. These furnaces may be
equipped with a single tube or multiple
tubes. They can be used for processing
powders, grain, pellets or gases. As with the
 618 Design considerations for high temperature furnaces
~UL TIPLE LENGTHWISE ZONES
Of HEATING ELEMENTS
PRODUCT
fEEDER
MECHANISM
Figure 24.7 Rotary tube furnace schematic.
rotary tube furnaces, no trays, saggers or cru-
cibles are required, providing exceptionally
good energy efficiency. Heating elements
may be located on the sidewalls and/or
in between multiple tubes, with multiple
top-to-bottom control zones for maximum
temperature uniformity within the chamber.
These furnaces are operated in two common
formats, as a transport flow reactor or as a
moving bed reactor. In a transport flow
reactor, process material is fed into the top of
the vertical tube and carried with process gas
through the tube where it is reacted and sub-
sequently cooled downstream. This format
provides superior temperature uniformity
within the tube and a superior level of product
uniformity. In a moving bed reactor, process
material is fed into the top of the tube and
removed from the bottom at a controlled
rate. This forms a continuous moving bed of
process material within the tube. A flow of
process atmosphere upward through the bed
creates a free flowing fluid-like condition
DISCHARGE
CHUTE
within the bed of process material. Tempera-
ture uniformity across the tube and thus
product uniformity, is dependent upon the
tube diameter and the specific heat, thermal
conductivity and flow rate of the process
material. Powder synthesis processes using
vertical tubes as moving bed or transport
flow reactors are reviewed in Chapters 6, 10
and 12.
HIGH TEMPERATURE HEAT SOURCES
There are a number of electrical-resistance
heat sources available (Table 24.3) for high
temperature furnaces. Selection depends
upon maximum required temperature, atmo-
sphere exposure to process material and by-
product gases and general environment.
Since this chapter focuses on high tempera-
ture furnaces, relatively low temperature alloy
element materials such as nickel-chromium
and iron-chromium-aluminum are not dis-
cussed. Furthermore, fuel-fired heat sources

Figure 24.8 Rotary tube furnace. (Courtesy of Harper International Corporation, Lancaster, NY.)
are rarely used for the applications under
consideration and are therefore excluded.
SILICON CARBIDE (SiC)
These commercially available elements are
formed of fine-grained SiC with terminal
ends of lower electrical resistance. Although
available in a variety of configurations, the
most common is a long, slender rod or bar.
MOLYBDENUM DISILICIDE (MoSi2 )
Formed of slender MoSi2 rods with lower
resistance terminal ends, these commercial
elements are available in a V-shape and a
number of other shapes. When returned to
room temperatures after high temperature
operation, MoSi2 elements become quite
brittle and are easily broken when subjected
to physical shock.
High temperature heat sources 619
MOLYBDENUM (Mo)
Molybdenum ('moly') rod or twisted multiple
strands of wire can be used to fabricate a
variety of custom-designed configurations.
The two most common elements are a simple
serpentine shape and an element wound
around a refractory tube. 'Moly' elements are
readily oxidized and must not be operated in
an oxidizing atmosphere. For best element
life, a hydrogen-based atmosphere (minimum
5-10% H 2 ) is recommended. After being
heated, 'moly' elements also become quite
brittle at room temperature.
TUNGSTEN (W)
Tungsten elements are available in essentially
the same configurations and with the same
atmosphere limitations specified for 'moly'
elements. However, W elements have higher
Table 24.3 Capabilities and limitations of typical high temperature heating elements

Heating element Air Argon Nitrogen Hydrogen

Temperature Surface loading Temperature Surface loading Temperature Surface loading Temperature Surface loading
(K (DC)) (W/cm2) (K (DC)) (W/cm2) (K (DC)) (W/cm2) (K cac)) (W/cm2)

Globar Type 1923 (1650) 1.55 1923 (1650) 1.55 1644 (1371) 3.10-4.65 1572 (1299) 3.88-4.65
SG SiCa
Kanthal 2073 (1800) 10.25 1973 (1700) 10.10 1973 (1700) 10.10 1673 (1400) 8.25
Super 33
MoSi2 b
Molybdenumc 672 (399) 2171 (1898) 20.2-40.3 2171 (1898) 20.2-40.3 2171 (1898) 20.2-40.3
TungstenC 672 (399) 2171 (1898) 20.2-40.3 2171 (1898) 20.2-40.3 2171 (1898) 20.1-40.3
Graphited 673 (400) 3273 (3000) 6.2-12.4 3273 (3000) 6.2-12.4 3273 (3000) 6.2-12.4
a The Carborundum Company, Electric Products Division (1990) Globar Silicon Carbide Electric Heating Elements, Form A-703B, Rev. 3-90, pp. 10-11, Niagara Falls,
NY. Globar is a Registered Trademark of The Carborundum Company. Type LL Globar elements are limited to a maximum chamber temperature of 1811 K
(1538 DC) in air or argon at a surface loading of 4.06 WI cm2 .
bKanthal Furnace Products (1984) Kanthal Super Handbook, pp. 19,21, 35 and 36, Ljungforetagen Orebro, Sweden. Kanthal is a Registered Trademark of
Kanthal AB, Sweden. Data based upon a 9 mm diameter element with a maximum current flow of 220 A, a 6 mm element at 120 A or a 3 mm element at 42.3 A.
C Schwarzkopf Technology Corporation. How to Make Out with Moly, pp. 2, 7, 10 and 12. Holliston, MA.

d Data provided through the courtesy of Harper International, Lancaster, NY. Although graphite can be operated at temperatures up to 3273 K (3000 DC) and
over, it begins to deteriorate at an ever-increasing rate above 2973 K (2700 DC), reducing its useful life. Graphite reacts with both nitrogen and hydrogen, though
at a somewhat faster rate with hydrogen. Nevertheless, both gases are generally considered to be acceptable atmospheres for graphite heating elements.
Notes: The temperatures and wattage loadings stated are the recommended maximums for each element in combination with the atmosphere specified, based
upon data provided by the respective manufacturers. At lower temperatures, higher wattage loadings are permissible. Atmosphere dew points also affect
permissible surface loadings. Manufacturers should be consulted for specific information on other temperatures vs surface loadings for these and other atmo-
spheres, and for the effects of atmosphere dew point.
Data on Globar elements are based upon chamber temperature, all others are based upon element surface temperature.
The above heating elements are offered as a representative cross-section of those presently available, and must not be interpreted as an endorsement of any
particular product. Data are expressed as typical values, and intended only as a guide to material selection.

temperature capabilities. On the negative side,
they also share molybdenum's characteristic
brittleness at room temperature after having
been operated at high temperatures.
GRAPHITE (C)
Graphite elements are available in a wide
variety of configurations ranging from com-
mercial off-the-shelf units to custom designed
elements. Graphite is very susceptible to
oxidation and must be operated within the
driest, most oxygen-free environment avail-
able. A protective atmosphere with a dew
point of 201 K (-72 dc) and less than 2 ppm
of free oxygen may help compensate for
other possible sources of oxygen contamina-
tion. The most frequently used protective
atmosphere for graphite elements is nitrogen.
Although there is a reaction between graphite
and nitrogen, the rate of reaction is low
enough to still achieve good element life.
HIGH TEMPERATURE INSULATION
Thermal insulation in high temperature fur-
naces may be provided by a single material
or multiple layers of different materials. A
cross-section sampling of some current com-
mercial insulating materials and their thermal
conductivities is shown in Table 24.4.
Most insulating materials are available in
several forms from conventional insulating
firebrick to special custom shapes, bulk fiber
to fiber-based paper, felt and blanket, and
also as powders, grain and granules. Most
fiber-based low thermal mass insulation is
available as standard boards and cylinders,
as well as custom-designed shapes.
ALUMINA-SILICA AND ALUMINA-BASED
MATERIALS
Perhaps the oldest and the best known insu-
lating materials are those based on various
alumina-silica mixtures. As a general rule,
the temperature capabilities of these materials
Design package 621
are reflected in the percentage of alumina
present. Higher alumina content usually
means higher temperature capability. Usually,
however, it also means higher thermal con-
ductivity, greater sensitivity to thermal shock
and a higher price.
ZIRCONIA-BASED MATERIALS
Zirconia-based materials offer exceptional
high temperature insulating capabilities, well
above the temperature limits of high purity
alumina insulation, but at a higher cost.
High-zirconia materials start to become elec-
trically conductive at approximately 1473K
(1200C). As their temperatures increase from
this level, their electrical resistance decreases
sharply. Therefore, electrical heating elements
must be electrically insulated from contact
with high-zirconia materials at these high
temperatures. In addition, zirconia brick and
other similar structural shapes go through a
high temperature phase change that may
cause them to lose their bond and crumble
when cycled.
CARBON-BASED MATERIALS
Carbon and graphite (crystallized allotrope of
carbon) have the highest temperature capa-
bilities of any material and are among the
most abundant elements on earth. Further-
more, they are resistant to many forms of
corrosive attack. Unfortunately, they are very
susceptible to oxidation and can only be used
in a protected, dry, oxygen-free environment.
Graphite (and to a slightly smaller degree,
carbon) is electrically conductive at all
temperatures. Therefore, special consideration
must be given to electrically insulate carbon-
graphite materials from contact with electrical
heating elements.
DESIGN PACKAGE
Selecting and/or designing the best furnace
for a specific process application is a task
Table 24.4 Thermal conductivities of typical high temperature commercial insulating materials

Material Primary Maximum Thermal conductivity (W/m K (Btu in/jf . h OF) at mean temp. of
designation composition recommended
temperature 1273K 1523K 1773K 2023K 2273K 2773K
(K (DC (1000 DC) (1250 DC) (1500 dc) (1750 DC) (2000 DC) (2500 DC)
(1832 OF) (2282 OF) (2732 oF) (3182 OF) (3632 OF) (4532 OF)

K23 Bricka Alumina 39%, 1533 (1260) 0.207 (1.433)

Silica 44%
K28 Bricka Alumina 25%, 1811 (1538) 0.432 (2.998)
Silica 52%
K3000 Bricka Alumina 61 %, 1922 (1649) 0.461 (3.198) 0.551 (3.823)
Silica 36.5%
ZAL-45 Boardb Alumina 85%, 1922 (1649) 0.274 (1.866) 0.335 (2.282) 0.395 (2.732)
Silica 15%
SALI Boardc Alumina 80%, 1977 (1704) 0.294 (1.966) 0.329 (2.269) 0.365 (2.632)
Silica 20%
FBC Boardc Zirconia >98% 2272 (1999) 0.210 (1.433) 0.235 (1.613) 0.258 (1.793)
AN-599 Brickd Alumina 99.8% 2143 (1870) 1.24g (8.42) 1.3OS (8.98) 1.45g (9.73)
AN-299A Alumina 99.55% 2143 (1870) 2.48g (17.17) 2.31 g (16.04) 2.23g (15.49)
Brickd
Fiberform Carbon 99.9% 3023 (2750) 0.443 (3.07) 0.574 (3.98) 0.742 (5.14) 0.963 (6.67)
1800 Boarde
Fiberform Carbon 99.9% 3023 (2750) 0.623 (4.32) 0.738 (5.12) 0.874 (6.06) 1.037 (7.19) 1.228 (8.51) 1.725 (11.95)
2300 Boarde
CBCF Board f Carbon >99.9% 3273 (3000) O.54h (3.74) 0.62h (4.30) 0.78h (5.41) 0.98h (6.79) 1.35h (9.36)
CalCarb D Carbon >99.9% 3273 (3000) 0.59h (4.09) 0.91 h (6.31) 1.08h (7.49) 1.27h (8.80) l.38h (9.57)
Board f

a Thermal Ceramics Inc. (1990) Product Data 1991 Edition, p. 12, Augusta, GA. The 'K' designation is a Registered Trademark of Thermal Ceramics Inc.
b Zircar Products Inc. (1985) Zircar Fibrous Ceramics, Bulletin ZPI-308, Florida, NY. Zircar Fibrous Ceramics is a Registered Trademark of Zircar Products, Inc.
C Zircar Products Inc. (1988) Zircar Fibrous Ceramics, Bulletins ZPI-308 and ZPI-211, Florida, NY.

d Norton Company (1989) Advanced Ceramics Technical Bulletin, Sht S-P-A-BD4 and S-P-A-BD2, Worcester, MA.
e Fiber Materials, Inc. (1987) Fiberform Insulation, Biddeford, ME. Additional data provided with FMI letter of 23 January 1992, by L.L. Lander. Data based upon
use in a neutral, non-oxidizing atmosphere. Fiberform is a Registered Trademark of Fiber Materials, Inc.
f CalCarb Limited (1991) Calcarb C.B.C.F. and Thermal Conductivity, Bellshill, Scotland. (ISO 9002; 1987 B55750 Pt2 Intemational Quality Management and Quality
Assurance System registrant.)
g 'Hot face' rather than mean temperature.
h 'Spot' temperature in Ar atmosphere rather than mean temperature.
Notes: Atmospheres used may affect maximum temperature capabilities and thermal conductivities.
The thermal conductivities stated above are based upon published data provided by the respective manufacturers or derived from interpolations of same in
order to use a common temperature base for comparison.
The above insulating materials are offered as a representative cross-section of those presently available, and must not be interpreted as an endorsement of any
particular product. Data are expressed as typical values, and intended only as a guide to material selection.

that combines basic engineering technology
with practical experience and know-how.
However, like the majority of engineering
problems, there is usually more than one satis-
factory solution. Therefore, the engineer may
have to investigate several possible solutions
to select the one that best matches the specific
process and production requirements - and
budget.
SELECTION OF HEATING ELEMENTS
The first factors that must be considered are
those that are process related. What tempera-
tures are required and what is the overall
time-temperature profile specified? Does the
process need an atmosphere and is it an
integral part of the process or just to protect
the process material from oxidation? What is
the atmosphere and are there any special
atmosphere requirements, i.e. dew point,
oxygen content etc.? Are gaseous by-products
released by the process material during
thermal cycling? If yes, are they flammable,
toxic, corrosive etc.?
Answers to the above, when compared to the
temperature and atmosphere capabilities and
limitations summarized in Table 24.3, and
with comparable data available from a variety
of other sources, will quickly eliminate some
heating element materials and focus attention
on those that meet process criteria. It must
also be remembered that the element tempera-
ture will be higher than the desired chamber
temperature, depending upon the wattage
loading on the element surface. The higher
the wattage loading, the greater will be the
temperature differential between the element
and the surrounding chamber.
Example: heating element selection
A maximum temperature requirement of
2023 K (1750 C) within a nitrogen atmosphere
eliminates SiC and MoSi2 , but might permit
the use of Mo, W or graphite. All three meet
temperature and atmosphere requirements,
Design package 623
but W or graphite tend to be more costly over-
all (based upon both material and installation
costs). Thus, Mo would seem to be the most
practical choice, especially if a small per-
centage of hydrogen in the atmosphere is
acceptable. However, other factors, such as a
high carbon potential or the release of corro-
sive by-product gases within the heating
chamber, may eliminate both Mo and W, leav-
ing graphite as the best element material.
Every possible factor that may affect the
selection must be carefully evaluated.
SELECTION OF INSULATING MATERIALS
Some of the factors that apply to the selection
of heating element materials must also be con-
sidered in the selection of insulating materials.
Specifically, an insulation material must be
selected that is compatible with the product
being manufactured and its atmosphere
selected. Multiple layers of insulation may be
selected to optimize the balance between cost
and efficiency. Exposure to temperature and
the heating chamber environment can alter
the insulating properties over time. Insulating
material should be selected to minimize this
natural degradation. The selection of the
insulation dramatically affects the rate of
heating and cool-down as well as power
consumption. Some of the most commonly
used insulating materials are compared in
Table 24.4.
Furnace configuration may also influence
material selection. For example, a narrow
heating chamber generally permits the roof
to be constructed in anyone of several ways
using different types of materials. However,
depending upon temperature, a wider cham-
ber may offer fewer choices, both in material
selection and roof design.
When it has been determined which
materials are suitable for a particular appli-
cation, the engineer must first create a
theoretical insulating wall composed of one
or more thicknesses of suitable insulating
materials. With a specific wall in mind, the
624 Design considerations for high temperature furnaces
engineer must then calculate the rate at which
heat will flow through that wall. Furthermore,
heat flow through a roof or a floor is different
from that through a sidewall of the same
construction. This is due to the difference in
heat dissipation from a vertical outside surface
to the surrounding environment compared to
that of a horizontal surface etc. Hydrogen in
the furnace atmosphere increases the rate of
heat flow through insulation in relation to the
percentage of hydrogen present.
In addition to the rate of heat flow, the
amount of heat stored within an insulating
wall is also important, especially with periodic
or batch-type furnaces where the insulation
must be heated and cooled with each cycle.
Heat flow can be calculated manually using
basic heat flow or thermal transfer formulas,
together with thermal conductivity data pro-
vided by the manufacturers of the various
insulating materials. An excellent discussion
of heat transfer and how to use various formu-
las is presented elsewhere (Reed, 1986).
PRODUCTION FORMAT AND SELECTION OF
FURNACE CONFIGURATION
While it may appear that these are two sepa-
rate steps, they are so interdependent that
they must be considered as one. In addition
to the production rate requested, we must
consider all factors discussed thus far,
together with process time-temperature pro-
files and the sensitivity of the process material
to heating and cooling rates and soak times
(time at temperature).
If the characteristics of the process material
are affected by heating and cooling rates or
soak times, large, densely loaded formats are
to be avoided. With such load formats, process
materials near the outer surface of the charge
package heat and cool at one rate, while those
in the center of the charge package heat and
cool at a slower rate. If the whole charge is
held at soak temperature until full thermal
equilibrium is achieved throughout, that pro-
cess material near the outer portion of the
charge will be at soak temperature for a signi-
ficantly longer time than that at the middle of
the charge. Thus, the characteristics of the pro-
cess material will differ (perhaps significantly)
from one part of the charge package to
another, resulting in a non-uniform product.
If the process material is sensitive to heat
and cooling rates and to soak times, certain
furnace configurations such as the elevator,
bell, car with roll-in hearth etc., that use
large and generally densely loaded formats,
are unacceptable. Therefore, one of the contin-
uous furnace configurations would appear to
be most appropriate for such a process.
After all the above factors have been care-
fully evaluated, the engineer should have a
fairly accurate concept of the load format.
This should include a detailed sagger, tray or
crucible design including size, material and
weight, plus the amount of process material
per each sagger, tray or crucible.
If a batch furnace has been requested or
seems appropriate, the engineer must use the
container information above to establish a
practical loading arrangement including hori-
zontal and vertical spacing for the saggers,
trays or crucibles. The production capacity of
this arrangement must meet or exceed the
production requirements. However, the latter
must also be matched to the length of time
required for a specific heat-soak-cool process
cycle and the number of cycles that can be com-
pleted within a stated period of time.
Example: batch furnace
A production rate of 100kg (220lb) per 24h
day (three shifts per day) and a thermal cycle
time of 30 h have been specified. The process
material is not sensitive to heating and cooling
rates, or time at temperature, and the flexibility
of a batch furnace is preferred. A 400mm
(15.8 in) square sagger with a 2 kg (4.4lb) capa-
city is to continue to be used.
From the above and assuming a 2 h turn-
around time or 32 h for a complete cycle,
three cycles can be completed in four days.

Therefore, at a production rate of 100 kg/ day
(220Ib/day), a total of 400 kg (BBOlb) must be
produced in four days, or 133.3 kg (293.3Ib)
must be processed per each cycle.
If four saggers are arranged in a square
pattern, each loaded with 2 kg (4.4lb) of pro-
cess material, each layer of four saggers will
have a combined capacity of Bkg (17.6Ib).
Therefore, to obtain a loading of 133.3 kg
(293.3Ib) per cycle, a total of 17 layers will be
required. This will provide an actual produc-
tion capacity of 136kg (299.2Ib) per cycle, or
40B kg (B97.6Ib) in four days, i.e. a production
rate of 102 kg (224.4Ib) per 24h day.
If a gap of 100 mm (3.9 in) is allowed
between saggers for improved heat transfer
by radiation to the center of the charge and if
we assume that each layer (consisting of the
sagger, setter tile, vertical spacing for radiant
heat transfer etc.) is 100 mm (3.9 in) high, the
charge size is defined. The charge will be
900mm (35.4in) square by 1700mm (66.9in)
high. This charge format would appear to be
too big for a box furnace, but ideal for an
elevator or bell furnace. However, with a
different sagger arrangement, a car furnace
with a roll-in hearth could also be used.
If a continuous furnace has been requested,
the engineer must start with basic container
information and from this determine a practi-
cal unit loading arrangement. The arrange-
ment must be one that can be readily
handled by one of the continuous furnace
systems. It must include the width, length,
height and weight of the unit, plus its produc-
tion capacity. Based upon the unit load and
the time-temperature profile specified, the
length of the furnace and its individual sec-
tions (i.e. preheat, high heat, soak and cooling)
can be calculated. This information should
eliminate some furnace configurations and
focus attention on others.
Example: continuous furnace
A production rate of 50 kg (110Ib) per
24 h day (three shifts per day) and a 20 h
Design package 625
time-temperature cycle time that has a total
of five heat, soak and cool segments has been
specified. The temperature uniformity is criti-
cal during two segments of the cycle. A small
sagger 125 mm (4.9 in) square containing
0.5kg (1.llb) of process material is currently
being used. A large number of these saggers
are available for use in the new furnace.
If saggers of the size specified were to be
passed through a continuous furnace in a
single line, the furnace would be unacceptably
long and narrow, and therefore inappropriate
and uneconomical. On the other hand, if four
saggers are arranged in a square pattern
spaced 15-20 mm (O.6--O.B in) apart, they
could fit comfortably on a 300 mm (11.B in)
square setter tile. This should provide a
more reasonable and economical layout. At
0.5 kg (l.1lb) of production per sagger, there
will be 2kg (4.4Ib) of production per setter
tile. A single layer of saggers per setter tile
will insure uniform exposure to chamber
temperatures.
To obtain the specified production rate of
50kg/day (llOlb/day), a total of 25 setter
tiles must be cycled through the furnace
every 24 h. Since the specified time-tempera-
ture cycle time is only 20 h, the combined
length of the furnace preheat, high heat, soak
and cooling sections (exclusive of any furnace
automation or material handling) should be
sufficient to accommodate 20.B setter tiles or
6.250m (246. lin). To move 25 setter tiles
through this furnace in 24 h, they must be
moved at a nominal speed of 312.5mm/h
(12.3in/h) or 5.2mm/min (0.2in/min). Based
upon this information and the time-tempera-
ture profile, the theoretical individual lengths
of the furnace preheat, high heat, soak and
cooling sections are easily calculated.
The furnace thus defined is a relatively
small unit. For a high level of temperature
uniformity, one of the least expensive furnace
configurations that would offer optimum
temperature uniformity would be a pusher
type. Heating elements can be mounted
horizontally side-to-side, over and under the
626 Design considerations for high temperature furnaces
load supporting hearth, with the additional
option of independent temperature control
over and under the hearth and load for maxi-
mum control sensitivity.
Both of the above examples are greatly
simplified. The actual selection process is
much more complex and involves a number
of other interrelated factors. Therefore, each
set of requirements must be individually
analyzed.
HEAT BALANCE CALCULATIONS
Having finally determined what heating
elements and insulation are the best match for
the temperature and atmosphere requirements
and what production format and furnace con-
figuration are most appropriate, it now
becomes necessary to calculate the amount of
power (heat) that will be needed to accomplish
all of this. In multiple zone or multiple section
furnaces, these calculations must be performed
for each zone and/or each furnace section. If
adjacent zones and/or sections are present,
heat received from or lost to them must also
be taken into consideration.
Heat will be required to raise the process
material and any containers, carriers, furni-
ture and fixtures to the temperature specified
by the process time-temperature profile. In a
batch furnace, heat will also be required to
increase the adjacent insulating material to
an equivalent temperature and to replace
any heat transferred through the insulation
to the outside room environment. The heating
elements and furnace charge support refrac-
tories will also have to be brought up to
temperature along with the process material.
In a continuous furnace, the insulating
material is already thermally stabilized and
it is only necessary to replace that heat lost
through the insulation. Power will also be
required to heat any atmosphere within the
furnace to the appropriate temperature level.
This mayor may not be significant depending
upon the volume of atmosphere present and
its flow rate.
As already stated, any heat lost through the
insulation to the room environment must be
replaced. However, heat may also be lost con-
ductively through heating element terminals,
muffles or tubes that pass through exterior
walls or into adjacent zones or sections etc. In
the latter instance, heat can also be conducted
into the zone or section from an adjacent zone
or section operating at a higher temperature.
Radiant heat losses are another factor to be
considered. Whether it is a door, open throat
or port to the outside of the furnace or to an
adjacent zone or section, if it is at a lower
temperature, there will be radiant heat losses
that must be replaced. Conversely, radiant
heat can be received from an adjacent zone or
section operating at a higher temperature. The
amount of heat lost or gained through radiant
transfer depends upon the size and shape of
the opening, the length of the throat (if any)
and the temperature differential between the
adjacent zones or sections. All other factors
being equal, a rectangular opening will allow
greater radiant heat losses than a square or
round opening of the cross-sectional area.
The sum of the above (heat required, heat
lost and heat received) must be determined
for each zone and each furnace section. How-
ever, the total amount of heat or power thus
calculated is not sufficient to operate the
furnace. To provide a realistic safety factor
and to also give the furnace a reasonable
degree of flexibility and responsiveness, an
additional percentage of this total amount
must be added. Without this extra power,
the furnace would operate, but be unaccept-
ably sluggish and slow to respond. Further-
more, it would probably be unable to meet
any reasonable changes in production and/
or time-temperature requirements which can
be normally expected to occur. The calculated
heat (power) requirements are thus balanced
against the amount of power applied to the
various zones and sections of the furnace.
There is no accepted standard for the
amount of excess power that should be
available. Excess power requirements vary

from application to application and generally
range from 20% to 50%.
FURNACE POWER AND TEMPERATURE
CONTROL SYSTEMS
After having determined what heating ele-
ments will be used and the amount of power
to be applied to each furnace zone or section, it
is possible to design the electrical power and
control circuits and to select the appropriate
components. For this design, the engineer
must consider both the characteristics and
capabilities of the various power system
components that may be used in the circuit,
and the electrical characteristics unique to
each type of heating element. Power can be
controlled by either a simple onloff system
or on a proportional basis.
For use with silicon carbide
heating elements
Like most materials, the electrical resistance
of SiC heating elements changes with tem-
perature. Unlike some materials, however,
SiC elements have their highest resistance at
ambient room temperature. As SiC elements
begin to heat up, their resistance decreases
rather quickly. Then, at a temperature well
below their normal operating temperature,
their resistance begins to climb. Nevertheless,
at the maximum useful element temperature,
SiC electrical resistance is still significantly
less than its room ambient resistance. From
their lowest resistance level up to their
maximum temperature levels, they have an
electrical resistance range of approximately
1.5: 1. In addition, SiC elements also oxidize
as they are used, increasing their resistance.
For optimum element life and controllabil-
ity, SiC heating elements should be powered
through a tapped transformer, with the taps
selected to provide multiple output voltages
sufficient to cover the full range of their antici-
pated circuit resistance. The taps also permit
the output voltage to be matched to the
Design package 627
operating temperature and load, which in
turn permits optimum utilization of the cap-
abilities of any proportional power controller.
For use with molybdenum disilicide,
molybdenum and tungsten heating elements
These three element materials all share one
common characteristic. They have a low elec-
trical resistance at room ambient temperature
and their resistance increases steadily as their
temperature rises. From room ambient to
maximum temperatures, they undergo an
approximate 10: 1 increase in electrical resis-
tance. Therefore, a power system designed
for the resistance anticipated at normal oper-
ating temperatures should include a current
limiting device to prevent excessive current
and power component overload during start-
up or low temperature operation.
Since the electrical resistance of these
elements tends to change very little over
their useful life, a tapped transformer is not
normally required. The proportional capa-
bilities of the power controller are usually
sufficient to handle any resistance changes
due to aging.
For use with graphite elements
The electrical resistance of graphite initially
decreases from its room ambient level; then
at a temperature well below its normal operat-
ing temperature, it begins to increase. From
then on, the resistance continues to increase
as the element temperature rises. The rate of
increase is dependent upon the particular
grade or composition of graphite being used.
Depending upon these factors, the electrical
resistance may increase from about 1.4: 1 up
to over 1.7: 1, between its lowest resistance
level and that at maximum element tempera-
tures.
Graphite elements can be used over a very
wide range of temperature. If a power system
is designed for use at their upper temperature
capabilities, it will be greatly overpowered
628 Design considerations for high temperature furnaces
during start-up or lower temperature opera-
tion. Therefore, transformers are usually pro-
vided with reduced power taps for lower
temperature operation. Due to the relatively
low electrical resistance of graphite, power
systems normally provide low voltage and
high current outputs.
ATMOSPHERE, COOLING WATER AND
OTHER FURNACE SYSTEMS
Furnaces frequently operate under a protective
or process atmosphere and, at high tempera-
tures, may also require varying degrees of
water cooling. If either is required, an appro-
priate system should be provided to monitor
the supplies, to control or regulate their pres-
sures and flow rates, to insure that they are
piped to the proper furnace location and,
finally, to insure that they are properly
removed from the furnace.
An atmosphere system should include
pressure switches and gauges to monitor the
atmosphere supply pressures. If atmosphere
dew point, oxygen content or other possible
constituents of the furnace atmosphere are
critical, appropriate instrumentation to moni-
tor them should be incorporated into the
system. Lacking any definite instructions or
guidelines, an overall atmosphere flow rate
equivalent to approximately five atmosphere
volume changes per hour is a good starting
point for system sizing.
The water supply used for furnace applica-
tions should be clean; filtered if necessary.
Algae or sediment that can enter a cooling
system from a pond, or even a cooling tower,
can quickly block cooling circuits creating
significant safety hazards. Even if no hazards
are caused, repairing or replacing integral
cooling panels can be time consuming and
costly. If quality piping is used and effluent
water temperatures are kept below approxi-
mately 327K (54C; 130 OF), water hardness
equivalent to common city tap water should
pose no problems. For anyone set of operating
conditions, water consumption will increase
as the cooling water supply temperature
increases.
A safe, well designed cooling water system
places the water flow control and shutoff
valves on the supply side of the furnace
connections. The system should also include
a pressure switch and gauge to monitor the
cooling water supply.
If the furnace has an open gravity drain
system, supply-side valving allows safe un-
restricted release of any steam build-up
within the furnace cooling panels or lines.
Open drain systems also provide easy access
to effluent water allowing operating personnel
to measure water discharge temperatures and
check water flow rates. Where a closed or pres-
surized drain system is employed, appropriate
pressure relief devices must be installed in all
panels and lines exposed to high temperatures.
In either case, various types of instrumentation
can be provided to monitor effluent water tem-
peratures and flow rates, and sound an alarm if
unsafe conditions are detected.
Critical systems should also be provided
with emergency back-up systems to provide
these services in the event of a breakdown or
failure in the primary system, power failure
etc. The back-up systems should be sized to
maintain necessary flows and pressures suffi-
cient to cover furnace needs for the time it
takes to take the furnace safely out of service.
In addition to atmosphere and cooling water,
some furnaces also require supplies of
compressed air for operation of pneumatic
doors and various forms of material handling
etc. Others may require a supply of instru-
ment quality air to cool control cubicles or
to purge or pressurize them to minimize
infiltration of room air. The latter should be
considered if air-borne carbon dust or other
electrically conductive materials exist in the
room environment.
MATERIAL HANDLING
In addition to the various methods of moving
process material through a furnace already

discussed, the overall furnace design should
include provisions for handling process
materials outside of the furnace. Such provi-
sions may be manually controlled and as
simple as having an operator place a charge
on an entry hearth and pushing it into the fur-
nace chamber. Or they may be fully auto-
mated and as complex as the process or the
user may demand, tying into other systems
to feed material to the furnace automation,
as well as removing the processed materials
from the furnace area. The possibilities are
limitless.
FURNACE CONTROL
In the area of furnace control, the possibilities
are also limitless. Control can be a simple
individual stand-alone digital microproces-
sor-based temperature controller for each
control zone, to which a recorder can be
added to provide a permanent record of
furnace operation. Or it can be a sophisticated
all-inclusive microprocessor-based PLC (pro-
cess logic controller) unit, which is in reality
a factory-floor-hardened computer.
Units of the latter type are available that can
provide not only temperature control and
over-temperature protection for multiple
temperature zones, but also control all levels
of furnace automation, atmosphere and cool-
ing water system control etc. All of this is
programmed through a keyboard or keypad
terminal and can be vividly displayed on a
color video monitor with multiple display
References 629
options. In addition to their control functions,
they can be provided with the capability
to record multiple forms of data input from
the furnace and to display or print out this
information upon request, to show status or
operational trends etc. The use of and the
capabilities of these units are steadily increas-
ing. However, the system should not provide
greater control sophistication than the furnace
can reasonably use.
After all of these factors have been con-
sidered, evaluated, calculated and finally
assembled, a furnace has been created. For a
stock 'off-the-shelf' furnace, some of these
steps will not be necessary, while others will
help the engineer to select the one unit best
suited for the application.
REFERENCES
Reed, R.J. (1986) Heat transfer, in North American
Combustion Handbook, 3rd edn, Vol. I, pp. 80-
130.
Van Dijen, F.K., Metselaar, R. and Siskens, CA.M.
(1985) Large scale production of fine non-oxide
ceramic powders. Wid Ceram., 2, 15-18.
Wittmer, D.E. and Miller, CW. Jr (1991) Compari-
son of continuous sintering to batch sintering of
Si3N 4. Am. Ceram. Soc. Bull., 70(9), 1519-27.
Wittmer, D.E., Paulson, T.E. and Miller, CW. Jr
(1992) Continuous sintering of Si3N4 in a con-
trolled atmosphere belt furnace. Ceram. Eng. Sci.
Proc., 13(7-8), 546-62.
Wittmer, D.E., Conover, J.J., Knapp, V.A. and
Miller, C.W. Jr (1993) Economic comparison of
continuous and batch sintering of silicon
nitride. Am. Ceram. Soc. Bull., 72(6), 129-37.
ROTARY TUBE CALCINERS
David W. Dahlstrom
INTRODUCTION
Rotary tube calciners using metallic or oxide
ceramic tubes are well suited for a number
of operations in which processing tem-
peratures are typically below 1923 K
(1650C). These include applications such as
the removal of chemically bound water from
precursor oxides (e.g. boric acid to B2 0 3), the
carbonization of organic species such as bind-
ers which are contained in ceramic precursor
formulations, the removal of excess carbon
from carbo thermally produced non-oxide
powders (Chapter 19), the removal of NH3
from diimide intermediates to produce amor-
phous Si3N 4 (a) (Chapter 15), and the crystal-
lization of amorphous powders (e.g. Si3N 4 (a)
to a-Si3N 4 ; Chapter 15).
Water removal operations are normally
carried out irt air and require low tempera-
tures 773 K, <500C) where stainless steel
tubes are suitable. The large scale removal of
free carbon from carbo thermally produced
non-oxide powders can be achieved through
the use of rotary tube calciners equipped
with metallic alloy tubes operating at tem-
peratures between 773 and 1173K (500-
900C), using air as well as oxygen-enriched
atmospheres. Carbonizing applications typi-
cally use inert atmospheres suitable for pyro-
lysis. Again, metallic tubes are usually
adequate. Higher temperature operations
(> 1473 K, > 1200 C) such as the crystallization
of amorphous non-oxide powders require
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
25
ceramic tubes, typically of alumina or
mullite construction. The synthesis of non-
oxide powders by carbothermal reduction
(Part Two) typically requires even higher
temperature capability (1773 K < T < 2673 K,
1500C < T < 2400 C) and the use of graphite
tubes as reported in Chapter 7.
Rotary calciners can be designed for con-
tinuous processing of these powders with
retention times of 1-2h or more, and product
rates up to 1000 kg (2203lb) /h. If much longer
residence times are required, then rotary batch
calciners can also be utilized.
In high temperature rotary calciners, the
process material can be handled in either
direct or indirectly heated units, as shown in
Figure 25.1. For most applications, the con-
siderations for determining whether an
indirect or direct approach is appropriate are
as follows.
1. Can the process material be brought into
contact with products of combustion?
2. Are special purge or reaction gases needed
to achieve an inert, reducing or oxidizing
atmosphere?
3. Is the process material extremely fine
and/or does it have a low specific gravity
that would permit entrainment and
correspondingly improper processing?
4. Would the process off-gas volume be
greater if products of combustion were
present and necessitate larger off-gas treat-
ment equipment?
632 Rotary tube calciners
OFF-GASES

HOT
GASES IN

PRODUCT OUT
[aj

OFF-GASES
PURGE IN

AGITATING J~::::;:~
FLIGHTS

PRODUCT OUT
INDIRECT HEAT SOURCE
(bj

Figure 25.1 (a) Direct-heat rotary unit; (b) indirect-heat rotary unit. (Courtesy of ABB Raymond, Lisle, IL.)

5. Is a special temperature profile required to or oxidizing as well as contain products of com-

properly heat the process material?
6. Does the calciner tube have to be con-
structed of a certain type of material for
process compatibility considerations?
For removal of carbon from non-oxide ceramic
powders, the indirectly heated rotary calciner is
the proper selection because the material is fine
and an oxygen-rich atmosphere is required for
effective carbon burnout. Directly heated units
or refractory-lined rotary kilns (Figure 25.2)
would be provided for applications where the
process conditions could be slightly reducing
bustion, the process material was pelletized or
very coarse powder, or process temperatures to
1923 K (1650 C) would be required.
GENERAL EQUIPMENT DESCRIPTION
A typical indirect rotary calciner (Figures 25.3
and 25.4) consists primarily of a rotating
cylinder housed within a stationary insula-
tion-lined furnace. The furnace can employ
electric heating elements, light oil and/ or gas
burners for heating. Most calciners are gas
 General equipment description 633

Discharge
Breeching
Optical
Pyrometer

B~rne~'1
Feed / ~ u,
Chute -I-----w-n=i=E
Feed
Breeching

Support Frame
Trunnion Rolls

Support Base

Figure 25.2 Direct fired rotary calciner. (Courtesy of ABB Raymond, Lisle, IL.)

Exhaust Stack
.-- / ThermoCouple
/ ~Cylinder
Refractory and
Insulation
Furnace
Burner
Sight Hole
and Plug F

Drive Assemblies

Figure 25.3 Indirect-heat rotary calciner; gas-fired with cooler. (Courtesy of ABB Raymond, Lisle, IL.)
634 Rotary tube calciners
Section C-C
Furnace Area
Thermocouple
Heating Elements
~ Cylinder
Refractory and
Insulation
Figure 25.4 Indirect-heat rotary calciner; electrical with cooler. (Courtesy of ABB Raymond, Lisle, 11.)
fired and about 30-40% efficient without heat
conservation equipment. Electric units are in
the 70-80% efficiency range, but the cost of
electricity is generally two to three times that
of natural gas for a given amount of energy
delivered to the process. So even with the
much higher thermal efficiency, electrically
heated units are generally not as cost effective
as gas-fired ones.
The ends of the cylinder extend beyond
the furnace and are fitted with riding rings,
each rotating on a pair of trunnion rolls.
Both ends of the rotating cylinder are enclosed
in stationary breechings featuring seals and
purge fittings for maintaining the atmospheric
requirements for non-oxide ceramic powder
applications. The breechings are fitted with
airlocks such as rotary or double-flap valves
to minimize or prevent air leakage at these
points. In applications where it is necessary
to cool the treated material before discharge,
Bellows
Type Seals
an indirectly water-cooled section is added
to the calciner cylinder.
Depending on the amount of solids to be
processed, the type of application and how
fine the particle size of the powder, the unit
can be arranged for the purge/reaction gas
to be passed through the unit, counter-current
or co-current to the flow of solids.
The process material is continuously screw
fed through the feed-end breeching of the
calciner to the cylinder and continuously
emptied from the discharge breeching of the
calciner. The time of passage for the process
material through the unit is controlled by the
cylinder speed, cylinder slope, material flow
characteristics and cylinder internals such as
flights and dams.
Calciner cylinders are provided with a short
section of helical flights on the interior of the
feed end of the cylinder to rapidly advance the
process material into the furnace section, as

well as to prevent back-spilling of the material
out of the feed end of the cylinder. The furnace
section of the calciner will be normally pro-
vided with internal flights that are specifically
designed to gently mix the material so that
entrainment is minimized. However, for
applications requiring a gas-solid reaction
such as carbon removal from non-oxide cer-
amic powders, the flights should be designed
to promote exposure of the reaction gases and
the process solids. Proper design will result in
the more homogeneous treatment of the pro-
cess material and reduced retention times.
MATERIALS OF CONSTRUCTION
As far as materials of construction in process
contact area, the most critical component for
selection is the cylinder. Indirect rotary cal-
ciners normally feature stainless steel or
various high temperature alloy cylinders,
with the selection depending on the tem-
perature and the chemical considerations for
the application as discussed above. In cases
where the temperature requirements exceed
1473 K (1200 DC) or there are extremely corro-
sive process conditions present, then some
ceramic or graphite materials can be utilized.
EQUIPMENT SELECTION
For a new process, it is desirable that a labora-
tory or pilot test be perfomed on a test unit to
determine the proper parameters for scaling-
up to a larger production piece of equipment.
Typical parameters that should be defined are:
1. the type of feeder;
2. the transport properties of the process
material per time of passage (equation
25.1 below);
3. the bulk densities of the feed and treated
product;
4. the optimum product temperature;
5. the thermal properties of the process
material such as specific heats and heat of
reactions;
Equipment selection 635
6. the retention time for the hot zone of the
calciner and, if required, the time at tem-
perature for the product;
7. the purge gas rate, composition, direction
and temperature;
8. the off-gas composition, particulate load-
ing and temperature.
The off-gas data should be utilized to prop-
erly select the pollution control equipment
for compliance with the local environmental
regulations and proper operation of the
rotary calciner. In the specific case of burning
carbon off non-oxide ceramics, trace levels of
CO will be present in the off-gases and most
likely will require a secondary combustion
chamber for proper oxidation.
The test should also establish if the produc-
tion unit will be designed on a basis of reten-
tion time or heat transfer. Should retention
time be the requirement, the heated length of
the calciner would be determined based on
the desired feed rate of solids and a normal
loading percentage of approximately 10% of
the gross cylinder volume. Higher loading
values can be considered, but the possibility
of a nonhomogeneous product exists for a
given retention time. On the other hand, if
the size is to be determined by heat transfer,
the heated length of the calciner will be cal-
culated, based on the necessary surface area
to transfer the heat to the process material.
At temperatures above approximately 823 K
(550 DC), this will be primarily by radiation
heat transfer. In some applications, the
product will be heated rapidly and then held
at a given temperature. With this approach,
both a thermal and retention time selection
will be required to determine the heated
length of the calciner.
Indirectly heated rotary calciners are com-
mercially available in cylinder sizes from 0.1
to 3 m (0.33-9.8 ft) in diameter and from 1 to
40 m (3.3-131 ft) in length. After establishing
a practical furnace length for a given diameter
(typicallength-to-diameter ratios for the 823-
1173K (550-900 DC) range would be around
636 Rotary tube calciners
10 to I), the slope and speed of the cylinder
can be selected to achieve a desired retention
(or residence) time. To determine these values,
use the following equation that applies to
most free-flowing solids:
(25.1)
where
Dc = cylinder diameter (m),
Ec = empirical constant as determined by
testing,
Lf = furnace length (m),
Rc = cylinder speed (rpm),
Sc = slope of cylinder (deg),
t = residence time (s).
APPENDICES
SELECTED PROPERTY DATA

DISCLAIMER compiled. No warranty is expressed or

implied with the accuracy or completeness of
This information is provided in good faith. the data. No responsibility will be taken for
The reader should review the cited sources claims that might arise from the use of these
of information from which the data were data.

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
CRYSTALLOGRAPHIC PROPERTIES A

Table A.I Formula, formula weight, color, theoretical density (Pth), crystal structure and lattice parameters

Formula Formula Colora Theoretical Crystal Lattice parameters

weight density, Pth structure
(kg/m 3 x 10-3 ) a b c
(nm) (nm) (nm)

Borides
a-AIB12 156.70 2.58b Tetragonalb 1.016b 1.428b
,B-AIB12 156.70 2.60b Orthorhombica 1.234b 1.263b 1.016b
CrB 62.81 6.14b Tetragonalb 0.294b 1.572b
CrB 2 73.62 Gray 5.20b Hexagonal b 0.2973b 0.3071 b
HfB2 200.11 Gray 11.l9b Hexagonalb 0.3142b 0.3476b
NbB 2 114.53 Gray 7.00b Hexagonalb 0.3089b 0.3303b
TaB 2 202.57 Gray 12.54b Hexagonalb 0.3098b 0.3227b
TiB2 69.54 Gray 4.52 b Hexagonalb 0.3030b 0.3230b
VB 61.75 5.60b Orthorhombica 0.3060b 0.8048b 0.2972b
VB 2 72.56 Gray 5.07b Hexagonalb 0.2998b 0.3056b
ZrB2 112.84 Gray 6.10b Hexagonalb 0.3169b 0.3530b

Carbides
Al4 C3 143.96 2.99 c Rhombohedral c 0.3330 a 2.489 a
B4 C 55.25 Black 2.52c Rhombohedralc 0.561 a 1.212 a
CaC 2 64.10 2.20a Cubica 0.588a
Cr3C2 180.01 Gray 6.68 c Orthorhombicc 0.5533 a 0.2829 a 1.l472a
HfC 190.50 Gray 12.6~ Cubicc 0.4642 a
Mo2C 203.89 Dk gray 9.12c Hexagonal C 0.3012 a 0.4736 a
NbC 104.92 Ltbrown 7.82c Cubicc 0.4469 a
a-SiC 40.10 3.21c Hexagonal (6H)a 0.3080 a 1.5098a
,B-SiC 40.10 3.21c Cubica 0.4358 a
TaC 192.96 Lt brown 14.50c Cubicc 0.4454 a
TiC 59.91 Lt gray 4.92c Cubicc 0.4327a
VC 62.95 Gray 5.48c Cubicc 0.4166 a
WC 195.86 Gray 15.8c HexagonalC 0.2906a 0.2837a
W 2C 379.71 Gray 17.3c HexagonalC 0.5814a 0.4721a
zrC 103.23 Gray 6.56c Cubicc 0.4697a

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
640 Crystallographic properties
Table A.l (continued)

Formula Formula Colora Theoretical Crystal Lattice parameters

weight density, Pth structure
(kg/m3 x 10-3 ) a b c
(nm) (nm) (nm)

Nitrides
AlN 40.99 Lt gray 3.26d Hexagonal d 0.3113 a 0.4982a
,B-BN 24.82 White 3.48d Cubicd 0.3615a
a-BN 24.82 White 2.28 d Hexagonald 0.255a
CrN 66.00 Black 6.14 d Cubic d 0.4149 a
HfN 192.50 Lt brown 13.94d Cubicd 0.4518a
Mo2 N 205.89 Dk gray 8.04d Cubicd 0.4169a
NbN 106.91 Lt gray 8.36d Cubicd 0.4392 a
a-Si3N 4 140.29 Lt gray 3.18d Hexagonald 0.7818a 0.5591a
,B-Si3N 4 140.29 Lt gray 3.19d Hexagonald 0.7595a 0.2902a
TaN 194.96 Gray/blue 14.36d Hexagonald 0.519 a 0.291 a
TiN 61.91 Yellow 5.44d Cubicd 0.4249a
VN 64.95 Lt brown 6.08d Cubicd 0.4136 a
ZrN 105.23 Lt yellow 7.35 d Cubicd 0.4577a

Other
MoSi2 152.11 Gray 6.26a Tetragonala 0.3203 a 0.7855a

Sources:
aKosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications, Hemisphere
Publishing Corp., New York.
bCutler, R.A. (1991) Engineering properties of borides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S.}. Schneider, }r), ASM International, Metals Park, OH, pp. 787-803.
cMCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 2, Carbides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 2, Battelle, Columbus, OH.
dMCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 1, Nitrides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 1, Battelle, Columbus, OH.
THERMODYNAMIC AND THERMAL B
PROPERTIES

Table B.l Heat capacity at constant pressure, cp

cp = A + 1.0E - 3 * B * T(K) + 1.0E5 * C * T- 2 + 1.0E - 6 * D * T2 (J/mol K)

Formula Phase cp range, T (K) A B C D

Borides
AlB12 Solid 298--2473 211.292 115.060 -85.354 0
CrB Solid 298--1200 42.468 15.899 -10.125 0
CrB2 Solid 298--1200 40.221 44.852 0 0
HfB2 Solid 298--1500 65.145 18.410 -18.828 0
NbB2 Solid 298--1400 46.986 38.535 -9.414 0
TaB2 Solid 298--3373 59.463 18.807 -15.071 0
Liquid 3373-3500 125.52 0 0 0
TiB2 Solid 298-3193 56.379 25.857 -17.464 -3.347
Liquid 3193-3500 108.784 0 0 0
VB Solid 298--1200 37.886 22.615 -7.335 -4.033
Solid 1200-2500 44.589 6.799 -1.117 4.280
VB2 Solid 298--1200 50.053 44.497 -13.548 -12.347
Solid 1200-2500 63.459 12.866 -1.117 4.280
ZrB2 Solid 298--3323 64.212 9.427 -16.581 0
Liquid 3323-4466 96.232 0 0 0

Carbides
Al4 C3 Solid 298--1800 154.691 28.727 -41.940 0
B4 C Solid 298--2743 96.554 21.924 -44.978 0
Liquid 2743-3500 135.980 0 0 0
CaC2 Solid-A 298--720 68.618 11.883 -8.661 0
Solid-B 720-1275 64.434 8.368 0 0
Cr3C2 Solid 298--1600 125.646 23.347 -30.962 0
HfC Solid 298--3000 47.447 5.439 -13.021 0
Mo2C Solid 298--1400 69.036 9.623 -11.464 0
NbC Solid 298--1800 45.145 7.238 -8.996 0
SiC Solid (ex) 298--662 36.489 14.652 -13.037 0
Solid (ex) 662-3200 49.597 2.636 -35.606 0
Solid ({3) 298--678 35.648 15.954 -12.523 0
Solid ({3) 678--3200 50.576 1.992 -37.639 0

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
642 Thermodynamic and thermal properties
Table B.1 (continued)

Formula Phase cp range, T (K) A B C D

Carbides (continued)
TaC Solid 298-4000 43.292 11.351 -8.799 0
TiC Solid 298-3290 49.953 0.979 -14.774 1.887
Liquid 3290-3500 62.760 0 0 0
VC Solid 298-2000 36.401 13.389 -7.113 0
WC Solid 298-2500 43.376 8.636 -9.318 -1.021
W2 C Solid 298-3068 89.747 10.878 -14.560 0
ZrC Solid 298-3500 51.116 3.385 -12.983 0

Nitrides
AlN Solid 298-600 32.267 22.686 -7.904 0
Solid 600-1000 50.216 1.172 -26.054 0
Solid 1000-2000 50.141 0.389 -17.397 0
BN Solid 298-1200 33.89 14.728 -23.054 0
CrN Solid 273-800 41.171 16.318 0 0
HfN Solid 298-1700 46.442 7.029 -7.196 0
Mo2 N Solid 298-800 46.819 57.739 0 0
NbN Solid-A 298-600 36.359 22.594 0 0
Solid-A 600-1643 44.932 8.305 0 0
Solid-B 1643-2323 62.76 0 0 0
Liquid 2323-3000 62.76 0 0 0
Si3N4 Solid 298-2151 76.337 109.039 -6.535 -27.083
TaN Solid 298-3363 55.271 2.720 -12.636 0
Liquid 3363-3500 62.76 0 0 0
TiN Solid 298-3223 49.831 3.933 -12.385 0
Liquid 3223-3500 66.944 0 0 0
VN Solid 298-1600 45.773 8.786 -9.247 0
ZrN Solid 298-3225 46.442 7.029 -7.196 0
Liquid 3225-3500 58.576 0 0 0

Other
MoSi2 Solid 298-2303 67.831 11.970 -6.569 0

Source: Thompson, W.T., Pelton, AD. and Bale, C.W. (1985) Facility for the Analysis of Chemical Thermodynamics (FACT).
Thermfact Ltd, Mount-Royal, Quebec, Canada.
 Thermodynamic and thermal properties 643
Table B.2 Enthalpy of formation (il f H z98 ), Gibbs free energy of formation (il fG298)' entropy (5298)' melting
point temperature (Tmp) and heat of fusion (ilfusHO)

Farmula ilf H298 ilf G298 5298 Tmp ilfusHo

(klima/) (klima/) (J/mal.K) (K) (klima/)

Barides
a-AlB12 -200.8a -206.7a 118.8b 2435a
,B-AlB12 2485a
CrB -75.3a -73.7a 24.1 b 2343c
CrB 2 -94.1a -91.4a 26.2 b 2473a
HfB2 -336.0 a -332.2a 42.7b 3653a
NbB 2 37.3b 3309a
TaB2 -209.2a -206.5 a 44.4b 3373b 83.7b
TiB2 -279.5 d -275.3 d 28.5 d 3193d lOO.4 d
VB -138.5 a -136.8 a 29.3b 2843a
VB2 -203.8a -200.6 a 30.1 b 3020a
ZrB 2 -322.6a -318.2a 36.0d 3323d lO4.6d

Carbides
Al4 C3 -215.~ -203.4d 89.0d 2500d
B4 C -62.~ -62.1 d 27.1 d 2743 d lO4.6 d
CaC 2 -59.8c -64.9c 70.0c 2570e
Cr3C2 -85.4d -86.3 d 85.4d 2073(d/
HfC -208.4c -205.6 c 40.1 c 4201 e
Mo 2C -46.1 b -46.9c 65.8b 2773f
NbC -138.9 d -136.8d 35.5d 3770e
a-SiC -71.6d -69.1 d 16.5d 3103(d)f
,B-SiC -73.2d -70.9d 16.6d
TaC -144.1 d -142.~ 42.4d 4273 d lO4.6d
TiC -184.1 d -180.4d 24.2 d 3290d 71.1 d
VC -100.8b -99.0c 27.7b 2972e
WC -40.6c -38.8c 32.4c 3073(d)f
W 2C 3058f
ZrC -196.~ -193.3d 33.3d 3805d 79.5d

Nitrides
AlN -318.0d -287.0d 20.1 d 2572(d)g
BN -250.9d -225.0d 14.8d 2600(d)d
CrN -117.2 d -92.8d 37.7d 1773(d)g
HfN -373.6c -345.5 c 44.8 c 3660g
Mo2N 1173(d)g
NbN -220.3 c -194.8c 35.3c 2323c 46.0c
a-Si 3N 4 -744.8d -647.3d 113.0d 2151(d)d
TaN -252.3c -223.9c 41.8 c 3363c 67.0c
TiN -337.~ -308.9d 30.2d 3223g 66.9d
VN -217.2d -191.1 d 37.3d 2450g
ZrN -365.3d -337.0d 38.9d 3225d 67.4d
644 Thermodynamic and thermal properties
Table B.2 (continued)

Formula Ilf H298 Ilf G298 5298 Tmp IljusHo

(kllmol) (kJlmo/) (JJmol K) (K) (klima/)

Other
MoSi2 -118.8 c -118S 65.1c 2553h

Ll I H 298 (kJ/mol) = Enthalpy of formation at 298K; standard state, pure phase, at 0.1 MPa (1 atm).
Ll I G298 (kJ/mol) = Gibbs free energy of formation at 298 K; standard state, pure phase, at 0.1 MPa (1 atm).
5298 (J/mol K) = entropy at 298 K.
Tmp (K) = melting point temperature (or decomposition (d at 0.1 MPa (1 atm).
LlfusW (kJ I mol) = heat of fusion.
Sources:
a Cutler, RA. (1991) Engineering properties of borides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S.J. Schneider, Jr), ASM International.
b Thompson, W.T., Pelton, A.D. and Bale, C.W. (1985) Facility for the Analysis of Chemical Thermodynamics [FACT].
Thermfact Ltd, Mount Royal, Quebec, Canada.
C Kosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications, Hemisphere

Publishing Corp., New York.

d Chase, M.W., Davies, c.A., Downey, J.R, Frurip, D.J., McDonald, RA. and Syverud, A.N. (1985) JANAF Thermochemical
Tables, 3rd edn, J. Phys. Chem. Ref. Data, 14, Suppl. l.
e MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 2, Carbides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 2, Battelle, Columbus, OH.
I Shaffer, P.T.B. (1991) Engineering properties of carbides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S.J. Schneider, Jr), ASM International.
g MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 1, Nitrides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 1, Battelle, Columbus, OH.
h Shackelford, J.F., Alexander, W. and Park, J.5. (eds) (1994) CRC Materials Science and Engineering Handbook, CRC Press,
Ann Arbor, Ml.
 Thermodynamic and thermal properties 645
Table B.3 Thermal expansion (a) and thermal conductivity (k)

Formula Thermal Temperature Thermal Temperature

expansion range conductivity, k (K)
coefficien t, a (K) (WjmK)
(10- 6 jK)

Borides
CrB 12.3a 300-1300 20.1 a 300
12.6a 1300-2300
CrB 2 lOS 300-1300 31.8a 300
11.8a 1300-2300 34.0a 1300
55.0a 2300
HfB2 6.3a 300-1300 6.3 b 300
6.8a 1300-2300
NbB 2 8.0a 300-1300 24.0a 300
8.5a 1300-2300 23.4a 1300
40.3a 2300
TaB2 8.2a 300-1300 1O.9b 300
8.8a 1300-2300 13.8b 473
TiB2 4.6a 300-1300 24.0b 300
5.2a 1300-2300 26.3b 473
VB 6.1a 300-2300 26.3a 300
VB 2 7.6a 300-1300 42.2a 300
8.3a 1300-2300 42.0a 1300
67.3a 2300
ZrB2 5.9a 300-1300 23.6b 300
6.5a 1300-2300 24.1 b 473

Carbides
B4C 4.78b 298-773 28.0b 300
5.54b 773-1273 16.0c 1248
6.02b 1273-1773
6.53b 1773-2273
CaC 2 6.3a 300-1400
Cr3C2 11.7a 300-1400 19.1a 300
HfC 6.8a 300-1300 16.3a 300
30.0a 1870
37.0a 2870
Mo2C 7.33d 294-2200 31.8a 300
NbC 7.21a 300-1300 15.0a 300
32.0a 1770
46.8a 2670
a-SiC 5.12e 298-1273 41.0e 293
5.48e 298-1773 33S 873
5.77" 298-2273 25.5e 1073
5.94e 298-2773 21.3e 1273
,a-SiC 3.8e 473 42.0a 300
4.3e 673 19.0a 1000
4.8e 873 13.0a 1500
5.2e 1073
5.8e 1273
646 Thermodynamic and thermal properties
Table B.3 (continued)

Formula Thermal Temperature Thermal Temperature

expansion range conductivity, k (K)
coefficien t, a (K) (WjmK)
(10- 6 jK)

Carbides (continued)
TaC 7.09a 300-1300 21.9a 300
16.0a 1500
21.9a 2000
29.1a 2500
35.9a 3000
TiC 7.95a 300-1300 17.2d 293
VC 7.16d 298-863 9.8a 300
WC 5.76d 294-2477 29.3a 300
W2C 6.4 [OO1]a 29.3a 300
8.1 [100]a
zrC 7.01 a 300-1300 27.2a 1770
39.7a 2770

Nitrides
AIN 4.8a 300-600 320 (theor.)f 300
5.0a 600-1300 180f 300
130f 375
a-BN 2.7 (Par.)g 348-1271 20 (Par.)g 300
6.1 (Par.)g 348-2270 33 (Perp.)g 300
1.1 (Perp.)g 348-1271 13 (Par.)g 1273
2.0 (Perr)g 348-2270 27 (Perp.)g 1273
CrN 0.7 294-477 12.0a 294
1.5h 477-700
3.1 h 700-811
HfN 6.5h 297-1644 19.0a 300
20.6a 1573
Mo2 N 1.8h 294-477 17.8a 294
4.1 h 477-700
5.4h 700-811
NbN 10.1 a 300-1300 4.2a 300
Si3N 4 2.6i 300-1400 29.5i 400
2.9i 1400-1600 25.5i 600
3.0i 1600-1700 23.0i 800
20.5i 1000
18.0i 1200
16.0i 1400
14.0i 1600
13.0i 1700
TaN 3.6h 294-977 5.5a 300
12.1a 1300
TiN 8.1 h 298-866 28.9b 298
9.0h 866-1700 23.9b 400
16.7b 473
 Thermodynamic and thermal properties 647
Table B.3 (continued)

Formula Thermal Temperature Ther11Ul1 Temperature

expansion range conductivity, k (K)
coefficient, a (K) (WjmK)
(10- 6 jK)

Nitrides (continued)
TiN 11.3b 923
VN 8.1 h 294-1366 2.9a 300
1O.Oa 800
ZrN 7.0h 300-1400 28.2a 300
27.2a 1300
Other
MoSi2 8.2Sa 300-13S0 54.0 423
31.0 698
22.2 813
a Kosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications, Hemisphere
Publishing Corp., New York.
b Shackelford, J.F., Alexander, W. and Park, J.5. (eds) (1994) CRC Materials Science and Engineering Handbook, CRC Press,
Ann Arbor, MI.
C Shaffer, P.T.B. (1991) Engineering properties of carbides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses

(Vol. Chairman S.J. Schneider, Jr), ASM International, pp. 804-1l.

d MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 2, Carbides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 2, Battelle, Columbus, OH.
e Shaffer, P.T.B. and Mroz, T.J. (1991) Silicon carbide, in ART Handbook of Advanced Ceramic Materials, Advanced Refrac-
tory Technologies, Inc., Buffalo, NY.
fShaffer, P.T.B. and Mroz, T.J. (1991) Aluminum nitride, in ART Handbook of Advanced Ceramic Materials, Advanced
Refractory Technologies, Inc., Buffalo, NY.
g Hampshire, S. (1991) Engineering properties of nitrides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S.J. Schneider, Jr), ASM International, pp. 812-20.
h MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 1, Nitrides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 1, Battelle, Columbus, OH.
i Shaffer, P.T.B. and Goel, A. (1991) Silicon nitride, in ART Handbook of Advanced Ceramic Materials, Advanced Refractory
Technologies, Inc., Buffalo, NY.
MECHANICAL PROPERTIES AT 293K c

Table C.l Microhardness (Rv ), Young's modulus (E), Poisson's ratio (v), bend strength (O"bend), compres-
sive strength (O"c), tensile strength (O"t) and fracture toughness (K Ic )

Formula Microhardness Young's Poisson's Bend Compressive Tensile Fracture

Hv at load modulus E ratio strength strength strength toughness
(CPa) v O"bend O"c O"t KIc
(CPa) (N) (MPa) (MPa) (MPa) (MPa- m1/ 2 )

Borides
a-AIB 12 23.5 0.3 1a
,B-AIB12 22.5 1.0 1a
CrB 22.8 0.34 O.5b 361 b
11.8-12.7 1a
CrB2 20.7 0.13 0.3b 450b 620b 1279b 731 c
20.6 0.8 O.5a
10.9 1a
HfB2 28.4 5.0 0.3a 500a O.12a 350 70a
21.2 1a
23.5 1.6a
NbB 2 25.5 0.3 a 638 a
20.9 1a
TaB 2 24.5 0.4 0.3 a 687b
19.6 O.5 a
TiB2 33.0 0.6 0.3a 541 b 0.09-0.11a 450 70b 1350b 12r 6.4 O.4a
25.5 1a
VB 531 b
VB2 27.5 0.1 0.3 a 340b
23.6 1.5 1b
ZrB2 22.1 0.2 0.3 a 496b 0.144d 265 b 1587b 198d
17.9 1a

Carbides
A14 C 3 16.0 19.0b
B4 C 35.8 0.6 O.lb 427b 0.17-O.21e 340b 1660b 73b 2.9-3.71
31.5 1.0 19

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
650 Mechanical properties at 293 K
Table C.l (continued)

Formula Microhardness Young's Poisson's Bend Compressive Tensile Fracture

Hv at load modulus E ratio strength strength strength toughness
(GPa) v O'bend O'c O't K[c
(GPa) (N) (MPa) (MPa) (MPa) (MPa m1/ 2 )
0

Carbides (continued)
CaC2
Cr3C2 (10.6-20.6) 1.7b 370b 1048b SOb
(at 1173K)
HfC 26.0 1.0 Oo5b 480 lOb 239h 44b
(at 2914K)
21.0 Ib
Mo2C 1605 1.5 Oo5b S31 b SOb
15.4 1.5 Ib
14.2 1.5 2b
NbC 21.7 1.3 Oo5b 42 1b 3S0b 2423b 67b 3.Sb
20.3 Oo5 Ib
a-SiC 30.0 Ib 408b 0.14e 350 40b 4600e 411b 4.6e
,B-SiC 432b S60b
TaC 17.0 1.0 Oo5b SSOl1 b 0.17-0.24c 220b 100b
TiC 30.0d 494 lOb 0.19c Soob 1380b 6Sb 2.0b
VC 24.8 1.1 Oo5b 430b 620b
WC 21.8b 737 lSb 0.24c S30c 2721 b 3S0b
W 2C 18.1-20.6 Ib
zrC 20.5 Oo5b 49Sb 0.26c 520 80b 834b 10Sb 2.8b

Nitrides
AIN 15.3 1.0 Ib 400b 26Si lS80b 320b
,B-BN 80.0 2.Sb 974b 300b 2S00-32oob 6.0b
72.0 S.Ob
67.0 705b
65.0 1O.0b
40.0 SO.Ob
a-BN 0.1 Ib 100 (Par.)i 20b 240-320b Sl-l11b 16-18b
20 (Perp.)i
CrN 1O.80.9b 320b
HfN 16.7 Ib 480b
MOzN 6.3 0.9b
NbN 18.3 Oo5 Ib 484b 28b
(at 1800K)
a-Si3N 4 2S.0b 313b 0.20-0.2~ 6S6b 689-2760k 4S0b 6.20.6b
,B-Si3N 4 30.8 2b 29Sb 373b
TaN 14.4 Ib S76b
TiN 19.9 O.Sb 390b 260b 1298b 37b
(at 2256K)
VN 13.0 Oo5 Ib 3S0b
 Mechanical properties at 293 K 651
Table C.l (continued)

Formula Microhardness Young's Poisson's Bend Compressive Tensile Fracture

Hv at load modulus E ratio strength strength strength toughness
(CPa) 1/ O'bend O'c O't K 1c
(CPa) (N) (MPa) (MPa) (MPa) (MPa .mII2 )

Nitrides (continued)
ZrN 15.0 35b
(at 2277K)

Other
MoSi2 12.0-13.5 0.16--0.17 370b
(at 1073K)

Sources:
a Cutler, R.A (1991) Engineering properties of borides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses (Vol.
Chairman S.J. Schneider, Jr), ASM International.
b Kosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications, Hemisphere
Publishing Corp., New York.
e Shackelford, J.F., Alexander, W. and Park, JS. (eds) (1994) CRC Materials Science and Engineering Handbook, CRC Press,
Ann Arbor, MI.
d Shaffer, P.T.B. (1991) Zirconium diboride, in ART Handbook of Advanced Ceramic Materials, Advanced Refractory Tech-
nologies, Inc., Buffalo, NY.
e Shaffer, P.T.B. (1991) Engineering properties of carbides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S.J. Schneider, Jr), ASM International.
f Shaffer, P.T.B. (1991) Boron carbide, in ART Handbook of Advanced Ceramic Materials, Advanced Refractory Technologies,
Inc., Buffalo, NY.
gWeimer, AW., Roach, R.P., Haney, CN., Moore, W.G. and Rafaniello, W. (1991) Rapid carbothermal reduction of
boron oxide in a graphite transport reactor. AIChE J., 37, 759.
h MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 2, Carbides, Metals and Ceramics Information Center,
Report No. MCIC-HB-07-Vol. 2, Battelle, Columbus, OH.
I MCIC (1987) Engineering Property Data on Selected Ceramics, Vol. 1, Nitrides, Metals and Ceramics Information Center,

Report No. MCIC-HB-07-Vol. 1, Battelle, Columbus, OH.

)Shaffer, P.T.B. and Goel, A (1991) Silicon nitride, in ART Handbook of Advanced Ceramic Materials, Advanced Refractory
Technologies, Inc., Buffalo, NY.
k Hampshire, S. (1991) Engineering properties of nitrides, in Engineered Materials Handbook, Vol. 4, Ceramics and Glasses
(Vol. Chairman S,J. Schneider, Jr), ASM International.
ELECTRICAL AND MAGNETIC D
PROPERTIES AT 293 K

Table D.l Electrical resistivity (p), temperature coefficient of resistivity (a), Seebeck coefficient (a), Hall
coefficient (RH ), work function (cp), and molar magnetic susceptibility (X)

Formula Electrical Temperature coefficient Seebeck Hall Work Molar

resistivity, of resistivity coefficien t, coefficient, function, magnetic
p x 108 thermoelectric RH x 1010 cp susceptibility,
mm) a x 103 Range power, a (m 3 IK) (eV) X x 106
(11K) (K) (flYIK) (limo/)

Borides
CrB 45.5 1.1 300-1200 -4.7 -1.0 3.16
CrB 2 30 1.2 300-1200 -3.0 -1.2 3.21 390
HfB2 10.6 3.3 293-1523 -1.0 -18.0 3.60 -4.0
NbB2 25.7 1.0 293-1250 -2.8 -1.5 4.08 8.0
TaB 2 32.5 1.2 293-1523 -2.8 -2.1 4.10 -64.8
TiB2 9 2.0 293-1523 -2.9 -19.6 4.10 31.3
VB 35 -5.00.5
VB 2 22.7 2.1 293-1523 -5.8 -0.82 4.03 34.1
ZrB2 9.7 2.3 293-1523 -1.2 -19.0 3.74 -67.7

Carbides
B4C ~1000 0.032 1273-1773 +80 +219
CaC 2 6
Cr3C2 75 2.33 273-373 -6.7 0.5 -0.47
HfC 39 1.42 573-2273 -11.7 -12.4 3.63 ~ -30
Mo2C 71 3.78 473-1073 -1.9 -0.85 3.80 25.3
NbC 36 ~1.35 293-1273 -5.5 0.3 -1.05 3.83 ~18
a-SiC 4 x 105 0.264 1173-1773 >0 4.5
j3-SiC (0.17-1) x 106 >0 5.1
TaC 22 1.07 673-2273 -11.5 -1.11 3.77 ~10
TiC 200 ~1.8 293-1273 -4.5 ~ -14 4.34 ",5
VC 78 1.41 -0.5 0.1 '" -0.7 3.85 ",25
WC 19.2 0.495 293-1773 -23.3 -21.8 3.6 9.8
W 2C 75.7 1.95 473-2273 -8.17 0.02 -13.1 4.58
zrC 76.5 ",1.55 293-1273 -6.30.3 -10.4 3.58 '" -20

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
654 Electrical and magnetic properties at 293 K
Table 0.1 (continued)

Formula Electrical Temperature coefficient Seebeck Hall Work Molar

resistivity, of resistivity coefficien t, coefficien t, function, magnetic
p x 108 thermoelectric RH x 1010 'P susceptibility,
(nm) a x 103 Range power, a (m 3 IK) (eV) X x 106
(11K) (K) (j1VIK) (lImo/)

Nitrides
AIN >10 19 5.35
a-BN 1.7 x 1019 11.8
erN 640 -92.04.0 -264
HfN 32 1.5 77-300 -2.9 -4.0 4.27
Mo2 N 19.8 +2.18 0.5 2.83
NbN 54 3.1 77-300 -1.5 0.52 3.92
Si3 N 4 1019 _1020
TaN 180 0.1 77-300 -1.0 -0.53 25
TiN 40 0.44 273-1473 -7.7 -0.55 4.09 37
VN 60 0.07 273-1473 -5.0 -0.46 130
ZrN 18 2.0 77-300 -5.9 -1.44 3.97 22

Other
MoSi2 21.6 6.38 293-393 -3.0 12.7 4.73 -36.5

Source: Kosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications,
Hemisphere Publishing Corp., NY. Reproduced by permission of Taylor & Francis, Inc., Washington, DC. All rights
reserved.
CHEMICAL PROPERTIES E

Table E.1 Effect of reagent and treatment on solubility or decomposition and degree of oxidation (stability
of 10-15t-tm powder)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Borides
CrB H 2O 373K 0
HCI (d = 1.19) 353K, 5 min 50
HCI(1:1) 373K, 5 min 15
HN03 (d = 1.4) 393K,3.5h 15
HN03 (1:1) 383K,2.5h 15
H 2SO4 (1: 1) 423K,5min 85
Airb 1173-1273K,0.5-5h 2
CrB2 H 2O 373K 0
HCI (d = 1.19; 1: 1) 353K,5min 60
HN0 3 (d = 1.4; 1 : 1) 393K,I-2h 40
H 2S04 (1: 1) 423K,5min 90
NaOH (5%) 353K, 1 h 0
NaOH (20%) 353K, 1 h 0
NaOH (5%) + H 20 2 353K, 1 h 30
Airb 973-1273K,0.5-4.5h 43-75
1373K,5h 20
1473K,I-5h 50-310
1513 K, 1.5-5 h 55-450
HfB2 H 2O 373K 0
HCl (d = 1.19) 293K,2h 20-40
373K,2h 100
H 2S04 (d = 1.84; 1 : 1) 2h 100
HCl04 (d = 1.7) 24h 20-40
HN0 3 (d = 1.4) Boiling, 30 min 100
HN0 3 + 3HCl Boiling 100
HN03 + HF Boiling 100
H 3 P04 Boiling,2h 100
NH4 0H 2h 0
H 20 2 2h 0
Airb 773-873 K, 1-5 h None

Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
656 Chemical properties
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed" weight gain
(g/m2)

Borides (continued)
HfB2 Airb 973-t073 K, 1-5 h to
1273K,1-5h to-25
1373-1473K,1-5h 15-70
NbB2 H 2O 0
HCl 1h 0
HN03 1h 0
HCl+ H 2C20 4 1h >50
HCl+ H 20 2 1h <5
H 2SO4 (1 :1) 1h 50
H 2S04 + H 2C20 4 1h 40
HN03 +3HCl 0
H 2S04 +H20 2 Heating, 1 h >50
H 3P04 (1:1) 393K, 1 h 25
NaOH (5%) 353K,lh 0
NaOH (20%) 353K, 1 h 25
NaOH (6%) + H 20 2 353K,lh tOO
Airb 723-973 K, 1 h 2.5-49.9
t073-1273K, 1 h 162-325
TaB2 H 2O 0
HCl (1: 1) 1h 0
HCl+ H 20 2 1h 0
HCl+H2C20 4 0
HN03 +3HCl 1h 0
H 2S04 (1: 1) 40
H 2S04 +H20 2 40
H 2S04 + H 2C20 4 40
HN03 (1: 1) 0
H 20 2 75
H 20 2 + H 2C20 4 90
H 3P04 (1: 1) 0
NaOH (5%) 353K,lh 50
NaOH (20%) 353K, 1 h 50
NaOH (5%) + H 20 2 353K,lh tOO
Naf03 Melting >50
Air 973-1173K,1-2h 12.4-33.4
TiB2 H 2O 0
HCl (1: 1) Heating, 1 h 40
HCl (d = 1.19) + H 20 2 12 min tOO
HCl+H2C20 4 Heating,lh 40
H 2S04 (1: 1) Heating, 12 min tOO
H 2S04 +H20 2 1h >50
H 2S04 + H 2C20 4 tOO
HN03 (1:1) 12 min tOO
H 20 2 tOO
NaOH (5%) 353K,lh 0
 Chemical properties 657
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Borides (continued)
TiB2 NaOH (20%) 353K, 1 h 15
NaOH (5%) + H 20 2 100
Na2C03 Melting 100
O2 1273K, 0.68-102h 4-200
1373K,20h 60-300
1473K, 2-100h 260
Airb 1573K,1-5h 100-740
1673K,lh 130-220
1773-1873K,1-5h 40-110
VB 2 H 2O 0
HCI(1:l) 373K, 1 h 20
HCl+ H 20 2 1h 100
HCI+ H 2C20 4 Boiling, 1 h 20
H 2SO4 Boiling, 1 h 60
H 2 S04 +H 20 2 1h 100
H 2 S04 + H 2C 20 4 1h 50
HN03 (1: 1) 1h 100
HF 0
H 20 2 12 min 100
NaOH (5%) 353K, 1 h 0
NaOH (5%) + H 20 2 353K, 1 h 100
O2 973K Intensive oxidation
ZrB2 H2O 0
HCI(1:l) 373K, 1 h >50
HCI+ H 20 2 1h >50
H 2S04 (1: 1) 1h >50
H 2S04 +H2 0 2 1h >50
HN0 3 (1: 1) 1h <5
H 20 2 1h <5
H 20 2 + H 2C20 4 1h >50
H 3P04 (1: 1) 1h 100
NaOH (5%) 353K,lh <5
NaOH (25%) 353K, 1 h 25
Airb 1073 K, 1-5 h None
1173-1273K, 1-5h 10
1373-1473K,1-5h 10-60
1273K, 150h 300
1373K,20h 220
1573K, 1-5h 90-270
1673 K, 30 min-3 h 160-300

Carbides
B4 C Mineral acids Boiling 10
Alkali solutions Boiling 10
O2 1273K >50
658 Chemical properties
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Carbides (continued)
B4 C Cl2 1273K >50
Br2 0
CaC2 H 2O 293K >50
Dilute mineral acids 293K >50
Alkali solutions 293K >50
H 2S04 (d = 1.84) 553K >50
HN03 (d = 1.43) 383K 0
H2 (dry) 2473K 0
N2 1223-1323K >50
O 2 (dry) 973-1073K >50
Cl2 (dry) 523K >50
NH3 923K >50
Cr3C2 HCl (d = 1.19) 293K,48h 0
HCI (1 :1) 381 K, Ih 0
H 2S04 (d = 1.84) 553K, 1 h 65-70
H 2S04 (1: 1) 409K, 1 h 30
HN0 3 (d = 1.43) 383K, 1 h 0
HN0 3 +3HCl 379K, 1 h 10
HN0 3 (d = 1.43)+ HF 393K, 1 h 0
H 2S04 (d = 1.84) + cr03 393K, 1 h 70
NaOH (30%) 383K, 1 h 0
O2 673-773 K, 1 h 0.4
1273K, 1 h 44
HfC HCI (d = 1.19) 373K, 1 h 0
H 2S04 (d = 1.84) 503-533 K, 1 h >50
H 2S04 (1 :4) 373K, 1 h 10-12
HN0 3 (d = 1.43) 373K, 1 h >50
H 3P04 (d = 1.7) 533K, 1 h >50
H 20 2 (30%) 383K,lh 0
HN0 3 +3HCl 383K,lh 100
H 20 2 (30%) + C4 H s07 383K,lh 0
H 20 2 (30%) + C 2H 20 4 383K,lh 100
Organic acids 383K,lh 0
O2 873-1173K Oxidation begins
1273K 100
Mo2C HCI (d = 1.19) 403K,2h 10
H 2S04 (d = 1.84) 553K,2h >50
H 2S04 (1 :4) 383K,2h 10-15
HN03 (1 :1) 383K,2h 100
H 3 P04 (1 :3) 393K,2h 25
HCl04 (1 :3) 393K,2h 100
HCI04 (d = 1.35) 393K,2h 40
HN03 +3HCl 393K,2h 100
NaOH (20%) 393K,2h 0
NaOH (20%) + H 20 2 (30%) 393K,2h 60
 Chemical properties 659
Table E.l (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Carbides (continued)
Mo 2C O2 773-1073K Insignificant
>1073K Actively oxidized
NbC HCl (d = 1.19) 383K, 1 h 0
H 2S04 (d = 1.84) 553K, 1 h >50
HN03 (d = 1.43) 383K, 1 h 0
H 3 P04 (d = 1.7) 583K, 1 h 0
H 20 2 (30%) 383K, 1 h 100
(NH4hS208 (20%) 383K, 1 h 10-15
HN03 (d = 1.43) + HF 383K,30min 100
02b 823K Noticeable oxidation
SiC Mineral acids (not H 3 P04) Boiling 0
H 3 P04 (d = 1.75) 473-523K >50
H 2O 1773K,15min llg/m2 .h
1923K, 15 min 52g/m2 .h
2373K 58000 g/m2 .h
2723 K, 15 min 73400 g/m2 . h
O2 1773 K, 15 min 35g/m2 .h
1923K,30min 36g/m2 .h
2373K,30min 15000 g/m2 . h
2723K,15min 33700 g/m2 . h
CO2 1773K,15min 4.3g/m2 .h
1923K,15min 34.1 g/m2 . h
2373K,15min 30400g/m2 h
2723K,15min 48600g/m2 .h
TaC HCI (d = 1.19) 1673K,15h 0
H 2S04 (d = 1.84) 553K,15h 80
HN0 3 (d = 1.43) 383K, 1 h 0
H 3 P04 (d = 1.7) 583K, 1 h 0
H 20 2 (30%) 583K, 1 h 15-17
(NH4hS208 (30%) 583K,lh 10-12
HCl + H 20 2 (30%) 583K, 1 h 0
H 2S04 + H 20 2 (30%) 583K, 1 h 20-25
HN03 (d = 1.43) + HF 583K,30min 100
H 20 2 (30%) + C4H 80 7 583K, 1 h 50
O2 773-873K Insignificant oxidation
973K Active oxidation
TiC HCl (d = 1.19) 383K, 1 h 0
HCl (1: 1) 383K, 1 h 0
H 2S04 (d = 1.84) 533-573 K, 1 h >50
H 2S04 (1 :4) 413K, 1 h 0
HN03 (d = 1.43) 383K, 1 h >50
HN03 (1: 1) 383K,lh 100
H 3 P0 4 (d = 1.7) 573K, 1 h 0
H 20 2 (30%) 373K, 1 h 100
(NH4hS208 (25%) 383K, 1 h 15-20
660 Chemical properties
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed" weight gain
(g/m2)

Carbides (continued)
TiC O2 1173K, 1 h 1210
02 b 1473K Noticeable oxidation
N2 1673K,36.5-37h Interacts
N2 2073K,8h Interacts
WC HCI (d = 1.19) 403K,2h 50
HCI (1: 1) 403K,2h <5
H 2S04 (d = 1.84) 553K,2h 100
H 2S04 (1 :4) 383K,2h <5
HN03 (d = 1.43) 383K,2h 100
HN0 3 (1 :1) 383K,2h >50
H 3 P04 (d = 1.75) 573K,2h 10
HCI04 573K,2h 60
HN03 +3HCl 393K,2h 100
NaOH (20%) 393K,2h 0
NaOH (20%) + H 20 2 393K,2h 10--15
O2 773K Oxide film appears
zrC HCI (d = 1.19) 383K, 1 h 0
H 2S04 (d = 1.84) 553K, 1 h >50
H 2S04 (1 :4) 413K,1h <5
HN03 (d = 1.43) 383K,1h >50
H 3 P04 (d = 1.7) 503-533 K, 1 h >50
H 20 2 (30%) 383K, 1 h 0
(NH4 hSzOs (25%) 383K,1h 60-70
HN03 +3HCl 383K,lh 90
HCI+ H 20 2 383K, 1 h 50
H 2SO4 + H 20 2 (30%) 383K, 1 h 100
H 20 2 + C4 H s07 383K,1h 0
H 20 2 + C2H 20 4 383K, 1 h >50
Organic acids 383K, 1 h 0
O2 1173K 46000
02 b 1373K Oxidized
N2 1673K,36.5-37h Interacts
N2 2073K,8h Interacts

Nitrides
AlNe H 2O 373K,1h 60
HCI (1: 1) 373K, 1 h 75
HCl (d = 1.19) 378K,1h 50
H 2SO4 (1: 1) 413K, 1 h 100
H 2S04 (d = 1.84) 553K, 1 h 5
HN03 (d = 1.4) 378K,1h 80
NaOH (10-40%) Boiling, 1 h 100
Air 1173-1193K Completely oxidized
Cl2 1033K >50
 Chemical properties 661
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Nitrides (continued)
AlNd H 2O 373K,lh 0
HCI (1: 1) 373K, 1 h 5
HCl (d = 1.19) 378K, 1 h 5
H 2S04 (1 :1) 413K, 1 h 5
H 2S04 (d = 1.84) 553K, 1 h 5
HN03 (1: 1) 378K, 1 h 5
HN03 (d = 1.4) 393K,lh 0
NaOH (10--20%) Boiling, 1 h 100
NaOH (40%) 393K,lh 70
o:-BNe H 2O 373K,lh 30
HCl (1: 1) 373K,lh 6
HCl (d = 1.19) 378K, 1 h 0
H 2S04 (1 :1) 413K, 1 h 5
H 2S04 (d = 1.84) 553K, 1 h 40
HN03 (1:1) 378K,lh <5
HN03 (d = 1.4) 393K,lh 20
NaOH (10--40%) Boiling, 1 h 0
O2 973-1073K Oxidation begins
Cl2 Red heat Interacts
o:-BN f H 2O 373K, 1 h 0
HCl (1: 1) 373K,lh 0
HCI (d = 1.19) 373K, 1 h 0
H 2SO4 (1: 1) 413K, 1 h 0
H 2SO4 (d = 1.84) 553K,lh 30
HN03 (1 :1) 393K,lh 0
HN03 (d = 1.4) 393K,lh 0
NaOH (10--40%) Boiling, 1 h 0
erN H 2O Boiling,6h 0
HCI (1: 1) Boiling,2h 5
HCl (d = 1.19) 5
H 2SO4 0
H 2SO4 (d = 1.84) 0
HN03 (1: 1) 0
HN03 (d = 1.4) 10
HCl04 (d = 1.35) 100
H 20 2 (30%) 0
NaOH (10--40%) 0
O2 1173-1273K Completely oxidized
H2 Stable on heating
HfN H 2O 373K,6h 0
HCI (d = 1.19) 303K, 1 h 0
HCI (1: 1) 323K, 1 h 5
HCI (d = 1.19) 323K, 1 h 10
HCI(1:l) 368K, 1 h 85
HCl (d = 1.19) 368K,lh 95
662 Chemical properties
Table E.l (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Nitrides (continued)
HfN H 2S04 (d = 1.84) 303K, 1 h 0
H 2S04 (1: 1) 323K, 1 h 10
H 2S04 (d = 1.84) 323K, 1 h 5
H 2S04 (1: 1) 368K, 1 h 95
H 2S04 (d = 1.84) 368K,lh 75
HN0 3 (d = 1.4) 303K, 1 h 0
HN03 (1:1) 368K,lh 85
HN03 (d = 1.4) 368K,lh 75
Hel (1:1) + K2S04 (5%) 373K, 1 h 100
H 20 2 (30%) Boiling, 1 h 0
NaOH (10-40%) Boiling, 1 h 100
O2 923K Oxidized
M02N Hel (dilute) Boiling 0
HCl (cone.) Boiling 0
HN0 3 (dilute) Boiling 0
HN0 3 (cone.) Boiling 0
NbN Hel (1 :3) Boiling,2h 5
HCl (d = 1.19) Boiling,2h 0
H 2S04 (1: 1) 293K,24h 0
H 2S04 (1: 1) 413K,2h 15
HN0 3 (1: 1) Boiling,2h 0
HN0 3 (d = 1.4) 0
HCl04 (1 :3) 0
3HCl+ HN0 3 0
HCl04 + Hel (1 : 1) Boiling,2h 5
HN0 3 + HF (1 : 1) 5 min 100
K2S04 + H 2SO4 2 min 100
H 20 2 (30%) 2h 85
NaOH (10-40%) 2h 15
NaOH (40%) + H 20 2 Boiling,2h 100
O2 773K Oxidized
H2 Up to high Stable
temperatures
Si3N4 HCl (d = 1.19) Boiling, 500 h 0
HN0 3 (d = 1.4) Boiling, 500 h 0
H 2S04 (10%) 343K,500h 0
H 2S04 (77%) 293K,500h 0
H 2S04 (85%) 293K, 500h 0
HP03 293K,500h 0
H 2P20 7 293K,500h 0
NaOH (20%) 293K,500h 0
NaOH (50%) 293K, 5h 0
HF (48%) 343K,3h 0
H 2S04 (d = 1.84) 553K, 6h 100
O2 High temperatures No interaction
 Chemical properties 663
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed a weight gain
(g/m2)

Nitrides (continued)
Si3N4 O2 1273K Slowly oxidized
H2 High temperatures No interaction
Cl2 623-693K No interaction
TaN H 2O Boiling,6h 0
HCl (cone.) Boiling,2h 0
H 2SO4 (cone.) Boiling,2h 0
HN03 (cone.) Boiling,2h 0
H 3P04 (cone.) Boiling,2h 0
HCI04 (cone.) Boiling,2h 0
HN03 +3HCI Boiling,2h 0
HN03 + HF (1 : 1) 5 min 100
H 20 2 (30%) 2h 60
H 2SO4 + H 20 2 (2: 1) 2h 5
K2S04 + H 2SO4 5h 100
NaOH (40%) + H 20 2 2h 100
O2 >1073K Oxidized
H2 Heating Decomposed
TiN H 2O 373K, 6h 0
HCI (1: 1) 373K, 1 h 0
HCI (d = 1.19) 378K, 1 h 0
H 2SO4 (1:1) 413K, 1 h 5
O2 973-1073K Completely oxidized
H2 >1473K No interaction
CO2 1373K Oxidized
Cl2 573-673K Decomposed
VN H 2O 373K,6h 0
HCI(1:1) 368K, 1 h 0
H 2 SO4 (1:1) 413K, 1 h 0
H 2SO4 (d = 1.84) 368K, 1 h 0
H 2SO4 (d = 1.84) 553K, 1 h 15
HN03 (1:1) 323K, 1 h 70
HN03 (1:1) 368K,lh 100
HN03 (d = 1.4) 323K, 1 h 85
HN03 (d = 1.4) 368K,lh 100
H 20 2 (30%) Boiling, 1 h 20
NaOH (10-40%) Boiling, 1 h 0
O2 773K Oxidized
ZrN H 2O 373K,6h 0
HCI (d = 1.19) 303K, 1 h 0
HCI (1: 1) 368K, 1 h 55
HC} (d = 1.19) 378K,lh 95
H 2SO4 (d = 1.84) 303K, 1 h 0
H 2S04 (1 :1) 368K,lh 90
H 2S04 (d = 1.84) 368K,lh 90
HN03 (1:1) 323K, 1 h 0
664 Chemical properties
Table E.1 (continued)

Formula Reagent Treatment % soluble Degree of oxidation

or with gases
decomposed" weight gain
(g/m2)

Nitrides (continued)
ZrN HN03 (d = 1.4) 323K, 1 h o
HN0 3 (1 :1) 368K,lh o
HN0 3 (d = 1.4) 368K,lh 10
HN03 (d = 1.4) 368K,6h 35
HN03 +3HCI 293K, 24h 20
HN03 +3HCl 378K,2h 75
HCI04 + HCI (1 : 1) 293K,24h 25
HCl04 + HCl (1 : 1) 378K,2h 90
HN03 +HF Boiling, 5 min 100
HN03 + H 20 2 (1 : 1) 293K,24h 5
HN03 + H 20 2 (1 : 1) Boiling,2h 35
H 2S04 + H 20 2 (2: 1) 293K,24h 75
NaOH (10%) 378K, 1 h o
NaOH (20%) 393K, 1 h 100
NaOH (40%) 393K,6h 100
O2 833-953K Initial oxidation
O2 1373K Completely oxidized
H2 1373K No interaction

Other
MoSi2 HCI (d = 1.19; 1: 1) 378K,3h o
HN03 (5%, 10%) 343K,lh o
H 2 SO4 (d = 1.84) 553K,2h o
H 2 SO4 (1 : 1, 1 : 10) Boiling, 2-4 h o
H 3 P04 (d = 1.21) Boiling,2h o
HF+HN03 2h 100
HN0 3 +3HCl o
NaOH (40-80%) Ih 85
O2 1373K,20h 14
O2 1423 K, 8-200 h 20-80
O2 1473K,4-100h 3-21
O2 1773K,4h 13

a <5 is 'practically not decomposed'; >50 is 'decomposed'.

b Hot-pressed samples with porosity close to 1%.
c 20 /-Lm reagent grade power.
d High purity O.5/-Lm single crystals.
e 10 /-Lm reagent grade powder.
f 10 /-Lm high purity powder.
Source: Kosolapova, T.Ya. (ed.) (1990) Handbook of High Temperature Compounds: Properties, Production, Applications,
Hemisphere Publishing Corp., New York. Reproduced by permission of Taylor & Francis, Inc., Washington, DC. All
rights reserved.
INDEX
Page numbers appearing in bold refer
to figures and page numbers
appearing in italics refer to tables.
Abrasive jet mixing head 23
Abrasive waterjet cutting 20-2, 22
Acheson process 115-29
basic description 116-26
crushing and grading 126
effluent CO 123
furnace design and operation
120-5, 122
history 115-16
manufacturing cost factors 126-7
original furnace design 115, 116
product form 117, 117
raw materials preparation 118-20
SiC separation 125-6
Activation energies of transition
metal borides 203
Adiabatic reaction temperature 187
Advanced ceramics
classifications 5
functionality 5
origins 4-5
recent status trends 5
Aerosols, aerosol processes 307--42
applications 317-36
design and operation 315-17
dynamics 281-93
externally heated reactors 316
flame reactors 316-17
fundamentals 308-15
gas-to-particle conversion 308-14,
308,337
chemical reaction and particle
formation 309-10
particle growth 310-12
particle morphology 312-14
precursor gases 308-9
general dynamic equation 284
nucleation 282-3
particle deposition 293
particle growth 283-92
particle-to-particle conversion
312-15,313,338
chemical reaction and particle
morphology 314-15
liquid and solid precursors 314
vapor deposition 292-3
Agglomeration and regrowth 467
Aggregate particles 287-92, 290, 293
AlN-H20 reaction 2
Al 2 0 3
carbothermal nitridation 103
vaporization rates 89, 89
A120rC-N2 system phase stability
diagram 99
Alumina-based composites 221
Alumina-based materials insulation
621
Alumina-silica insulation 621
Aluminum nitride (AlN) 7
aluminum chloride routes 404
applications 317
carbothermic reduction in flowing
nitrogen atmosphere 102
chemical purification 499-500
controlled direct nitridation 245-9,
245, 247, 248
effect of additives 101
effect of impurities 65-6
effect of oxygen 62--4, 65
effect of Si on thermal conductivity
479,481
effect of syntheSis method 66-7
effect of temperature on degree of
reaction 101
film deposition 586-9, 587, 590
gas-to-particle conversion 319-23,
319-22
liquid phase synthesis processes
403--4
moving bed furnace synthesis
process 145
organoaluminum compound
routes 404
particle-to-particle conversion
318-19,319
plasma synthesiS 365-9, 368
powder characteristics 58-67
powder synthesis 97-104
precursor and nitrided product 100
property comparison 255
pusher furnace synthesis process
144
reaction kinetics 251-5, 252-4
self-propagating direct nitridation
249-51,249,250,251
sintering additives 62, 64
sintering constant 44
sintering developments 60-2
spray drying 540-2
synthesis kinetic data 102
thermal conductivity (TC) 66
Amidogen radicals (NH2) 300
Amorphous transition metal borides
405
Arc plasmas 361
Armor systems 22-3
Automotive applications 27-35
Automotive-related engine
components 31
B20 3 vaporization 86, 88, 89, 89
B4 C-TiB2 composite powders 356
Ball mills 467
stirred 467-9, 468, 469
vibrating 471-3, 472, 472, 473
Ballistic performance of ceramic
targets 28, 29
Bearings 19
Borides 15
amorphous transition metal 405
carbothermal reduction reactions
80,81,82
liquid phase synthesiS processes
405
plasma synthesis 382-3, 382
Boron carbide (B 4C) 12-14
aerosol processes 330-3, 333, 334
applications 330
B/C ratio 13, 14
chemical purification 499
crushing and grading 134-5
electric arc furnace process 131-5
film deposition 599
platelets 428, 429
powder grades 134, 134
powder properties 135
powder synthesis 89-94, 91, 92, 94
pusher furnace synthesis process
142
raw materials preparation 132
666 Index
Boron carbide (B 4 C) contd
synthesis kinetics 94
thermite reactions 236-8, 237, 238,
243,244
Boron-carbon phase system 12, 13
Boron nitride (BN) 7-8
aminoborane and related routes
404
applications 326
film deposition 589-91, 591
gas-to-particle conversion 326-7,
327
liquid ammonia-liquid boron
trichloride route 403-4
liquid phase synthesis processes
403-4
particle-to-particle conversion
327-8,329
Burners 23-5
Cam followers 32
Carbides 10-15
carbothermal reduction reactions
80,81,82
film deposition 596-9
liquid phase synthesis processes
405
molten salts 405
plasma synthesis 372-3, 373-82
powder synthesis 89-94
Carbon-based materials, insulation
621
Carbon monoxide monitors 76
Carbon removal
bound carbon 492, 493, 493
free carbon 483-92, 484--91, 486,
488,492
Carborundum, see Silicon carbide (SiC)
Carbothermal nitridation
process 179
reactions 147
Carbothermal reduction reactions 80,
163,81,82
free energy change vs temperature
82
gas phase in 88-9
kinetics 146
reported models 84
whiskers 416-19, 418
Carbothermal reduction synthesis
79-113
kinetics 81-7
overall process 79-81
safety issues 76-7
see also specific processes
Carbo thermal synthesis reactions
enthalpies of reaction 147
material and energy balance 151-2
unique features 148
Centrifugal impactors 475
Ceramic armor 22-3
Ceramic fibers, see Fiber properties;
Fiber synthesis processes
Ceramic matrix composites (CMC)
433, 452, 453
process overview 409-10
Chemical impurities, origin of 480-3
Chemical ovens 207-8, 235
Chemical properties 655-64
Chemical purification 479-503
effect of chemistry on processing
and properties 479-80
Chemical vapor deposition (CVD)
276,433,547-63
bench-scale reactors 548, 550
ceramic materials 549,558-60,
559-61
chemical kinetics 554-5, 555
cold-wall reactors 548, 550
commercial reactors 550-2, 551
flow control 560-2
fundamentals 552-7
history 547-8
hot-wall reactors 548, 550
interrelated parameters 552
mass transport 555-7, 556
modeling 552-7
organometallic (OMCVD) 557-8
organometallic precursors 557-8
overall process 545
particle-precipitation-aided 293
practical systems 560-3
pressure 562
processes 552, 552
reaction classifications 557
reactions/materials 557-60
safety issues 545-6
system configurations 548-52
temperature 562
thermochemical analysis/
assessment 553-4, 553, 554
see also Plasma-assisted chemical
vapor deposition (PACVD);
Plasina-enhanced chemical
vapor deposition (PECVD)
Chemical vapor infiltration (CVI)
563-73
commercial isothermal-isobaric
system 571
developmental forced system 572
evolution of microstructure 567
fiber-matrix interface 570-3
fibrous preforms 569-70
fundamentals 565-7, 566
general relationships 565-7
history 564
load-displacement curves for
four-point flexure tests 570
markets 564-5
modeling 567-8
overall process 545
practical systems 573
preform geometries 569-70
properties of fibers 569, 569
safety issues 545-6
techniques 563-4, 563
CHEMKIN codes 302
Coatings 545-6
Cold plasmas 359
Collision frequency function 286, 288
Colloid stability 508-9
Combustion front
structure 192-9
velocity 204, 204, 205
Combustion modes 207
Types I-IV 195,196
Combustion nitridation 189-90, 191
Combustion syntheSis processes
181-2
overall process 181-2
principles 183-6
safety issues 182
schematic 184
Combustion technology, historical
development 183
Combustion wave 186, 186, 192, 193,
195,195,196,197
Comminution 462-7
Composites 15, 221-2, 356
aerosol processes 335-6
thermite reactions 240-2, 244
see also specific types
Continuous stirred tank residence
(CSTR) 176
time distribution of solids 169, 171
Corrosion resistant applications 26-7
Counter-current filtration
combustion 220
Counter-flow liquid injection plasma
reactor 364, 365
Crucibles 25
Crystal field stabilization energy
(CFSE) 513
Crystallographic properties 639-40
CRYSTAR@ SiC diffusion
components 36
DC-RF combined plasma torch
device 363-4, 364
Debye-Huckel approximation 506
Decomposition 85,87
Densification techniques 16-17
Diffuse double layer 506, 506
Diffusion control, product layer 83-5,
84
Dispersion, see Solids dispersion in
liquids

Ditungsten carbide (W2 C) 44-5
Electric arc furnace process 131-6
boron carbide manufacture 131-5
crushing and grading 134--5
design and operation 132-4, 133
non-oxide ceramics 135
Electric double layer 507, 507
Electrical properties 653-4
Electrically conductive ceramics 25-6
Electronic substrates 37, 37, 38
Electrothermal fluidized bed (EFB)
171-6
above bed product discharge 173,
174-5
advantages 176
below bed product discharge
171-4, 172
petroleum coke macro porosity
175-6, 175-6
product properties 175
Energy balance, carbothermal
synthesis process 151-2
Fiber properties 446-52, 447
electrical properties 451-2
fracture toughness 448-9
high temperature phenomena
449-51,449,450
relationship with process and
structure 433, 434
tensile strength 446-8, 448
thermal properties 446, 451
Young's modulus 448
Fiber synthesis processes 433-55
amorphous phase 441-2, 442, 443
applications of fibers 452
,B--SiC phase 442-3
carbon phase 443-4, 444
composition and structure 438-46,
439,440,440,441,441
future developments 452-3
general process 434-6, 434
large scale structure 445-6
nanoporous phase 444--5, 445, 446,
447
overview 409-10
pyrolysis process 435
Si-C-O fiber 436-7
Si-N fiber 438
Si-N-C fiber 438
Si-N-O fiber 438
specific processes 436-8
Films 545-6
Filtration combustion 184
Finishing of monolithic ceramics 17
Fluid energy mills
loop type 473-5, 474
pancake type 474, 474
Fluidized bed jet mill 474-5, 475, 475
Fluidized bed reactor processes
169-80
applications 170-9
background 169-70
batch process 179
heated by radiation from
exothermic combustion
reaction 178,179
miscellaneous processes 176-9
multi-staged 176-9, 177
see also Electrothermal fluidized
bed (EFB)
Fracture mechanics 462-7
Fuchs-Sutugin factor 311
Fuel injectors 32
Gas phase 88-9
Gas phase synthesis 307
overall process 273
reaction kinetics 278-81
safety issues 273-4
thermodynamics 276-8
see also Aerosols, aerosol processes
Gas pressure sintering (GPS) 55
Gas-solid combustion 183, 190, 193,
208-24
Gas-solid reactions 217-21, 244-69
reactor configuration 183, 184
Gas turbines 34, 35
Gasless combustion 183-4, 190, 193,
197, 199-208
macro kinetics and structural
changes 199-202
mechanism 200
melting effects 202-5
phase transformation 202-5
with reducing step 205-7
Glow discharge plasmas 580-1,583
Glow discharge tube 581, 581
Glow plugs 27-8, 31
Goldschmidt process 236
Graphite heating elements 621, 627-8
Green forming of monolithic
ceramics 16
Grinding
autogenous 467
specific energy 466-7
very fine / ultrafine 467
Gun barrel 38
Halogen-based precursors 415-16
Halogen precursors 300-1, 300
Hamaker constant 508
Hammer mills 475
Hard metals 43
compositions 45-7
Heat balance calculations, high
temperature furnaces 626
Index 667
Heat capacity estimation 187, 188, 189
Heat transfer behavior 150-1, 150
Heat transfer mechanisms, heat flux
values for high temperature 150,
151
Helicopter seats 27
HEPA cartridge filters 2, 76
HfB 2 , SHS diagrams 198
High efficiency particulate air
(HEPA) vacuum filtering
equipment 2, 76
High frequency discharges 361-2
High pressure plasmas 359
High temperature applications 23-5
High temperature furnaces
atmosphere 628
batch 611-13, 611, 624--5
bell (removable heating chamber)
612
box (front loading) 611
car (roll-in hearth) 612-14
Carpet Hearth 616--17
configurations 610-18, 624-6
continuous 613-18, 614, 625-6
control systems 627-9
cooling water 628
critical systems 628
design considerations 609-29
design package selection 621-9
elevator (bottom loading) 611, 612,
613
heat balance calculations 626
heat sources 618-21, 620
heating elements 623
insulation 621, 622, 623--4
material handling 628-9
pit (top loading) 611
process and product
considerations 609-10
production format 624-6
pusher 614-15, 615
roller hearth 616
rotary tube 617, 618, 619
safety issues 607-8
types 605-7, 606
vertical tube 617-18
walking beam 615-16, 616, 617
High temperature graphite reactors
76
High temperature rotary kiln (HTRK)
160
Hot isostatic pressing (HIPing) 17
Hot pressing 17
Hybrid plasma reactor 362
Igniters 30
Ignition of reacting systems 190-2,
208
Inductively coupled plasma (ICP) 362
668 Index
Inert gases 76
Infiltration processes 545-6
see also Chemical vapor infiltration
(CVIl
Interaction energy curves 508, 509,
512
Isoelectric point (IEP) 513-15, 514, 515
Kelvin equation 311
Kinetic expressions, forms of f(X)
and F(Xc) 195,196
Knudsen number 286
Krieger-Dougherty equation 516
Laser mirror 37
Laser processes 343-58
applications 351-7
chemistry 344-6
consolidation 352-5, 355
economic considerations 349-50
fundamentals 346-9, 347-9
powder characteristics 349
powder processing and properties
346,350,351-2,354,355-7,355
powder synthesis cell 345
reactor design 344
Laser sources 343-4
Leaching
applications 496-500
fundamentals 492-6
kinetic models 494, 494
two-stage process 496, 497
Liquid phase synthesis processes
389-410
overall process 389
safety issues 389-90
Local thermodynamic equilibrium
(LTE) 359
Low pressure densification
techniques 16
Low pressure plasmas 359, 360
MAEROS multi-component sectional
code 285-6
Magnesium-thermite reaction 206,
206,236-40,238,239,241,242
Magnetic properties 653-4
Manufacturing 15-17
Market for advanced non-oxide
ceramics 18
Mass transfer processes 140, 148-50,
148
Material balance, carbothermal
synthesis process 151-2
Material Safety Data Sheets (MSDS) 2,
76,182
Mechanical properties 649-51
Melting effects 202-5
Metal impurities 492-500
Metal matrix composites (MMCs) 452
Metal matrix precursors 242-4
Microwave coupled plasma (MWP)
362
Mixed metal carbides, rotary tube
reactor processes 166-7, 167
Molybdenum disilicide, heating
elements 619, 627
Molybdenum heating elements 619,
627
Monolithic ceramics 5-15
finishing of 17
green forming of 16
Moving bed furnaces 137
advantages 140-1
design considerations 154
design parameters 147
disadvantages 141
feed characteristics 147
industrial powder synthesis
processes 144-6
schematic 139
synthesis process summary 145
Multiple plasma torch reactor 362-3,
363
Nickel aluminide synthesis 200
Nickel-aluminum phase diagram 200
Niobium-nitrogen system 190, 195
Nitridation
diffusion controlled 211
kinetically controlled 211
Nitrides 7-10
carbothermal reduction reactions
80,81,82
film deposition 586-96
molten salts 405
plasma synthesis 365-73, 366
powder properties 404
powder synthesis 89-94
thermochemistry 404
Non-aqueous media 509-10
Non-oxide ceramics 3-43
applications engineering 18-38
commercial markets 1
electric arc furnace process 135
growth of 1
trace impurities 147
typical properties 5, 6
see also specific materials and
applications
Non-oxide slips, rheology 516-19,
517,518
Nucleation
aerosols 282-3
kinetic mechanism 85
Nuclei-growth control 84, 85-6
Order of reaction 84, 87
Organometallic chemical vapor
deposition (OMCVD) 557-8
O-ring fittings 397, 397
Oxide-based precursors 416-19
Oxygen removal 492-500
Particle deposition, aerosols 293
Particle growth, aerosols 283-92
Particle-precipitation-aided chemical
vapor deposition (PP-CVD) 293,
335
Petroleum coke macroporosity 175-6,
175-6
Phase boundary reaction control 84,
86-7
Phase transformation 202-5
Physical vapor deposition (PVD) 7
Plasma-assisted chemical vapor
deposition (PACVD) 545, 580
Plasma characterization 581-4
Plasma classification 359, 360
Plasma-enhanced chemical vapor
deposition (PECVD) 545, 579-603
advantages and limitations
599-600
chemical characteristics 583-4
electrical characteristics 582
film deposition 586-99
kinetics 588
microwave apparatus 589
overall process 583
physical characteristics 582
plasma process parameters 584-6
Plasma generation 361-2
Plasma processes 359-87
interaction of homogeneous and
heterogeneous 585
particle synthesis 359-60
powder synthesis 365-83
Plasma reactors 362-4
Plasma state, definition 359
Plastic matrix composites (PMCs) 452
Platelets
process overview 409-10
synthesis 426-30, 426-9
Plug flow reactor (PFR) 138, 170
Point of zero charge (PZC) 513
Polycarbosilane 436-7, 437
Powder characteristics 43-73
Pre-combustion cups 31, 32
Pressure densification techniques
16-17
Pressureless densification techniques
16
Product layer diffusion control 83-5,
84
Pump seals 19-20
Purification, see Chemical
purification

Pusher furnaces 142-4, 143, 144,
614-15,615
advantages 137-9
characteristics as reactor 137
common features 138
disadvantages 139-40
effect of pore size on calculated
mass transfer flux rates 149,
150
flexibility 138-9
fundamental physio-chemical
considerations 146-52
heat transfer behavior 150-1, 150
industrial powder synthesis
processes 141-4, 141
mass transfer processes 148-50, 148
modified process for WC powder
synthesis 143
N2 flux rates 149
process scale-up considerations
154-6,155
reactor design advantages 137, 138
system design considerations
153-4
Pyrophoric powders 2
Reaction-bonded silicon carbide
(RBSC) 25
Reaction-bonded silicon nitride
(RBSN) 10,355
Rheology of non-oxide slips 516-19,
517,518
Rice hulls 378, 379, 379-81, 417
ROC (rapid omnidirectional
compaction) process 21, 24
Rocker arm pads 32, 33
Rocker arm tips 31
Rocker arms 32
ROCTEC 100 21, 24, 25
Roller followers 34, 35
Rotary tube calciners 631-6
direct-heat 632, 633
equipment description 632-3
equipment selection 635-6
indirect-heat 632, 633, 634
materials of construction 635
Rotary tube reactor processes 159-68
applications 165--8
arrangement of high temperature
furnace 162, 163
comparison of indirectly heated
furnace design options 162
directly heated furnace design
161-2
feed preparation 165-6
furnace design configurations
160-2
indirect, externally heated furnace
design 161, 161, 162
indirect, internally heated furnace
design 160-1
mixed metal carbides 166-7, 167
operating difficulties 164-5
process considerations 162-4
product discharge 163-4
reactant feeding 163
reactions 163
reactor size limitations 165
scale-up issues 167-8
silicon carbide 166
tube plugging 164-5
tungsten carbide 166-7, 167
wall build-up 164-5
Safety issues 2
carbothermal reduction synthesis
76-7
chemical vapor deposition 545-6
chemical vapor infiltration 545-6
combustion synthesis processes
182
gas phase synthesis processes
273-4
high temperature furnaces 607-8
liquid phase synthesis processes
389-90
size reduction 476
whiskers 410
Seebeck effect 37
Self-preserving particle size
distribution (SPDF) 287
Self-propagating high-temperature
synthesis (SHS) 183, 198, 233-6,
234-6,240,242,251,263-7,265
Semiconductor processing 36-7, 36
SiC-BN composite particles 336
Silazanes 401-3
Silene radical (SiH3 ) 299
Silicon, effect of iron in 479, 480,
482
Silicon carbide (SiC) 14-15
aerosol processes 328-30, 330-2
automotive pump seals 21
basic manufacture process 116-26,
116
chemical purification 496-7, 498
chemical vapor deposition 294
coating on particles of petroleum
coke 175-6, 175-6
commercial purities 126
comparative reaction rate and
activation energy for synthesis
by carbothermal reduction
98-9
crushing and screening 126
crystal aggregates fire polished at
temperatUl::es exceeding
2700K 124
Index 669
crystals formed by condensation of
silicon carbide vapors in 'blow'
channel 124
densification behavior 479, 481
effect of impurities 50-2
effect of oxygen 47-9
effect of particle size and method of
synthesis 52-3
film deposition 596-8, 597, 598
gas phase reactions 296
grain morphology 51
heating elements 619, 627
history of manufacture 159-60
manufacturing cost factors 126-7
moving bed furnace synthesis
process 145-6
overall reactions for synthesis from
vapor phase precursors 295,
295
plasma synthesis 373-81, 374, 375,
377,377,378,379-81
platelets 426-30, 426-9
polytype development as function
of sintering temperature 48
powder characteristics 47-53
powder synthesis 94-7, 95-7, 98-9
product form 117, 117
product properties 175
pusher furnace synthesis process
142
rapid expansion of solution route
405
raw materials preparation 118-20
reaction mechanisms and kinetics
295-9
rotary tube reactor processes 166
separation process 125-6
sintered density 50, 52
sintering developments 49-50
solid-solid reactions 233-6, 234-6
spray drying 540
thermochemistry 294-5
whiskers, see Whiskers
see also Acheson process
Silicon-carbon system, surface
reactions 298
Silicon nitridation 213-17, 216
Silicon nitride (Si3 N 4 ) 5, 7, 8-10
a/ (3 phase ratio 56
adverse effect of carbon 479
adverse effect of chlorine and
fluorine 479
carbothermal nitridation reaction
105, 105, 106
chemical purification 498-9
combustion-synthesized 217, 218,
219
controlled direct nitridation
258-61, 259, 260
670 Index
Silicon nitride (Si3N 4) contd
crack path 61
crude product powder 105, 105, 106
crystallization by thermal
decomposition 398-9, 399
direct nitridation of silicon metal
255-62,256,257,258
effect of ammonia on carbothermal
nitridation reaction rate 109
effect of impurities 56-7
effect of impurities and additives
108, 109
effect of particle size 55-6
effect of precursor seed and
C/Si02 ratio 107
effect of synthesis method 57--8
engineering practice 396-9
fabrication parameters 63
film deposition 591-2,593
fracture toughness enhancement 61
free energy of reaction 394-6
gas-to-particle conversion 323-4,
324
gaseous ammonia-liquid silicon
tetrachloride routes 392-3
imide intermediate routes 392-401
liquid ammonia-liquid silicon
tetrachloride route 393, 393
liquid ammonia-organic-diluted
silicon tetrachloride route
393-4,394
liquid ammonia route 396--8, 397
liquid formation temperatures for
reactive oxides with 54, 55
liquid phase processes 392
liquid silicon tetrachlOride-liquid
ammonia route 398, 399, 400
manufacturing processes 323
mechanical properties 8, 9
microstructures 10
net-shape components 10
nucleation 107
organic-diluted silicon
tetrachloride-liquid ammonia
route 398, 401
overall reactions for synthesis from
vapor phase precursors 299,
299
particle-to-particle conversion
324-6, 326, 327
plasma synthesis 369-70, 369, 370,
371,371
powder characteristics 53--8
powder properties 399-401
powder specifications 62
powder synthesis 104-10
precursor C/Si02 ratio 103
property comparison 267-9, 268
rare earth sintering additives 55, 57
reactor concepts 261-2, 262
self-propagating direct nitridation
262-7,263,264
self-reinforced structure (SRS) 56,
60
silazane intermediate routes 401-3
process descriptions 403
thermochemistry 403
sintering developments 53-5
sliding and rolling elements 19
spray drying 540
synthesis by reaction of SiH4 with
NH3299
synthesis from chlorosilanes and
NH3300
synthesis routes 61
thermodynamic considerations
107,108
thermodynamic stability diagram
58
vapor chloride-liquid ammonia
route 394, 395, 396, 398
vapor silicon tetrachloride-liquid
ammonia route 394, 401, 402
weight percent vs surface area of
precursor Si02 and C 104
Silicon-nitrogen-hydrogen system,
gas phase reactions 299
Single-source precursors 301-2
Si3N4-MxOy-Si02 system 55, 57
Si3N 4-SiC composites 221-2, 222, 223
Si02
liquid formation temperatures for
reactive oxides with 54, 55
vaporization rates 89, 89
Size reduction 459-77
general definitions and principles
459-62
hardness and specific energy for
grinding 466-7
safety factors 476
selection of equipment 475-6
very fine and ultrafine grinding
467-75
see also specific methods
Slip-cast parts 29
Solid-solid reactions 200, 229-44
Solid solutions 222-4, 224
Solids dispersion in liquids 505-23
Spherical particles 286-7, 288
Spray drying 505, 516, 519-21, 525-43
agglomerate size and shape 531-2
aqueous slurry formulations 541
atomizer types 529, 530
basic systems 525-6
capital investment 538-9
closed cycle systems 534-6, 534, 537
component sizing 532-3
non-oxide systems 540--2
open loop systems 526-33, 526
operating cost 539-40
pilot plant 527
powder output as function of
weight percent solids in feed
slurry 539
process control 536--8
production plant 528
scale-up 533
solvent based slurry formulations
541
system design 532-3
Stable combustion 193-7
STANJAN chemical equilibrium
code 278
Steric stabilization 510--13, 512
Stirred media mills 467-71, 468, 469
Stokes-Einstein relationship 286
Structural applications 30
Sulfur-based precursors 416
SUPERSiC 36-7
Surface chemistry 513-16
Swirl chambers 31
Tantalum nitride (TaN), combustion
synthesis 210, 212, 213
Tantalum-nitrogen system 190, 194
Thermal explosion 207--8, 233, 234
Thermal plasmas 359, 361
Thermal properties 641-7
Thermite reactions 206, 206, 236-42,
238,239-42
Thermochemistry 75-6,187-90
Thermocouple protection tubes 25
Thermodynamic properties 641-7
Thermodynamics 187-90
Thread guides 18-19
TiC-WC solid solutions 194
Time-resolved x-ray diffraction
(TRXRD) patterns 199-200
Ti02-B20 r Mg system 207, 207
Titanium-boron system 204
Titanium carbide (TiC) 47
aerosol processes 333-4
applications 333
combustion-synthesis 229-33, 230,
231,232
film deposition 598-9, 599
formation 199, 200
pusher furnace synthesis process
143
Titanium carbonitride, combustion-
synthesized 223, 224
Titanium-carbon phase diagram 47,
203
Titanium diboride (TiB2) 15, 25, 81
aerosol processes 335
applications 335
plasma synthesis 383

platelets 428
pusher furnace synthesis process
143-4, 144
SHS diagrams 198
thermite reactions 238-40, 241, 242
Titanium nitride (TiN) 7
film deposition 593--6, 594, 595, 596,
596
plasma synthesis 371
Titanium-nitrogen phase diagram
189,190
Transition metal borides, activation
energies of 203
Transition metal-boron compounds
405
Transition metal interactions with
nitrogen and hydrogen 208-13,
209-15
Triple torch plasma reactor (TTPR)
367
Tube furnaces, see Pusher furnaces
Tungsten carbide (WC) 10-12
aerosol processes 334-5
applications 334
plasma synthesis 381-2
powder characteristics 43-7
pusher furnace synthesis process
142-3, 143
rotary tube reactor processes 166-7,
167
spray drying 540
transition metal additions 44
Tungsten-carbon phase diagram
44-3,45
Tungsten-carbon stoichiometry 44-3
Tungsten heating elements 619-21,
627
Turbocharger model 31
Turbocharger rotors 32-4, 33-5
Ultrafine non-oxide ceramic
powders 2
Unstable combustion 197-9
Valves and guides 31-2
Vapor deposition, aerosols 292-3
Vapor phase ceramic synthesis
293-302
Vapor phase reaction intermediates
148
Vaporization rates 86, 89, 89
Vibrating media mills 471-3, 472
Water reactive powders 2
WC-Co cermets 46
WC-Co compositions 46
WC-Co system 47
Wear components 18-22
Wear resistance 24
Whiskers 411-26
bulk chemistry 419-25, 424
carbothermal reduction reactions
using oxide-based precursors
416-19,418
Index 671
characterization 419-26
definition 411
growth from melt solutions 412
growth mechanisms 412-13
mechanical properties 425--6, 425
morphology 419, 420-3
physical properties 419, 419
process overview 409-10
safety issues 410
surface chemistry 419-25
vapor-liquid-solid (VLS) method
412-15,414
vapor phase chemical reaction 412,
415-19
using halogen-based precursors
415-16
using sulfur-based precursors
416
vapor phase formation and
condensation 412, 413
X-ray mirrors 37
Zeta potentials 510, 511, 519
Zirconia-based materials, insulation
621
Zirconium carbide (ZrC), pusher
furnace synthesis process 143
Zirconium diboride (ZrB 2 ) 15
platelets 428
SHS diagrams 198
Zirconium-nitrogen system 190, 193