Introduccion A Mat Ceramicos

Ralf Riedel (Editor)
Handbook of Ceramic Hard Materials
@WILEY*VCH
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Ralf Riedel (Editor)
Handbook of
Ceramic Hard Materials
@WILEY-VCH
Weinheim . New York . Chichester . Brisbane . Singapore . Toronto
Editor:
Prof. Dr. Ralf Riedel
Fachgebiet Disperse Feststoffe
Fachbereich Materialwissenschaft
Technische Universitit Darmstadt
PetersenstraRe 23
64287 Darmstadt
Germany
This book was carefully produced. Nevertheless, authors, editor and publisher do not warrant the
information contained therein to be free of errorb. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No. Applied for

A catalogue record for this book is available from the British Library
Deutschc Bibliothek Cataloguing-in-Publication Data:
A catalogue record for this publication is available from Die Deutschc Bibliothek
ISBN 3-527-29912-6
C WILEY-VCH Verlag GmbH, D-69469 Weinheiin (Federal Republic of Germany), 2000

Printed on acid-free and chlorine-free paper
All rights reserved (including those of translation in other languages). N o part of this book may be reproduced in any form by photoprinting, microfilm, or any other means nor transmitted or translated into
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Composition: Alden Bookset, Oxford
Printing: betz-druck, Darmstadt
Bookbinding: Buchbinderei Osswald, NeustadtiWstr.
Printed in the Federal Republic of Germany
~
This book is dedicate to
Ute, Vincent, Lorenz and Marlene
Preface
With increasing demand for improved efficiency of engines, plants and production
processes, ceramics have gained great importance as structural engineering
materials in recent years. Within the group of the so called advanced materials,
carbon in form of diamond or diamond-like structures, carbides, nitrides and borides have reached an outstanding position due to their excellent hardness and
thermo-chemical and thermo-mechanical properties. The distinct covalent bonding
of the aforementioned structures positively influences their hardness and their tribological behavior. Moreover, a series of oxides such as stishovite, a high pressure
modification of silica, or boron sub-oxides have been recently discovered to exhibit
high hardness apart from the well known alumina.
There is presently much effort in basic science and applied research to work on
novel ceramic hard materials denoted as super- or ultra-hard materials that can
compete with the hardness of conventional diamond. Aim and scope of the research
in this field is to develop hard materials with superior mechanical and chemical
properties and with similar hardness. Moreover, calculations of properties of
hypothetical carbon nitrides like C3N4 indicated that there might be compounds
exhibiting even higher hardness values than that of diamond. The low-temperature
synthesis of diamond and cubic boron nitride on the one hand as well as the successful research on new carbon nitrides on the other hand have caused an enormous
impact around the world on both the basic science and the technological development of these novel ultra-hard materials.
With the present book we wish to review comprehensively and concisely the state
of the art concerning the structure, synthesis, processing, properties and applications of ceramic hard materials in general. In particular, the synthesis, modeling
and properties of novel hard materials like binary carbon nitrides, ternary boron
carbonitrides and others are also addressed. It is the aim of this reference book
not only to reflect the state of the art and to give a sound review of the literature,
but to delineate the underlying concepts and bearing of this interdisciplinary field.
With the present edition we wish to show that the field of hard materials research
and development has to be recognized into the wider context of chemistry, physics
as well as materials science and engineering.
The book is organized in two volumes and three parts, covering the structure
and properties of ceramic hard materials (Volume 1, Part I), synthesis and processing (Volume 1, Part 11) as well as the typical fields of applications (Volume 2,
Part 111).
Volume 1 starts with an introduction into novel ultra hard ceramics including
diamond and diamond-like carbon, carbon nitrides and silicon nitrides as well as
boron containing carbides, nitrides and carbonitrides. Here we wish to recognize
the great fundamental and technological challenge of developing new superhard
VIII
Preface
materials which can compete with the hardest counterparts such as diamond and
cubic boron nitride.
In dealing with properties, the first Chapter in Part I is then devoted to the structure of crystalline and amorphous ceramic hard materials. The structural features
are responsible in particular for the intrinsic materials properties such as melting
point and hardness. It has been found that in many cases the hardness of a crystalline substance correlates with its melting point. Therefore, detailed knowledge of the
3dimensional arrangement of the atoms is required to understand the materials
behavior under certain conditions. More details of the individual crystal structures
with respect to a 3dimensional view can be found on our hard materials homepage
under the web address www.hardmaterials.de. Phase transitions and materials
synthesis under high pressure in laser heated diamond cells is the topic of the
continuing Chapter. The materials behavior under high pressure and temperature
is of fundamental interest for the synthesis of hard materials since many of the
ultra-hard substances like diamond, cubic boron nitride or stishovite are formed
naturally or synthetically under these harsh conditions. The next three Chapters
are concerned with the mechanical behavior and corrosion of ceramic hard
materials and their relation to microstructure. This correlation is an important
feature since hardness is not only governed by the intrinsic atomic structure of
the respective material but also to a great extend by its polycrystalline nature. Therefore, the grain morphology and grain boundary chemistry play a decisive role in the
materials response under environmental or mechanical load. In the following
Chapter transition metal carbides, nitrides and carbonitrides are discussed with a
focus on their structure and bonding, thermodynamic behavior as well as on their
physical and mechanical properties. Part I is then completed by two Chapters
which deal with the theoretical design of novel sp2-bonded carbon allotropes and
novel superhard materials based on carbon and silicon nitrides. These Chapters
tribute to the fact that with proceeding computerization the number of calculated
novel solid structures that led to the prediction of new materials with hardness
comparable to or exceeding that of diamond has increased enormously in recent
years.
Part I1 continues with the synthesis and processing of ceramic hard materials.
Since the conventional powder technological synthesis and processing of ceramics
has been treated in a large number of published review articles here we concentrate
on novel synthetic routes that provide ceramic hard materials. Consequently, six
Chapters report on i) directed metal oxidation, ii) self-propagating high temperature
synthesis, iii) hydrothermal synthesis of diamond, chemical vapor deposition of
diamond (iv) and cubic boron nitride (v) films and finally vi) the polymer to ceramic
transformation. All these processes are particularly suitable for the formation of
refractories with high hardness. Part I1 is then closed by a Chapter on nano
structured superhard materials. In the course of this work high hardness is achieved
by microstructural control rather than by the synthesis of a distinct crystal structure.
In Volume 2 ceramic hard materials are highlighted in the light of their applications. Chapter 1 of Part I11 concisely reviews the history of diamond and diamondlike super abrasive tools while Chapter 2 and 3 are concerned with the application of
chemical vapor deposited diamond and diamond-like carbon films. These sections
Prejace
IX
include the synthesis of optical grade CVD diamond windows and discuss their
physical and mechanical properties. The most important and wide-spread ceramic
hard materials are based on alumina. Chapter 4 reports on the processing developments to increase the hardness of alumina based ceramics for grinding and cutting
applications. Silicon carbide and silicon nitride materials are the most technologically important non-oxide compounds and have gained great significance in the
field of cutting ceramics and are treated in Chapters 5 and 6. Boron-based ceramics
are a further group of either established or candidate materials with extreme hardness. Therefore, Chapter 7 deals with boron carbide or transition metal borides like
titanium diboride and their distinct properties and applications. In Chapter 8, classical hard metals comprised of tungsten carbide as the hard phase and cobalt as the
binder phase are discussed. Volume 2 is finally completed by a data base (Chapter 9)
containing approximately 130 hard materials including carbides, nitrides, borides,
silicides and oxides. The data base references the crystal structure, physical properties like melting point and density, mechanical properties (Youngs modulus, micro
hardness) and oxidation resistance of the respective compounds. Future developments of novel hard materials such as the recently discovered intermetallic phase
A1MgBl4will be updated on our internet homepage www.hardmaterials.de.
In closing these introductory remarks, I would like to emphasize that the special
chance to place a summary of the outstanding expertise on the field of present hard
materials research and development would not have been possible without the great
enthusiasm and commitment of all the colleagues who contributed in the writing of
this two volume set. I am grateful for their enormous efforts in compiling a fascinating series of articles imparting depth insight into the individual fields of modern hard
materials research. Finally, I wish to thank the Wiley-VCH Editors Peter Gregory
and Jorn Ritterbusch for encouraging me in the preparation of this book and for
their continuous support throughout the editorial process.
Ralf Riedel
March 2000
Darmstadt
Foreword
One of the clearest hierarchies in materials science and engineering is provided by

the property of hardness. There are, of course, many properties where remarkable
differences exist between groups of materials. An example is provided by electrical
conductivity where a ratio of 10l8can be readily found; with electrical conductivity,
however, the different materials do not come into direct competitive opposition. In
the case of hardness, the very value of this property lies in the ability of one material
to demonstrate a higher place in the hierarchy than another; the one material is used
in effect to overpower the other.
The existence of this hierarchy, which has been long recognised in the traditional
measurement scale for the property, has direct relation to applications. In any use of
materials it is important to be able to shape them to be fit for purpose; where the
shaping process involves some type of machining, as it most commonly does,
then the property of hardness becomes the unambiguous figure of merit.
It is for these reasons that there has been long standing and productive interest in
hard materials, in their design, in their fabrication, in their use, and in the underlying
science and engineering. It is thorougLlv in keeping with this tradition of research
relevant to application that the present book brings together a set of authoritative
reviews of the progress which has been made.
The organisation of the book is a direct reflection of the logic which has been used
in developing hard materials. One of the great attractions of the subject has been the
close link that exists between hardness on the one hand and the bonding and structure of the material on the other. The link between these two has proved to be one of
the best foundations on which to base materials development. The link is a central
theme in the first part of the book where fine examples are given of the rich contribution which has been made and which continues to be made by fundamental
studies of bonding and structure to materials performance.
It has long been recognised that the very aspect of their extreme resistance to
deformation would make it a particular challenge to manufacture hard materials
in reliable and cost-effective ways. It is here that the materials community has
shown itself to be imaginative and forward looking in seeking innovative
fabrication routes. These are well presented in the second part of the book
where specific attention is given to the paths which can be used to assemble
materials of precisely defined form without sacrifice of their characteristic mechanical resilience.
The most striking aspect of hard materials, however, is the direct link to applications. This link has brought an unusual degree of purpose to materials development
which has enjoyed the benefits of being conducted in full recognition of the target to
be reached. It has also meant that the progress made in research can be rapidly
evaluated since the testing procedures relate so directly to the end use. The third
XI1
Foreword
part of the book accordingly gives close accounts of the performance of the different
classes of hard materials in the applications context.
The contributors to this text are to be congratulated on bringing their many disciplines to bear on this central theme. Materials science is well known to undergo
fashions as materials are developed and discarded and indeed as sectors of application grow and decline. The one requirement which will remain is that the forming
and shaping of materials will always be necessary whatever the eventual sector of
application. We can accordingly be confident that the long history of hardness
studies, not least in the last two hundred years from the carbon tool steels, to
high speed steels, to stellite, to tungsten carbide, to cermets, to ceramics, and now
to diamond, boron, nitride and other special systems, will be continued with
informed imagination and with creative innovation. The present book is a splendid
platform on which to base such future development.
Richard Brook
January 2000
Oxford, UK
Contents
List of Contributors XXVII

List of Symbols XXXIII
List of Abbreviations XXXIX
Introduction: Novel Ultrahard Materials
A . Zerr and R. Riedel
Introduction XLV
Hard Materials XLVI
Hardness XLVII
Carbon-based Hard Materials L
Diamond LII
Diamond-like and Amorphous Carbon LV
Novel Hypothetical Three-dimensional Carbon Phases
Fullerenes LIX
Carbon Nitride (C3N4) LIX
Boron-based Hard Materials LXIV
Boron Nitrides LXIV
Boron-rich Boron Nitrides LXVII
Nitrogen-rich Boron Nitride LXVIII
Boron Carbonitrides (B,C,N,)
LXVIII
Boron Suboxides LXXI .
Silicon-based Materials LXXI
Concluding Remarks LXXII
Acknowledgement LXXIII
References LXXIII
Part I
Structures and Properties
Structural Chemistry of Hard Materials

W . Jeitschko, R. Pottgen, and R.-D.
Hoffmann
1.1
Introduction 3
Diamond and Diamond-Related Structures 5
The Crystal Structure of Diamond 5
The Isoelectronic Compounds c-BN and S i c 6
Crystal Chemistry of Borides and Boron Carbides 8
The Structures of Transition Metal Carbides 12
Silicides and Silicide Carbides of Transition Metals 20
1.2
1.2.1
1.2.2
1.3
1.4
1.5
LVI
XIV
Contents
1.6
1.6.1
1.6.2
1.6.3
1.7
1.7.1
1.7.2
1.8
Nitrides 23
Nitrides of Main Group Elements 24
Transition Metal Nitrides 25
Perspectives: Nitridosilicates 29
Oxide Ceramics 30
Hard Ceramics of Main Group Elements 30
Transition Metal Oxides 32
Amorphous Hard Materials 36
References 37
Phase Transitions and Material Synthesis using the C02-Laser

Heating Technique in a Diamond Cell
A . Zerr, G. Serghiou, and R . Boehler
2.1
2.2
2.2.1
2.2.2
2.2.3
Introduction 41
Technique of C02-Laser Heating in a Diamond Anvil Cell 42
Sample Assemblage in a Diamond Anvil Cell 42
Pressure Conditions in the Sample Volume 43
Experimental Set-up for C02-Laser Heating in a Diamond Anvil
Cell 44
Temperature Determination 45
Temperature Stabilization 45
Radial Temperature Gradients 48
Raman and Fluorescence Spectroscopic Analysis of Samples in a
Diamond Anvil Cell 48
Determination of Melting Temperatures at High Pressures 49
Melting of Cubic BN at 10 GPa 49
Melting Temperatures of Materials Relevant to the Earths Lower
Mantle 51
Phase Diagrams, Decomposition Reactions, and Stability of Solids at
High Pressures and Temperatures 54
Coesite-Stishovite Phase Boundary 55
High Pressure and Temperature Phase Diagram and Decomposition
Reactions in a Ternary System 56
Stability of a Perovskite Oxide with Respect to its Component
Oxides 59
C02-laser Heating Experiments on Organic Compounds 60
Conclusion 62
Acknowledgments 62
References 62
2.2.4
2.2.5
2.2.6
2.2.7
2.3
2.3.1
2.3.2
2.4
2.4.1
2.4.2
2.4.3
2.5
2.6
Mechanical Properties and their Relation to Microstructure

D. Sherman and D . Brandon
3.1
3.1.1
Introduction 66
Applications and Engineering Requirements
66
Contents
XV
3.1.2
3.1.3
3.1.4
3.2
3.2.1
3.2.2
3.2.3
3.2.4
3.3
3.3.1
3.3.2
3.3.3
3.3.4
3.3.5
3.3.6
3.4
3.5
3.5.1
3.5.2
3.5.3
3.6
Bulk Components 68
Coatings 70
Engineering Requirements 70
Principal Mechanical Properties 7 1
Elastic Modulus 71
Strength 72
Fracture Toughness 74
Hardness 79
Mechanical Testing of Hard Materials 81
Elastic Modulus 81
Fracture Strength 8 1
Fracture Toughness 83
Hardness 84
Indentation Toughness 86
Erosion, Wear and Scratch Tests 89
Microstructural Parameters and Mechanical Properties 9 1
Failure Mechanisms 94
Creep Behavior 94
Mechanical Fatigue 95
Ballistic Properties 97
Conclusions 98
References 99
Nanostructured Superhard Materials

S. Veptek
4.1
4.2
4.2.1
4.2.2
4.3
Introduction 104
Concept for the Design of Superhard Materials 109
Nanocrystalline Materials 110
Heterostructures 114
Preparation and Properties of Superhard Nanocrystalline
Composites 116
Preparation 116
Properties of the ncM,N/aSi3N4 Composites 119
Other Superhard Nanocomposites and the General Validity of the
Design Principle 124
Discussion of the Possible Origin of the Hardness and Stability of the
Nanostructure 128
Conclusions 133
Acknowledgments 134
References 134
4.3.1
4.3.2
4.3.3
4.4
4.4
Corrosion of Hard Materials

K . G. Nickel and Y. G. Gogotsi
5.1
Introduction
140
XVI
5.2
5.3
5.3.1
5.3.2
5.4
5.4.1
5.4.2
5.4.3
5.4.4
5.4.5
5.5
5.5.1
5.5.2
5.6
5.6.1
5.6.2
5.6.3
5.6.4
5.6.5
Contents
Corrosive Media 140

Corrosion Modes 141
Active and Passive Corrosion 141
Homogeneity and Location of Attack: Internal, External and
Localized Corrosion 141
Corrosion Kinetics 142
Physical Boundary Conditions 142
Active Corrosion Kinetics 143
Basic Passive Corrosion Kinetics 145
Kinetic Breaks 147
Complex Kinetics 148
Corrosion Measurement 150
Experimental Methods 150
Corrosion Data 151
Materials 154
Diamond and Diamond-like Carbons 154
Carbides 155
Nitrides 166
Carbonitrides 173
Titanium Diboride 176
References 177
Interrelations Between the Influences of Indentation Size, Surface

State, Grain Size, Grain-Boundary Deformation, and Temperature on
the Hardness of Ceramics
A . Krell
6.1
6.2
Introduction 183
The Assessment of Residual Porosity and Flaw Populations: A
Prerequisite for any Hardness Investigation 184
Theoretical Considerations 185
The Role of the Lattice and of Grain Boundaries in the Inelastic
Deformation at an Indentation Site in Sintered Hard
Materials 185
Quantitative Understanding the Load Effect on the Hardness:
Theoretical Considerations Compared with Single Crystal Data 188
Influences of the Grain Size and the State of the Surface 191
The Grain Size Influence on the Load Effect of the Hardness:
Modeling Experimental Results 191
The Effect of the Grain Size and the Surface State in Ceramics when
Recorded by Different Measuring Approaches 193
Comparing the Grain Size Effect and the Indentation Size Effect: The
Role of Grain Boundaries at Room Temperature 195
The Effects of Temperature on the Hardness of Ceramics 198
Summary 199
References 20 1
6.3
6.3.1
6.3.2
6.4
6.4.1
6.4.2
6.5
6.6
6.7
Contents
XVII
Transition Metal Carbides, Nitrides, and Carbonitrides

W. Lengauer
7.1
7.2
7.2.1
7.2.2
7.3
7.4
7.4.1
7.4.2
7.5
7.5.1
7.5.2
7.5.3
7.5.4
7.5.5
7.6
Introduction 202
General Features of Structure and Bonding 205
General Structural Features 205
General Features of Bonding 206
Preparation 207
Characterization 2 10
Chemical Analysis 2 10
Physical Microanalysis 21 1
Thermodynamics 2 12
Stability of Carbides 212
Nitrogen Partial Pressure of Nitrides 212
Phase Equilibria of Important Carbide Systems 213
Transition Metal-Nitrogen Systems and Structure of Phases 216
Carbonitride Systems 221
Properties of Important Transition Metal Carbides, Nitrides, and
Carbonitrides 224
Melting Points 224
Color 224
Thermal and Electrical Conductivities 225
Thermal Expansion 228
Diffusivities 229
Elastic Properties 23 1
Microhardness 234
Industrial Applications 238
Cemented Carbides and Carbonitrides 238
Deposited Layers 241
Diffusion Layers 246
Acknowledgments 248
References 248
7.6.1
7.6.2
7.6.3
7.6.4
7.6.5
7.6.6
7.6.7
7.7
7.7.1
7.7.2
7.7.3
New Superhard Materials: Carbon and Silicon Nitrides

J . E. Lowther
8.1
8.2
8.2. I
8.2.2
8.2.3
8.2.4
8.3
8.3.1
8.3.2
8.3.3
Introduction 253
Modeling Procedures 254
Semi-empirical Approaches 254
Tight-binding Schemes 255
Ab initio Pseudopotential Approach 256
Transition Pressures and Relative Stability 256
Carbon Nitride 257
Crystalline Structures 258
Graphitic Structures 259
Amorphous Structures 261
XVIII
Contents
8.3.4
8.4
8.4.1
8.4.2
8.4.3
8.5
Relative Stability 263

Silicon Carbon Nitride 264
j3SiC2N4 265
Near-cubic Forms of SiC2N4 266
Relative Stability 268
Conclusions 268
Acknowledgements 269
References 269
Effective Doping in Novel sp2 Bonded Carbon Allotropes

G. Jungnickel, P. K. Sitch, T. Frauenheim, C. R. Cousins, C. D. Latham,
B. R. Eggen, and M . I. Heggie
9.1
9.2
9.3
9.4
9.5
9.6
Introduction 271
Lattice Description 274
Computational Methods 276
Static Properties 278
Electronic Properties 279
Conclusions 282
Acknowledgments 283
References 283
Part I1
Synthesis and Processing
Directed Metal Oxidation

V. Jayaram and D. Brandon
1.1
1.2
1.2.I
1.3
I .4
1.5
1.5.1
1.5.2
1.5.3
1.5.4
1.5.5
1.5.6
1.6
1.6.1
1.6.2
1.6.3
1.6.4
1.6.5
1.6.6
Historical Background 289

Oxidation and Oxide Formation 290
Initial Oxidation 291
Related Ceramic Processing Routes 293
Directed Metal Oxidation Incubation 295
Directed Metal Oxidation Growth 300
Introduction 300
Directed Metal Oxidation Composites from Al-Mg Alloys 300
Directed Metal Oxidation Growth from other Aluminum Alloys 304
Microstructural Scale 305
Growth into Particulate Preforms 307
Growth into Fibrous Preforms 309
Mechanical Properties 310
Elastic Modulus 310
Strength and Toughness 3 11
Thermal Shock 313
High Temperature Strength 313
Wear Properties 314
Mechanical Properties of Fiber-reinforced DMO Composites 3 14
Contents
XIX
1.7
1.8
1.9
1.9.1
1.9.2
1.9.3
Corrosion of Directed Metal Oxidation Composites 3 16

Other Properties 316
Applications 3 I6
Wear Resistant Components 317
Ceramic Composite Armor 3 17
Thermal Barriers and Heat Sinks 318
References 3 18
Self-propagating High-Temperature Synthesis of Hard Materials

Z . A . Munir and U. Anselmi-Tumburini
2.1
2.2
2.3
2.3
2.4
Introduction 322
Mechanistic Characterization of the Process 327
Effect of Experimental Parameters 33 1
Synthesis of Dense Materials 342
Synthesis by Field-Activated Self-propagating High-temperature
Synthesis 348
Selected Recent Examples of Synthesis of Hard Materials 356
Acknowledgment 368
References 368
2.6
Hydrothermal Synthesis of Diamond

K. G. Nickel, T. Kruft, and Y. G. Gogotsi
3.1
3.2
3.3
3.3.1
3.3.2
3.4
Introduction 374
Evidence from Nature 376
Hydrothermal Synthesis 377
C-H-0 System 377
Hydrothermal Treatment of S i c 382
Outlook 387
Acknowledgments 387
References 387
Chemical Vapor Deposition of Diamond Films

C.-P. Klages
4.1
4.2
4.2.1
4.2.2
4.2.3
Introduction 390
Preparation Methods for Diamond Films 391
Hot-filament Chemical Vapor Deposition 392
Microwave-plasma-based Methods 397
Preparation of Special Forms: Textured and
Heteroepitaxial Films 400
Thermochemistry and Mechanism of Chemical Vapor Deposition
Diamond Growth 407
Transformation of Graphite to Diamond at Low Pressures 407
4.3
4.3.1
xx
4.3.2
4.4
4.4.1
4.4.2
4.4.3
4.4.4
4.5
Contents
Reactive Species in Diamond Chemical Vapor Deposition, the Role

ofCH3 408
Properties and Applications of Chemical Vapor Deposited
Diamond 410
Diamond Coated Cutting Tools 41 1
Thermal Conductivity of Chemical Vapor Deposited Diamond:
Thermal Management Applications 412
Electrical Properties and Electronic Applications 413
Electrochemical Use of Chemical Vapor
Deposited Diamond 415
Summary 417
References 4 17
Vapor Phase Deposition of Cubic Boron Nitride Films

K. Bewilogua and F. Richter
5.1
5.2
5.2.1
5.2.2
5.2.3
5.3
5.4
5.4.1
5.4.2
Introduction 420
Empirical Results 421
Deposition Methods 421
Morphology and Structure of cBN Films 423
Film Adhesion 427
Models of cBN Formation 427
Sputter Deposition of cBN Films 429
Sputter Deposition with Conducting Targets 430
Deposition by d.c. Magnetron Sputter with a Hot Boron
Target 43 1
Discrimination between Nucleation and Growth Phase 433
Detection of hBNxBN Transition 433
RF Magnetron Sputtering 435
Properties of cBN Films 440
Mechanical and Tribological Properties 440
Optical Properties 440
Electrical Properties 441
Other Properties 441
Summary and Outlook 442
References 442
5.5
5.5.1
5.5.2
5.6
5.6.1
5.6.2
5.6.3
5.6.4
5.7
Polymer to Ceramic Transformation: Processing of Ceramic Bodies

and Thin Films
G. D. Soraru and P. Colombo
6.1
6.2
6.3
Introduction 446
Processing of Monolithic Components 450
Preparation and Characterization of SiAlOC Ceramic Bodies by
Pyrolysis in Inert Atmosphere 452
Experimental Procedure 452
6.3.1
Contents
6.4
6.4.1
6.4.2
6.4.3
6.4.4
6.5
6.6
6.6.1
6.7
6.8
6.9
6.10
6.10.1
6.10.2
6.1 1
XXI
Results 453
Characterization of the Pre-ceramic Precursors 453
Characterization of the Pre-ceramic Components 454
Characterization of the Ceramic Components 455
Mechanical Characterization at High Temperature 457
Discussion 458
Preparation and Characterization of SiAlON Ceramics by Pyrolysis
in Reactive Atmosphere 460
Experimental 460
Results and Discussion 460
Processing of Thin Ceramic Films 463
Experimental 463
Results and Discussion 464
Conventional Conversion Process: Annealing in
Controlled Atmosphere 464
Nonconventional Conversion Process: Ion Irradiation 467
Conclusions 472
Acknowledgments 473
References 473
Part 111
Materials and Applications
Diamond Materials and their Applications

Edited by R. J . Caveney
1.1
1.1.1
1.1.2
1.1.3
1.1.4
1.1.5
1.1.6
1.1.7
1.2
1.2.1
1.2.2
1.2.3
1.2.4
1.2.5
1.2.6
1.2.7
1.3
1.3.1
1.3.2
1.3.3
Superabrasive tools: A Brief Introduction 479

Introduction 479
Early History 479
Synthetic Diamond 48 1
Cubic Boron Nitride 482
Polycrystalline Diamond and Cubic Boron Nitride 482
Chemical Vapor Deposited Diamond 484
Outline of Chapter 485
The Crystallization of Diamond 485
The Carbon Phase Diagram 485
Diamond Crystallization at High Pressure 487
High Pressure Apparatus 490
The Synthesis of Particulate Diamond Abrasives 49 1
Growth of Large Synthetic Diamonds 496
Novel Diamond Synthesis Routes 504
Cubic Boron Nitride Crystallization 5 10
Polycrystalline Diamond and Cubic Boron Nitride 5 12
Natural Polycrystalline Diamond 5 12
Synthetic Polycrystalline Diamond 512
Mechanisms involved in Polycrystalline Diamond Manufacturing
Process 513
XXII
Contents
1.3.4
1.4
1.4.1
1.4.2
1.4.3
1.4.4
1.4.5
1.4.6
1.4.7
1.5
1.5.1
1.5.2
1.5.3
1.5.4
1.5.5
Polycrystalline Cubic Boron Nitride 5 18

New Ultrahard Materials 521
Introduction 521
Hardness 521
C3N4 523
Boron Rich Nitride 526
Boron Carbonitrides 526
Boron Suboxides 526
Stishovite 526
Industrial Applications of Diamond and cBN 527
Introduction 527
Abrasive Application 528
Machining of Stone and Concrete 540
Applications of Polycrystalline Ultra-hard Materials
Applications of Single Crystal Diamond 559
Acknowledgments 566
References 566
Applications of Diamond Synthesized by Chemical Vapor Deposition

R. S. Sussmann
2.1
2.2
2.2.1
2.2.2
2.2.3
2.2.4
2.2.5
2.2.6
2.3
2.3.1
Introduction 573
Properties of Chemical Vapor Deposited Diamond 574
Material Grades 574
Optical Properties 576
Strength of Chemical Vapor Deposited Diamond 580
The Young Modulus 581
Thermal Conductivity 582
Dielectric Properties 583
Optical Applications 583
Chemical Vapor Deposited Diamond for Passive Infrared Windows in
Aggressive Environments 584
Windows for High-power Infrared Lasers 589
Windows for High Power Gyrotron Tubes 597
Window Requirements 598
The Development of Chemical Vapor Deposited Diamond Gyrotron
Windows 599
Thermal Management of Laser Diode Arrays 606
Laser Diode Arrays: General Issues 607
Modelling of Submount Heat Resistance 607
Flatness of Submount 610
Thermal Stress 610
Cutting Tools, Dressers and Wear Parts 61 1
Cutting Tools Trends 61 1
Cutting Tool Application of Chemical Vapor Deposited
Diamond 612
2.3.2
2.4
2.4.1
2.4.2
2.5
2.5.1
2.5.2
2.5.3
2.5.4
2.6
2.6.1
2.6.2
548
Contents
XXIII
2.6.3
2.6.4
Chemical Vapor Deposited Diamond Dressers 616

Chemical Vapor Deposited Diamond Wear Parts 617
References 6 19
Diamond-like Carbon Films

C.-P. Klages and K . Bewilogua
3.1
3.2
3.2.1
3.2.2.
3.2.3
3.3
3.3.1
3.3.2
3.4.
3.4.1
3.4.2
3.5.
3.5.1
3.5.2
3.5.3
3.5.4
Introduction 623
Preparation Methods for Diamond-like Carbon Films 623
Hydrogenated Amorphous Carbon (a-C: H) 623
Hydrogen Free Amorphous Carbon (ta-C) 627
Metal-containing Amorphous Hydrocarbon 629
Microstructure and Bonding of Diamond-like Carbon 630
Amorphous Carbon and Hydrogenated Amorphous Carbon
Metal-containing Amorphous Carbon Films 634
Physical Properties of DLC Films 637
Electrical and Optical Properties 637
Mechanical Properties 639
Applications of DLC Films 640
Adhesion of DLC Films 640
Tribology of DLC Coatings 642
Tribological Applications 644
Other Applications 644
References 645
Ceramics Based on Alumina: Increasing the Hardness for Tool

Applications
A . Krell
4.1
4.2
Recent Trends in the Application of Ceramic Tool Materials 648

Technological Essentials for Producing Hard and Strong Tool
Ceramics 650
Typical Defects in Ceramics Tool Materials: The State of The
Art 651
Recent Trends in Ceramic Technologies Related to
Tool Ceramics 653
Tool Materials with Undefined Cutting Edge: Sintered Grinding
Materials 658
Technical Demands for Grinding Materials 660
661
Advanced Commercial Products: Sol/gel-derived Corundum
Sintered Alumina Grits Produced by Powder Processing
Approaches 665
New Trend for Cutting Hard Workpieces: Submicrometer Cutting
Ceramics for Tools with Defined Cutting Edge 666
Demands for Cutting Materials Used for Turning
Hard Workpieces 667
4.2.1
4.2.2
4.3
4.3.1
4.3.2
4.3.3
4.4
4.4.1
630
XXIV
Contents
4.4.2
4.4.3
4.4.4
Carbide Reinforced Composite Ceramics Based on A1203 669

Single Phase Sintered Corundum 670
Comparative Cutting Studies with Submicrometer Ceramics: A1203
and Composites Reinforced with Ti(C,N) and Ti(C,O) 670
Summary 680
References 68 1
4.5
Silicon Carbide Based Hard Materials

K. A . Schwetz
5.1
5.1.1
5.1.2
5.2
5.3
5.3.1
5.3.2
5.3.3
5.4
5.4.1
5.4.2
5.4.3
5.5
5.6
5.7
lntroduction 683
History 683
Natural Occurrence [7] 684
Structure and Phase Relations of S i c 685
Production of S i c 688
The Acheson/ESK Process 688
Other Production Methods 69 1
Dense S i c Shapes 699
Properties of Silicon Carbide 719
Physical Properties 719
Chemical Properties 720
Tribological Properties 723
Quality Control 734
Toxicology and Occupational Health 736
Uses of Silicon Carbide 736
Acknowledgments 740
References 740
Silicon Nitride Based Hard Materials

M . Herrmann, H. Klemm, Chr. Schubert
6.1
6.2
6.3
6.4
6.4.1
6.4.2
6.5
6.5.1
6.5.2
6.5.3
6.5.4
6.6
Introduction 749
Crystal Structure and Properties of the Si3N4Modifications 753
Densification 755
Microstructural Development 758
Microstructural development of P-Si3N4materials 758
Microstructural development of a-SiALON materials 768
Properties of Si3N4Materials 771
Mechanical properties at room temperatures 771
High-temperature properties of silicon nitride materials 777
Wear resistance of Si3N4materials 782
Corrosion resistance of Si3N4 786
Conclusions/Further potential of silicon nitride materials 792
Acknowledgements 795
References 795
Contents
xxv
Boride-Based Hard Materials

R. Telle, L. S . Sigl, and K. Takagi
7.1
7.2
7.2.1
7.2.2
7.3
7.3.1
7.3.2
7.4
7.4.1
7.4.2
7.4.3
7.4.4
7.4.5
7.5
7.5.1
7.5.2
7.5.3
7.6
Introduction 802
Chemical Bonding and Crystal Chemistry of Borides 803
Chemical Bonding of Borides 803
The Crystal Structure of Borides 804
Phase Systems 812
Binary Phase Diagrams of Technically Important Systems 813
Ternary and Higher Order Systems 818
Boron Carbide Ceramics 837
Preparation of Boron Carbide 837
Sintering of Boron Carbide 839
Properties of Boron Carbide 851
Chemical Properties and Oxidation of Boron Carbide 855
Boron Carbide-Based Composites 857
Transition Metal Boride Ceramics 874
Preparation of Transition Metal Borides 875
Densification of Transition Metal Borides 876
Properties of Transition Metal Borides Ceramics 878
Multiphase Hard Materials Based on Carbide-Nitride-Boride-Silicide
Composites 888
Boride-Zirconia Composites 888
Cemented Borides 895
Boron Carbide-Based Cermets 895
Titanium Diboride-Based Cermets 897
Cemented Ternary Borides 919
Potentials and Applications 927
Future Prospects and Fields of Application 933
References 936
7.7
7.8
7.8.1
7.8.2
7.8.3
7.8.4
7.9
The Hardness of Tungsten Carbidecobalt Hardmetal 946

S . Luyckx 946
8.1
8.2
8.2.1
8.2.2
8.3
8.3.1
8.3.2
8.3.3
8.3.4
8.3.5
8.4
Introduction 946
The Hardness of the Two Component Phases 947
The Hardness of Tungsten Carbide 947
The Hardness of Cobalt 948
Factors Affecting the Hardness of WC-Co Hardmetal 950
Cobalt Content and Tungsten Carbide Grain Size 950
Grain Size Distribution and Cobalt Mean Free Path 952
Binder Composition and Carbon Content 952
Porosity 953
Effect of Temperature 953
Relationships between Hardness and Other Hardmetal
Properties 960
XXVI
Con ten /s
8.4.1
8.4.2
8.5
Relationship between Hardness and Toughness 962

Relationship between Hardness and Abrasive Wear Resistance
Conclusions 963
Acknowledgments 963
References 964
Data Collection of Properties of Hard Materials

G. Berg, C. Fviedrich, E. Broszeit, and C. Bevger
9.1
9.2
9.3
Introduction 965
Profile of Properties 965
Organization and Contents of the Data Collection
Acknowledgement 967
Refercnces 99 1
Index 997
966
962
List of Contributors
U. Anselmi-Tamburini
Dipartimento di Chimica Fisica
Universita di Pavia
27100 Pavia
Italy
R. Bohler
Max-Planck-Institute for Chemistry
Saarstrasse 23
D-55020 Mainz
Germany
M. W. Bailey
De Beers Industrial Diamond
Division Pty Ltd
Diamond Research Lab
PO Box 1770
Southdale 21 35
South Africa
D. Brandon
Department of Materials Engineering
Technion - Israel Institute of
Technology
Haifa 32000
Israel
G. Berg
Fachgebiet und Institut fur
Werkstofiunde der TU Darmstadt
und Staatliche
Materialpru fungsanhalt
Grafenstrasse 2
D-64283 Darmstadt
Germany
C. Berger
und Staatliche
Materialpriifungsanhalt
Grafenstrasse 2
D-64283 Darmstadt
Germany
K. Bewilogua
Fraunhofer Institut fur Schicht und
Oberflachentechnik (IST)
Bienroder Weg 54 E
D-38 108 Braunschweig
Germany
J. R. Brandon
Division Pty Ltd
PO Box 1770
Southdale 2 135
South Africa
E. Broszeit
und Staatliche
Materialprufungsanhalt
Grafenstrasse 2
D-64283 Darmstadt
Germany
R. C. Burns
Division Pty Ltd
PO Box 1770
Southdale 21 35
South Africa
XXVIII
R. J. Caveney
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
G. J. Davies
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
S. E. Coe
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
B. R. Eggen
School of Chemistry, Physics and
Environmental Sciences
University of Sussex
Falmer
Brighton BNl 9QJ
UK
J. L. Collins
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
D. Fister
HC Starck Gmbh
Kraftwerkweg 3
D-79725 Laufenburg
Germany
P. Colombo
Universita di Bologna
Dipartimento di Chimica Applicata e
Scienza dei Materiali
viale Risorgimento 2
1-40I36 Bologna
Italy
M. W. Cook
Division Pty Ltd
PO Box 1770
Southdale 21 35
South Africa
C. R. Cousins
Department of Physics
University of Exeter
Stocker Road
Exeter EX4 4QL
UK
T. Frauenheim
Fachbereich Physik
Universitat/Gesamthochschule
Paderborn
D- 33095 Paderborn
Germany
C. Friedrich
Werkstoffkunde der TU Darmstadt
und Staatliche
Materialprufungsanhalt
Grafenstrasse 2
D-64283 Darmstadt
Germany
Y. G. Gogotsi
Institut fur Angewandte Mineralogie
Universitat Tubingen
Wilhelmstrasse 56
D-72074 Tubingen
Germany
J. 0. Hansen
Division Pty Ltd
PO Box 1770
Southdale 2 135
South Africa
M. Hoffmann
Fakultat fur Maschinenbau
Institut fur Werkstoffkunde I1
Universitat Karlsruhe
Kaiserstrasse 12
Postfach 6980
D-76 128 Karlsruhe
Germany
R. D. Hoffmann
Westfalische Wilhelms-Universitat
Miinster
Anorganisch-Chemisches Institut
Wilhelm-Klemm-Strasse 8
D-48 149 Miinster
Germany
M. I. Heggie
School of Chemistry, Physics and
Environmental Sciences
University of Sussex
Falmer
Brighton BN1 9QJ
UK
V. Jayaram
Department of Metallurgy
Indian Institute of Science
Bangalore
India
W. Jeitschko
Miinster
D-48149 Miinster
Germany
XXIX
G. Jungnickel
Fachbereich Physik
Paderborn
D- 33095 Paderborn
Germany
C. P. Klages
Fraunhofer Institut fur Schicht und
Oberflachentechnik (IST)
Bienroder Weg 54 E
D-38108 Braunschweig
Germany
T. Kraft
lnstitut fur Angewandte Mineralogie
Wilhelmstrasse 56
D-72074 Tubingen
Germany
A. Krell
Fraunhofer Institute for Ceramic
Technologies and Sintered Materials
Winterbergstrasse 28
D-0 1277 Dresden
Germany
C. D. Latham
University of Exeter
Stocker Road
Exeter EX4 4QL
UK
W. Lengauer
Institute for Chemical Technology of
Inorganic Materials
Vienna University of Technology
Getreidemarkt 9/161
A-1060 Vienna
Austria
XXX
J. E. Lowther
University of Witwatersrand
Johannesburg
South Africa
S. Luyckx
School of Process and Materials
Engineering
University of the Witwatersrand
Johannesburg 2050
South Africa
R. Pottgen
Munster
D-48149 Munster
Germany
Z. A. Munir
F. Richter
Technische Universitat ChemnitzZwickau
Institut fur Physik
D-09107 Chemnitz
Germany
Facility for Advanced Combustion

Synthesis
Department of Chemical Engineering
and Materials Science
University of California
Davis CA 95616
USA
R. Riedel
Fachbereich Materialwissenschaft
Technical University of Darmstadt
Petersenstrasse 23
D-64287 Darmstadt
Germany
K. G. Nickel
Applied Mineralogy
Wilhelmstrasse 56
D-72074 Tubingen
Germany
K. A. Schwetz
Advanced Ceramics Lab
Elektroschmelzwerk Gmbh
Max-Schaidhauf-Strasse 25
D-87437 Kempten
Germany
S. Ozbayraktar
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
P. K. Sen
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
C. S. J. Pickles
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
G. Serghiou
Max-Planck-Institute for Chemistry
Saarstrasse 23
Mainz
Germany
D. Sherman
Department of Materials Engineering
Technion - Israel Institute of
Technology
Haifa 32000
Israel
M. Sibanda
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
I. Sigalas
Division Pty Ltd
PO Box 1770
Southdale 2 135
South Africa
P. K. Sitch
Fachbereich Physik
Paderborn
D- 33095 Paderbron
Germany
G. D. Soraru
Universita di Trento
Dipartimiento di Ingegneria dei
Materiali
Via Mesiano 77
1-38050 Trento
Italy
R. S . Sussmann
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
XXXI
K. Takagi
Toyo Kohan Co. Ltd.
Tokyo
Japan
R. Telle
Institut fur Gesteinshuttenkunde
RWTH Aaachen
MauerstraBe 5
D-52056 Aachen
Germany
S. Veprek
Institute for Chemistry of Inorganic
Materials
Technical University Munich
Lichtenbergstrasse 4
D-85747 Garching b. Munich
Germany
C. J. H. Wort
Division Pty Ltd
PO Box 1770
Southdale 2135
South Africa
A. Zerr
Fachgebiet Disperse Feststoffe
Technical University of Darmstadt
Petersenstrasse 23
D-64287 Darmstadt
Germany
List of Symbols
a!
a
a!
a
a?P, x
P
P
Y
Yi
r(n)
"/S
r
s
tan 6
Ac
AG!98
ASint
AT
AX
&
&
i
rl
rl
0
8
20
6
6
61
62
x
x
x
x
x
x
x
absorption coefficient
atomic attraction constant
growth parameter
power absorption coefficient
polytypes or phases
atomic repulsion constant
geometrical factor
rake angle
secondary ion yield
orientational surface energy
surface energy
width of X-ray reflection
microplastic deformability
dielectric loss factor
concentratation difference
Gibbs free energy
interfacial entropy
temperature change
change of size or mass
elastic strain
emissivity
strain rate
degree of conversion to nitride
fraction of reaction completed
angle
constant relating tensile strength and hardness
X-ray scattering angle
entering angle
thermal conductivity
thermal conductivity of rectants
thermal conductivity of products
empirical parameter relating bulk modulus and
inclination angle
layer thickness, mean free path
polarity of bond
thermal conductivity
wavelength
X-ray wavelength
mean free path
degrees
J
J
K or "C
degrees
J cm-2 s-I
bond length
degrees
m
m
m
K-'
XXXIV
P
P
v
7r
P
P
P
Pm
U
U
ff
UO
ffb
ffij
ffS
UY
7
7-
4
4, w, 74
4
X
W
(4
0
a
a
a
a0
acr
ai
a, b
a, 6 , c
A
A
A
ABAB,
ABCABC
A,B,H,HA
b
B
B
(B4C)
List of Symbols
C/Ti ratio
coefficient of friction
Poisson ratio
complementary energy
J
density
kg m-3
dislocation density
resistivity
theoretical density of product
conductivity
electrical conductivity
stress
Pa
median failure stress
Pa
fracture strength in bending, modulus of rupture
local stress field
J cm-* sC1 KC4
Stefan-Boltzmann constant
yield stress
GPa
annealing time
S
help time
angle between crack and tensile stress
ternary phases
azimuthal angle between polarization vector and substrate direction
constraint factor
electron affinity
wear coefficient
average diffusion distance in time r
vacancy in crystal structure
indent size, half length of diagonal
crack length
depth of cut
equilibrium bond distance
critical flaw size
depth of lateral crack on erosion
heat capacity coefficients
crystal unit cell parameters
lattice constants
area
contact area
material constant
m
m
mm
m
m
m
nm
m2
m2
stacking sequences
stacking positions
Burgers vector
bulk modulus
GPa
designation of a dissolved species in, e. g., a liquid
designation of a non-stociometric compound (solid solution)
List of Symbols
Ci
CP
d
d
d
d
d
d
d
d
dP
D
D
D
D
DO
DH, DC
e
E
E
E
EO
E"
EC
EF
Ei
Eirnax
EP
f
f
f
f
h
F
XXXV
radius of radial crack

m
m s-'
velocity of light in vacuo
interfacial concentration
m
radius of lateral crack on erosion
proportionality constant
specific heat per unit volume
concentration of impurities
heat capacity
J g-' K-'
bond length
A
degree of dilution
diameter of Brinell impression
m
m
diameter of Vickers impression
grain size
m
height of beam
m
layer thickness
rad
spacing of powder diffraction rings
pore diameter
m
diameter of Brinell indenter
diameter of median crack
m
diffusivity
size of particles
diffusion factor
diffusion coefficients at high and low temperature
unit electron charge
activation energy
J
binding energy
J
Young's modulus
theoretical Young's modulus
E/(l-v2)
J
composite potential energy
Fermi energy
J
band gap
J
ion energy
J
maximum ion energy
J
potential energy
mm mine'
feed rate
Hz
frequency
volume fraction
Hz
Weibull safety factor
volume fraction of Z
N
force
statistical failure probability
ion flux
J
external work (linear elasticity)
vapor phase
shear modulus
XXXVI
i, a
I
IBB
4
IRB
ji
J
k
k
k0
hog
kL
k*
kr
K
K
KIC KICO
J
1
1
1
1
L
Lm,,
m
M
M
M
A4
Mi
n
n
List of Symbols
strain energy release rate

toughness, fracture energy, work of fracture
convective heat transfer coefficient
indentation depth
Planck constant
hardness
enthalpy
enthalpy of formation at 298 K
Brine11 hardness
Meyer hardness
Knoop hardness
plastic hardness
Vickers hardness
average applied compressive stress in hardness
GPa
fluxes of impinging ions and deposited atoms
rank order of test result
intensity of black body radiation
peak height
intensity of real body radiation
current density
mass flux
Boltzmann constant
constant for layer growth
reaction constant
logarithmic rate constant
linear rate constant
parabolic rate constant
reaction coefficient
proportionality constant
stress intensity factor
fracture toughness
diffusion path length
length of sample
long diameter of Knoop impression
span of beam
defined load
maximum load
Weibull modulus
mode of deformation (I, 11, or 111)
metal
Mohs hardness
weight
molecular mass of impurity
number
order of reaction
N m-l
J cm-2 s - ~K-'
GPa
GPa
GPa
GPa
test
m2s-l or kg2m-4s-'
Paris exponent for fatigue

refractive index
stress exponent
number of tests
average coordination number
no. of constraints for coordination number r
average coordination number
grain size exponent
momentum
porosity
fixed load
gas pressure
porosity
pressure
ambient and high pressure
confining pressure in powder
pressure of nitrogen
partial pressure of O2
Porod scattering vector
scattering vector
activation energy
heat of reaction
resonance factor
heat of transport
radius
distance from crack tip
interatomic distance
radius of curvature
equilibrium interatomic distance
gas constant
film growth rate
average roughness
radius of plastic zone
solid phase
elastic recovery
stoichiometric ratio
entropy
thickness of window
time
ChI4?
delay time
time for wave propagation
temperature
ternary phase
ambient temperature
temperature limits
Yo
GPa
Pa
Pa
Pa
J
J g-'
J
m
m
Yo
Jmol-' K-'
S
S
S
K or "C
K or "C
K or "C
XXXVIII
UP
List of Symbols
adiabatic combustion temperature

critical temperature and pressure
eutectic temperature
absolute melting temperature
substrate temperature
displacement
stoichiometry factor
wave velocity
internal energy
substrate bias voltage
elastic strain energy
plasma potential
surface free energy
average velocity
machining velocity
volume
wavenumber
longitudinal velocity of sound
volume of pores
volume
volume fraction
symbol for vacancy in a chemical formula
applied substrate bias voltage
volume lost in erosion impact
molar volume of metal
orientational growth rate
molar volumes of product and reactants
sample thickness
RF power
carbon-to-metal ratio
coordinate
layer thickness
liquid phase
lattice directions
Miller indices
K or "C
K or "C
K or "C
m
J
J
J
m min-'
m3
cm-'
m s-'
m3
V
m3
m
W
List of Abbreviations
3PB
4PB
ACC
AES
AFM
APW
AR
ASEA
ASTM
b.c.c.
b.c.t.
BB
BET
3C, 4H, 6R
CAD
CALPHAD
cBN
CCD
CED
CMC
COOP
CN
CVD
CVI
cw
d.c.
DAC
DCC
DF-TB
DH
DIN
dlC
DLC
DMO
DOS
DTA
ECH
ECR
three-point bend
four-point bend
amorphous covalent ceramics
Auger electron spectroscopy
atomic force microscope
augmented plane wave
antireflection
Swedish company
American Society for Testing and Materials
body-centered cubic
body-centered tetragonal
black body
Brunauer-Emmett-Teller method for determining porosity
polytype notations of Sic (C: cubic, H: hexagonal, R:
rhombohedral)
cathodic arc deposition
calculation of phase diagrams model
cubic boron nitride
charge coupled device
cutting edge displacement
ceramic matrix composite
crystal orbital overlap population
coordination number
chemical vapor deposition
chemical vapor infiltrated
continuous wave
direct current
diamond anvil technique
direct coagulation casting
density-functional tight-binding method
methy ldiethoxysilane
Deutsche Industrie Norm
diamond-like carbon
diamond-like carbon
directed metal oxidation
density of states
differential thermal analysis
electron cyclotron heating
electron cyclotron resonance
XL
EDAX
EELS
EP
EPMA
EPR
ERD
ERDA
ESCA
ESK
EXAFS
f.c.c.
FEPA
FTIR
FWHM
FZK
GA-XRD
gc
GEC
GFRP
GGA
h
hBN
HF-CVD
HIP
HK
HOMO
HOPG
HPHT
HPL
HPMS
HR
HR-TEM
HSS
HV
IBAD
ICSD
ICDD
IED
IR
ISE
IS0
ITER
JAERI
JFM
JIS
KFM
energy-dispersive analysis of X-rays

electron energy loss spectroscopy
electroplated
electron probe microanalysis
electron paramagnetic resonance
elastic recoil detection
elastic recoil detection analysis
electron spectroscopy for chemical analysis
Elektroschmelzwerk Kempten
extended X-ray absorption fine structure
face-centered cubic
Federation Europeen des Fabricants de Produits Abrasifs
Fourier transform infrared
full width at half maximum
Forschungzentrum Karlsruhe
glancing angle XRD
glassy carbon
General Electric Company, USA
glass-fiber reinforced plastic
generalized gradient approximation
hexagon a1
hexagonal boron nitride
hot filament CVD
hot isostatic pressing
Knoop hardness
highest occupied molecular orbital
highly ordered pyrolytic graphite
high-pressure high-temperature
high-pressure laminate
high-pressure microwave source
Rockwell hardness
high-resolution TEM
high-speed steel
Vickers hardness
ion-beam assisted deposition
inorganic crystal structure database
international center for diffraction data
ion energy distribution
infrared
indentation size effect
International Standards Organization
international thermonuclear experimental reactor
Japan atomic energy research institute
Johnson figure of merit
Japanese Standards
Keyes figure of merit
LAS
LDA
LDA
LIDT
LPI
LPSSiC
LPSSS
LRO
LSF
LSI
LWIR
MAK
MAS-NMR
Me-DLC
MMC
MOR
MOSFET
MS
MSIB
MTES
MTF
MW
MWP-CVD
NASA
ncTi02
NDE
Nd-YAG
NEA
NICALON
NIRIM
NMR
NRA
ORNL
PA-CVD
PAlC
PCS
p.p.m.
PBC
PC
pcBN
PcD
PCS
PCT
PTC
PTES
PTFE
XLI
lithium aluminosilicate
local density approximation
laser diode array
laser induced damage threshold
liquid polymer infiltration
liquid-phase sintered S i c
low-pressure solid-state source
long-range order
line spread function
liquid silicon infiltration
longer wavelength infrared
Maximal zulassige Arbeitsplatz Konzentration
magic angle spinning NMR
metal-DLC hybrid
metal matrix composite
modulus of rupture
metal-oxide silicon field effect transistor
mass spectroscopy
mass-selected ion beam
methy ltriethoxy silane
modulation transfer function
microwave
microwave plasma CVD
National Aeronautics and Space Administration (USA)
nanocrystalline titania
nondestructive evaluation
neodymium-yttrium-aluminum-garnet laser
negative electron affinity
branded Si-C-0 composite fiber from Nippon Carbon
National Institute for Research in Inorganic Materials (Japan)
nuclear magnetic resonance
nuclear reaction analysis
Oak Ridge National Laboratory
plasma assisted CVD
polyaluminocarbosilane
polycarbosilane
parts per million
periodic bond chain
potential cycling
polycrystalline boron nitride
polycrystalline diamond .
polycarbosilane
Patent Cooperation Treaty
polytitanocarbosilane
phen y ltriethoxy silane
polytetrafluoroethylene
XLII
PP
PVD
r
RBAO
RBM
rBN
RBS
RBSN
RF
RSF
RSSC
S.C.
s.c.cm.
SAD
SAXS
scs
SEM
SERR
SHS
SIALON
SiCAlON
Si-DLC
SIF
SIMS
SNMS
SP
SRO
STM
ta-C
taC
TD
TCNE
TEM
TGA
TH
TRS
TZP
UHP
UPS
uv
VAMAS
vc
VEC
VLS
vs
wBN
polymer pyrolisis
physical vapor deposition
rhombohedral
reaction bonded aluminum oxide
reaction bonded mullite
rhombohedral boron nitride
Rutherford back-scattering
reaction bonded silicon nitride
radio frequency
reduced spatial frequency
reaction sintered silicon carbide
simple cubic
standard cubic centimeters
small angle diffraction
small-angle X-ray scattering
Textron process Sic fibers with C core and C surface
scanning electron microscope
strain energy release rate
self-propagating high-temperature synthesis
Si-A1-0-N (silicon aluminum oxynitride) fiber
SiC-AlN-Al20C composite fiber
Si-DLC hybrid
stress intensity factor
secondary ion mass spectrometry
secondary neutron mass spectrometry
sintered powder
short-range order
scanning tunnel microscopy
hydrogen-free amorphous carbon
tetrahedral amorphous carbon
theoretical density
tetracyanoethylene
transmission electron microscope
thermogravimetric analysis
triethoxysilane
transverse rupture strength (= MOR)
tetragonal zirconia polycrystals
ultahigh purity
ultraviolet photoelectron spectroscopy
ultaviolet
Versailles Agreement on Materials and Standards
vapor phase formation and condensation process
valence electron concentration
vapor-liquid-solid process
vapor-solid reaction
wurtzitic boron nitride
XANES
XPS
XRD
YAG
YLF
XLIII
X-ray absorption near edge structure

X-ray photoelectron spectroscopy
X-ray diffraction
yttrium aluminium garnet, yttrium aluminate, Y2A15012
yttrium-lithium-fluorite

A. Zerr and *R. Riedel
Introduction
The synthesis of new materials with hardness comparable to or even harder than diamond is of considerable fundamental and technological interest and is a great challenge to chemists, physicists, and materials scientists. Most of the known ultrahard
materials, including diamond and cubic boron nitride, were first synthesized in the
1950s and industrially manufactured using high pressure-high temperature processes
[I-31. Extensive research in this domain continues and recently a few new materials
have been synthesized or rediscovered as superhard ones (Si02-stishovite [4], cubic
Si3N4 [5]). New vapor deposition methods (CVD, PVD, laser ablation etc.) which
allow the deposition of diamond, cubic boron nitride and other hard materials
films at low temperature and low pressure (i.e. often under metastable conditions)
on a variety of substrates have been developed since the early 1980s [&lo].
Diamond and cBN (cubic boron nitride) combine excellent mechanical, chemical,
and physical properties. However, owing to its instability at high temperatures,
diamond cannot be used, for example, as a cutting tool for steel. Moreover, with
increasing temperatures diamond and cBN weaken due to the onset of the transformation to the graphite structure so that above 1100C in a nonoxidizing atmosphere
boron carbide B4C(with a hardness of about 30 GPa) has been identified as the hardest
material [I I]. For this reason and because of the need to replace expensive diamond in
many other applications, new hard materials with comparable or even superior properties are required. Theoretical work on the carbon nitride C3N4predicted that this compound could have a hardness comparable to or even greater than that of diamond
[12,13]. The synthesis of polycrystalline C3N4films was first reported in 1992 [I41
and in 1993 [ 151and has been under extensive investigationsince then, resulting in hundreds of publications on this subject. However, in a few recent publications there has
been doubt the thermodynamic stability of theoretically predicted ultrahard C3N4
phases [ 161 and whether their hardness would be comparable to that of diamond
[ 171. In consequence, research on the low-temperature synthesis of diamond
and cubic boron nitride [18],the search for other possible candidate compounds as
well as microstructure design of known materials and their composites [ 19-21]
(heterostructures, whiskers, nanocomposites) remain the subject of experimental
and theoretical efforts. Microstructure design is addressed in this book by D. Sherman
and D. Brandon in Part I, by S. Vepfek in Part I1 and by A. Krell in Part 111.
This introduction deals with some of the latest experimental and theoretical
developments in the field of novel boron- and carbon-based ultrahard materials
as well as with new observations on a class of silicon-based compounds which
previously were not classified as ultrahard.
* This is a revised version of the paper published earlier [ 1521.
XLVI
Introduction: Novel Ultrahurd Materials
Hard Materials
Generally, hard materials are solids with high hardness in the range 8-10 on the
Mohs scale of hardness, given by the sequence of minerals which can be scratched
by the next (Table 1). Usually, common hard materials are subdivided into
compounds with metallic (like TIN or WC), ionic (Al2O3>,or covalent bounding
(diamond, Si3N4)[22]. The definition of ultrahard materials is that their hardness
values are comparable to that of diamond. Another definition often used in the
literature is that the hardness of such materials exceeds 40GPa. Among all
known single phase compounds diamond, cBN and probably boron carbides
(Bl3C2-Bl2C3)satisfy the latter definition. Accordingly one can expect that novel
ultrahard compounds will be found in the isothermal ternary phase diagram BC-N given schematically in Fig. 1. In particular, the carbon nitrides (e.g. C3N4)
and the boron carbonitrides (B,C,NZ) have been discussed as substitute materials
Table 1. Hardness ranking of minerals and some prominent synthetic ceramic materials according
to F. Mohs. In the case of the synthetic materials microhardness values are given in units of the
Knoop scale. The microhardness variations result from variations in the grain size, the load of
indentation, the phase composition and the used densification techniques. Modified after [ 1521.
Minerals/
synthetic
materials
Formula
Mohs
hardness
Talcum
Hexagonal
boron nitride*
Gypsum
Calcite
Fluorite
Apatite
Feldspar
Quartz
Topaz
p-Silicon nitride*
Mg,[(OH)z/Si4O,oI
hBN
CaS04 2 H 2 0
CaCO,
CaF2
Ca5[(F3OH)/(PO&I
K[AlSi,O,]
Si02
A1z[F2/Si041
BSi3N4
2
3
4
5
6
7
8
Corundumt
Titanium nitride*
Silicon carbide*
%-Silicon nitride
Titanium carbide*
Boron carbide'
Titanium diboride*
Boron suboxides
Stishovite*
Cubic boron nitride'
Diamond
Sic
%Si3N4
TIC
B4C
TiBz
B,O
Si02
cBN
C
Microhardness,'
Knoop 100
Wal
0.15-0.30
17
21
26
26-35
28
30
10
30-59
33
45
75-100
' The microhardness values are taken from published sources [7] and [102].
The microhardness varations are taken mostly from previous work [25].
* Synthetic material.
Synthetic material or natural mineral.
Microhardness
variations for
polycrystals' [GPa]
14-26
14-29
20-38
2648
13-32
20-38
19-35
Hard Materials
XLVII
Figure 1. Schematic of the isothermal ternary B C - N phase diagram at temperatures below the
decomposition of the stoichiometric compounds and the regimes of composition of some solid solutions discussed. For explanation of the compounds see text. First published in [I 521 and reproduced
with permission.
for diamond. One can also expect that metastable dense high pressure phases of the
compounds based on silicon or oxygen can belong to ultrahard materials. One of
these is the high pressure-high temperature stishovite phase of Si02 with a hardness
exceeding 33 GPa [4], which is almost an order of magnitude above that of quartz,
the ambient pressure phase of Si02 (Table 1). The second one is cubic Si3N4with the
spinel structure, whose hardness may be comparable to that of Si02-stishovite [5].
Hardness
Hardness is one of the quantitative parameters that describe resistance of a material
towards plastic (irreversible) deformation. Plastic deformations begin when the
shear component of the stress applied to a material exceeds some value called the
yield stress. There are many ways to create a plastic deformation and consequently
many ways to define and to measure resistance of a material towards such deformations. Hardness can be determined in several ways:
-
Scratching methods (Mohs, Martens),

Grinding methods (Rosiwal).
Indenting methods (Vickers, Knoop, Brinell, Rockwell, Shore).
For example, the Vickers hardness, Hv, is defined as the applied load P divided by
the surface area of the impression, while the Knoop hardness H K is derived from the
load P divided by the projected area of the impression:
1854.4P
Hv =
d2
14 229 P
HK=-
12
XLVIII
where d is the diagonal of the square-based diamond pyramid of the Vickers

indenter and I is the long diagonal of the rhombus-based diamond pyramid of the
Knoop indenter. In the case of applied test loads below 1.96N the determined
hardness is defined as microhardness and depends on the applied amount of load
[23]. Generally, the unit of the hardness measured is given in kgmm-* or in GPa
(1000 kgmmP2 = 9.81 GPa).
The Vickers or Knoop hardness can be also expressed in terms of Mohs hardness,
M , by the following expression [23]:
H v = 3.2M3.
(3)
However, this expression cannot be applied for superhard materials like diamond.
Each testing method yields different hardness values for one material. Thus, in
order to compare hardness values of different materials, the specific test method
and the test conditions have to be described carefully. Moreover, the hardness of
single crystals depends for many compounds on the crystallographic plane tested
and for the Knoop indentor additionally on the orientation of the indentors long
axis relative to the crystallographic axis of the examined crystal. For example, in
experiments on single-crystalaSi3N4the Vickers hardness measured on different crystallographic planes varied by more than 34% and the Knoop hardness measured on
the same crystallographic plane by 7% [24]. Hardness of polycrystalline materials is
strongly influenced by: residual stresses, toughening phases, microstructural textures,
the grain size, the applied load and the porosity as well as by the structure and
composition of grain boundaries. As a consequence, the hardness of polycrystals
may significantly differ from that of the single crystal counterpart. For example,
due to the above reasons the measured microhardness of polycrystalline TIC varies
between 1200 and 3250Hv or by more than 270% and that of polycrystalline
Si3N4between 1500 and 4800 (Hv)or by more than 300% [25]. In Table 1, the microhardness values and their variations for some prominent synthetic ceramic materials
are listed ranked according to the Mohs scale. The above topics are discussed in more
detail in Part I by D. Sherman and D. Brandon, and by A. Krell.
There are few theoretical attempts to describe hardness quantitatively in terms of
the elastic bulk or shear moduli of an ideal solid. The elastic moduli and the
corresponding hardness of a compound or element are strongly related to its
molar volume, to its chemical bonding, and to its crystal structure. Basically, it
can be stated that the higher the hardness the lower the molar volume and the
more covalent the bonding of the material.
Liu and Cohen suggested in their paper on hypothetical PC3N4 [12] that on the
microscopic level, for ideal systems, hardness is determined by the bulk modulus.
To estimate the bulk modulus they used an empirical model developed earlier
[26], where the bulk modulus scales as a homopolar energy gap divided by the
volume of the bond charge. The resulting relation gives theodependence of the
bulk modulus B (in GPa) as a function of the bond length d (in A) and the empirical
parameter A:
1971 - 220X
(4)
B=
d3.5
Hurd Materials
XLlX
Table 2. Calculated equilibrium volumes, bulk moduli, and cohesive energies of some postulated
ultrahard materials. The calculated and/or experimental values of diamond, lonsdaleite, cubic
BN, and !3Si3N4are given for comparison. The experimental volume and density values are derived
from crystal structure data. CH.6 = all sp2-bonded hexagonal carbon phase 26,73,74]; Cb,c,t,.4= all
sp*-bonded body-centered tetragonal carbon [26,72,76]; BNh.c.t.-4= all sp -bonded body centered
tetragonal BN [119]. First published in [152] and reproduced with permission.
Material
Crystal
symmetry
Vo
nm3/
atom]
Density
[g/cm3]
B,
[GPa]
Ecoh
444 (calc)
435 (exp)
440 (calc)
367 (calc)
369 (exp)
265 (calc)
256 (exp)
427 (calc)
372 (calc)
362 (calc)
268 (calc)
8.17/atom (calc)
7.37/atom (exp)
8.14/atom (calc)
13.2/BN pair (exp)
Cdiarnond
cubic
5.67 (exp)
3.51 (exp)
Clonsdalelte
cBN
hexagonal
cubic
6.47 (exp)
5.90 (exp)
3.52 (exp)
3.45 (exp)
hexagonal
10.42 (exp)
3.19-3.20
(exp)
3.49
3.17
2.97
2.82
hexagonal
hexagonal
tetragonal
tetragonal
6.25
6.29
6.72
7.37
Refs
[eVI
74.3/unit cell (calc)

81.5/unit cell
9.06/atom
8.47/atom
13.36/BN pair
X is 0 for homopolar solids of group IV elements, and 1/2, 1, and 2 for heteropolar
solids of group 111-IV, 111-V, and 111-VI elements, respectively. From this, it is
evident that increasing ionicity results in a decrease in B. This expression has
been further improved to account for non-octet compounds such as Si3N4 by
using the average coordination number N, # 4 [26]:
B=-
(N,.) (1971 - 220X)

4
d3.5
In Table 2, some experimental and calculated structural properties such as the

equilibrium volume, bulk modulus, and cohesive energies of candidate materials
with potentially ultrahigh hardness are summarized. The equilibrium volume
corresponds to the minimum of the total crystal energy as a function of volume [26].
The cohesive energy of a crystal represents the difference between the energy of the
isolated constituent atoms or molecules and the energy of the crystal at absolute
zero temperature [27]. It is evident from Table 2 that the higher the cohesive energy
and the lower the equilibrium volume the higher the bulk modulus of the material.
On the other hand materials deform plastically only when subjected to shear
stress. According to Frenkel analysis, strength (yield stress) of an ideal crystalline
solid is proportional to its elastic shear modulus [28,29]. The strength of a real
crystal is controlled by lattice defects, such as dislocations or point defects, and is
significantly smaller then that of an ideal crystal. Nevertheless, the shear stress
needed for dislocation motion (Peierls stress) or multiplication (Frank-Read
source) and thus for plastic deformation is also proportional to the elastic shear
modulus of a deformed material. Recently Teter argued that in many hardness
tests one measures plastic deformation which is closely linked to deformation of a
shear character [17]. He compared Vickers hardness data to the bulk and shear
Figure 2. Scattering of the Vickers hardness for a common set of hard materials when compared
with bulk modulus (gray region) and shear modulus (black region). Following this comparison
Teter suggested that the shear modulus is a significantly better qualitative predictor of hardness
than the bulk modulus [ 171.
moduli from over thousand measurements and found that the shear modulus of
polycrystalline aggregates is a significantly better qualitative predictor of hardness
than the bulk modulus (Fig. 2).
Experimental bulk moduli can be obtained from the measurement of lattice
parameters and volumes as a function of pressure [30]. The single crystal elastic
moduli can be measured using the Brillouin spectroscopy, inelastic neutron scattering, ultrasonic measurements or the Schaefer-Bergmann method [311. Once the
single crystal moduli are known one can derive the bulk B and shear G moduli of
a polycrystalline material [32].
Carbon-based Hard Materials

The most common allotropes of elemental carbon are graphite and diamond.
Graphite crystallizes in a sheet structure with hexagonal symmetry and sp2 hybridization of the trigonally coordinated C-atoms whereas diamond exhibits a cubic
lattice related to the zinc blende structure with sp3 hybridization of the tetrahedrally
coordinated C-atoms. Less common carbon polymorphs are lonsdaleite with
the hexagonal wurtzitic structure 1331, and the rhombohedral polymorph called pdiamond (3R polytype of wurzitic structure) [34,35]. The rhombohedral polymorph, which was reported as birefringent lamellae in natural diamonds, has not
yet been obtained in significant amounts needed for detailed studies [35]. Graphite,
LI
Figure 3. The different carbon modifications: (a) hexagonal graphite; (b) cubic diamond; and (c)
hexagonal lonsdaleite. First published in [ 1521 and reproduced with permission.
diamond, and lonsdaleite are, however, well investigated and their structures are
shown in Fig. 3. In lonsdaleite, comprised of the same tetrahedral configuration
as in diamond, the planes of six-membered carbon rings are in the chair and boat
conformation and are stacked in an ABAB sequence while in diamond, these
planes exhibit the chair conformation exclusively and are arranged in an
ABCABC sequence. The recent discovery of the c 6 0 molecule shown in Fig. 4,
which is the most prominent representative of the fullerene family, led to a new
type of carbon allotrope. In fullerenes, the carbon atoms form spherical clusters
comprised of six- and five-membered rings of the general composition C20+2m
(m = 0 , 2 , 3 . ..) where m is the number of hexagons. The c 6 0 fullerene has been
predicted by Kroto and Smalley since 1985 [36-38] and was isolated first in
macroscopic quantities by Kratschmer et al. in 1990 [39-41]. At present, the
spherical carbon clusters and their derivatives are discussed with respect to their
application in material science [42,43]. Furthermore, a variety of new polymeric
carbon networks have been postulated to exhibit interesting materials properties
[41,44]. Recently, carbon nitrides such as the hypothetical compound C3N4 have
been also considered for the synthesis of ultrahard materials [ 14,151.
LII
Figure 4. Molecular model of the fullerene C60.The gray carbon atoms illustrate one of the 12
pentagons present in C6,,. First published in [152] and reproduced with permission.
Diamond
Besides the aesthetic appearance of diamond in the form of gemstones, diamond is
the hardest material known, and is, therefore, on the top of the Mohs scale and has
the lowest molar volume (3.4cm3) of any material. Owing to this unique property,
diamond is used for many technological applications such as abrasion, cutting, and
polishing. Diamond also has the highest thermal conductivity (2000 W m-' K-') of
any material at room temperature, four times as high as the value of Cu or Ag, is a
good electrical insulator, it has a small dielectric constant and exhibits a high
electron/hole mobility. Boron doped diamond (Typ IIb) exhibiting a p-type conductivity has been known for a long time. Production of diamond with a reasonable
n-type conductivity was one of the most difficult tasks in diamond synthesis.
Koizumi and coworkers recently obtained diamond films exhibiting n-type conductivity by using microwave enhanced plasma CVD with phosphine PH3 as a donor
source for homoepitaxial deposition of n-type diamond 1451. Therefore, diamond
will be a most important candidate material for future applications in electronic
devices. In addition, diamond has low coefficients of friction and thermal expansion,
high chemical and corrosive resistance towards most acids and oxidizing substances,
it is transparent to visible and infrared light, withstands ionizing radiation and can,
therefore, also be used as window or lens material or as a protective coating for this
application.
Conventionally, diamond is synthesized at high pressure and high temperature
according to the method developed by the General Electric Company in the 1950s
LIII
[l, 461. Synthetic diamond is now commercialized and is utilized for cutting, grinding,
and polishing. Recent developments in the high-pressure synthesis technique allow
growth of diamond single crystals up to 25 carats in weight [47]. The high-pressure
synthesis of diamond is described in more detail by M. W. Bailey et al. in Part 111,
while hydrothermal synthesis is discussed in Part I1 by K. G. Nickel et al.
Since the mid-1980s the vapor deposition synthesis of diamond films has
attracted increasing scientific and industrial interest. At present, vapor-grown
diamond products are commercially viable as thin-film-coated cutting tools and
freestanding thick-film cutting tools, as substrates for thermal management
application and radiation detectors, as optical windows and for production of
high-range audio-speaker diaphragms. Commercialization of the vapor-grown
diamond became possible due to the cost reduction below $5/carat as a result of
the dramatic increase in growth rate and of improvements in energy-use efficiency
[481.
Advanced diamond films are synthesized using the gas-phase decomposition of
volatile carbon sources such as methane (CH4), acetone (H3C-CO-CH3),
carbon monoxide (CO), acetylene (HC-CH), or adamantane (CI0Hl6)and is
conducted under temperature and pressure conditions where graphite is the stable
polymorph (Fig. 5). The most important methods for producing CVD-diamond
under metastable conditions are:
-
Microwave Plasma Assisted Chemical Vapor Deposition (PACVD) [49,50],

Heated Filament Assisted Chemical Vapor Deposition (HFCVD) [5 13,
Figure 5. Pressure and temperature conditions of the diamond synthesis: (a) shock wave production
of diamond; (b) high temperature, high pressure regime for the synthesis of diamond; (c) catalytic
region for diamond formation; (d) chemical vapor deposited diamond; and (e) transformation of
CG0into diamond. The most recent review of the P, T phase diagram of carbon can be found
elsewhere [151].
LIV
-
Direct Current (DC) Plasma Jet Deposition [52,53],and

Oxygen-Acetylene Torch [54].
The chemical-vapor deposition of diamond films and their applications are reviewed
by C.-P. Klages and by R. S. Sussmann et al. in Parts I1 and 111, respectively. To date
the most effective CVD method (with the greatest mass deposition rate) is based on
the hydrogen/hydrocarbon gas mixtures. In this method diamond is formed for
kinetic reasons according to the simplified reaction:
H2
Cdiamond f 2H2.
In a typical process, the hydrocarbon precursor containing more than 95% H2-gasis
passed through a plasma (700-1000C) or over a heating filament ( T M 2000") at
less than atmospheric pressure. The reaction product, solid carbon, is then deposited
on a substrate heated at 800-1000C and contains both graphite and diamond. In
the presence of H2-gas, the formation of unsaturated carbon nuclei and hence the
growth of graphite is suppressed by atomic hydrogen formed under these conditions
and is due to the reaction of the solid carbon with hydrogen radicals (H') giving
volatile hydrocarbons. The reaction rate of Cgraphite
with H' is about 20 times as
high as the rate of diamond. Therefore, the formation of diamond is promoted.
Growth rates of up to 0.9 mm h-' [55] or 20 carats per hour [48] have been achieved
on a variety of substrates making the CVD-diamond a highly interesting material
for technological applications.
Diamond films have also been deposited from hydrogen-free gas mixtures such
as C60/Ar using microwave apparatus. The deposition rates are, however,
significantly lower. Additionally, use of hydrogen-poor plasmas results in nanocrystalline (3-10nm) diamond films in contrast to micrometer sized crystals from the
hydrogen-rich plasmas [56].
There are continuous theoretical attempts to describe the mechanism of CVDdiamond synthesis including mechanisms of surface reactions, diamond nucleation,
and film growth. To achieve this aim various phenomenological or first-principles
models, molecular dynamics and Monte Carlo simulations have been used [57,58].
While the dominant substrate for low pressure growth of diamond films is single
crystal silicon, several different materials such as Ta, Mo, W, Cu, Au, Ni, Sic, SO2,
and Si3N4have been coated with polycrystalline diamond or diamond-like deposits.
The nucleation rates and the adhesion of the generated films vary with the type of
substrate material, which is related to the formation of intermediate carbide layers
such as Sic or WC.
Identification of vapor grown diamond is accomplished by X-ray diffraction or
electron diffraction using a transmission electron microscope (TEM) and by
Raman spectroscopy. Diamond coatings show the characteristic first-order Raman
peak for diamond at 1332cm-' [59]. In many cases, an additional peak located at
~ 1 5 5cm-'
0
occurs in the Raman spectrum which is attributed to a highly disordered
carbon phase (diamond-likecarbon) [60]. This diamond-like carbon contains sp3 and
sp2 hybridized C-atoms which do not coincide with graphite.
Recently a new simple method for the synthesis of diamond, called metallic
reduction-pyrolysis-catalysis, was reported. In this method diamond powder was
CH4
LV
obtained as a product of reaction of carbon tetrachloride with metallic sodium in an

autoclave at 700C, where CC14 served as a carbon source [18]:
CC14
700C
+ 4NaCl- Catalyst
+ 4NaCl.
As a metal catalyst an Ni-Mn-Co alloy (70 :25 :5 wt%) was used. About 2% of the
carbon yield was well crystallized diamond and the residue was most probably in
an amorphous form, as was evident from X-ray powder diffraction and Raman
spectroscopic measurements.
Diamond-like and Amorphous Carbon

In the course of the research into the synthesis of diamond under metastable conditions, a new class of materials, diamond-like carbon and hydrocarbon phases, have
been discovered. The diamond-like hydrocarbons (aC :H) are generated by the R F
self-bias method, a technique derived from R F sputtering, developed by L. Holland
[61,62]. The molecular ions, C,H;, derived from the particular hydrocarbon used in
the plasma, disintegrate upon colliding with the substrate surface resulting in the
formation of diamond-like hydrocarbon films [63]. The main structural feature of
diamond-like hydrocarbons is the presence of both sp3- and sp2-carbon. Solid-state
NMR-investigations revealed that the material contains sp3-carbon atoms of the
form -C-H or H-C-H [6].
No quaternary carbon atoms could be detected while methyl groups, -CH3, were
found to be present in small amounts. In addition, resonant Raman spectroscopy
showed small 7r-bonded clusters of sp2 sites [64].
It was found that conducting the R F self-bias experiment with hydrocarbons
in the presence of H2 results in production of small diamond clusters. This experimental result indicates that aC : H could be considered as an intermediate
compound formed during the transformation of hydrocarbons to diamond in the
plasma processes [65].
The mechanical properties of diamond-like hydrocarbon films strongly depend on
the hydrogen content. Increasing the ratio of sp3 sites results in decreased hardness
values and lower wear resistance [66]. This phenomenon is attributed to the fact that
hydrogen is monovalent and cannot contribute to formation of a covalently bonded
and highly cross-linked carbon network as found in the diamond structure. However,
microhardness values in the range 30-50 GPa have been measured in aC :H films,
values significantly higher than the hardness of Sic (20-38 GPa). In contrast, diamond-like carbon (aC) is free of hydrogen or contains only little hydrogen and does
not represent microcrystalline diamond [67,68]. The preparation of aC has been
accomplished by magnetron sputtering [68]. Again, the structure and properties of
the aC phase is related to the ratio of the sp3/sp2 sites. However, hydrogen is not
responsible for the stabilization of the sp3-hybridizedcarbon atoms. Here, the mechanical constraints resulting from random covalent networks, which can be calculated
using the constraint-counting method developed by J. C. Phillips [69], can be reduced
by the generation of medium-range or long-range order by clustering or crystallization.
LVI
Another class of novel carbon material is amorphic carbon which can be obtained
by laser ablation [70]. This amorphous phase contains sp3 -bonded nodules of pure
carbon embedded in a matrix of other types of carbon phases. The mean particle size
of the nodules is 20 nm, the density of the films is between 1.85 and 2.89 g crnp3.The
internal stresses derived by distortions of the bonding angles in random networks
are counterbalanced by the high surface to volume ratios of the nanoparticles. Substrate discs 30mm in diameter were coated with uniform layers of amorphous
carbon by laser ablation of a graphite feedstock. Maximum growth rates of about
0.5 pm h-' and film thicknesses of up to 5 ym have been achieved on different substrate materials such as Si, Ge, ZnS, Cu, stainless steel, quartz, glass, and plastics.
One outstanding property of laser ablation in comparison with the CVD process
for the preparation of carbon films is that the substrate temperature does not
exceed 35C during the whole deposition procedure. In contrast to the CVD diamond, which develops polycrystalline columnar structures, the laser-ablated amorphous carbon is deposited in the form of self-seeding nodules. Diamond-like carbon
films are discussed in more detail in Part I11 by C.-P. Klages and K. Bewilogua.
Novel Hypothetical Three-dimensional Carbon Phases

A dense carbon phase with a calculated density of 4.1 g cmP3was predicted by N. N.
Matyusenko and V. E. Strel'nitzkii in 1979 [71]. Due to this high density value,
ultrahigh hardness of this carbon material is expected. In addition, several different
hypothetical three-dimensional polymeric carbon networks with interesting
materials properties have been proposed. The most relevant ones with respect to
the potential of high hardness are the following carbon networks.
(i) In 1983, R. Hoffmann published a metallic allotrope of carbon in which layers
of infinite polyene chains are connected by bonds parallel to the c-axis. Each
layer is rotated by 90" about the c-axis (Fig. 6a). The unit cell of the crystal
structure is primitive body centered tetragonal and contains four atoms
(b.c.t.-4 structure). In this network, carbon is present in the form of trigonal
sp2 atoms. However, in contrast to graphite where the carbon atoms are
arranged in a two-dimensional sheet structure, the trigonal carbon atoms of
the b.c.t.4 structure form a three-dimensional network [72].
(ii) A similar carbon allotrope was proposed by M. A. Tamor and K. C. Hass in
1990. In this structure, the chains of the trigonal sp2 carbon atoms are rotated
by 60" rather than 90" between the layers. The three-dimensional all sp2 phase
of carbon has a hexagonal Bravais lattice with six atoms in the primitive unit
cell and is known as the H-6 structure (Fig. 6b). However, theoretical calculations indicate that H-6 carbon is unstable with respect to the transformation to
diamond. This instability is probably due to the short distances between carbon
chains [73,74].
(iii) The 'super diamond' structure shown in Fig. 7 can be derived from tetraethynylmethane C(C2H)4. In principle, the polymeric network of the super diamond
could be obtained by oxidative coupling of the methane derivative [41,75].
Curbon-based Hard Materials
LVII
Figure 6. (a) Model of a section of the hypothetical polymeric network of the body centered
tetragonal structure (b.c.t.4) of carbon and BN suggested by R. Hoffmann et al. [72]. (b) Model
of a section of the hypothetical hexagonal structure (H-6) of carbon postulated by M. Tamor
and K. Hass [73,74]. In both structures, each carbon atom is considered to be trigonally coordinated
and sp2-bonded, exclusively. First published in [ 1521 and reproduced with permission.
(iv) The carbon skeleton of allene, 2HC=C=CH2, could also be utilized for the
formation of a three-dimensional carbon phase [41]. In this case, the oxidative
coupling of allene could provide a carbon structure with orthogonally arranged
chains of sp2 carbon atoms (Fig. 8). A similar carbon phase could be obtained
by the coupling of tetraethynylallene, (HCGC)~C=C=C(C=CH)~[75].Here,
the carbon chains are connected by butadiene units instead of single bonds.
Both the b.c.t.-4 and the H-6 phase of carbon are discussed in terms of intermediate
structures formed during the chemical vapor deposition of diamond. Furthermore,
these types of structures could play an important role in diamond-like phases. The
calculations of the structural properties of the b.c.t.-4 and H-6 carbon phase using
LVIII
Figure 7. Hypothetical super-diamond structure suggested earlier [41,75]. First published in [ I 521
and reproduced with permission.
the first-principles pseudopotential total-energy method revealed high bulk moduli

B of 350 GPa and 372 GPa, respectively [26,76]. The extraordinary high values of B
are in the range of cBN, the second hardest material known.
Presently, the synthesis of new carbon phases by the coupling of unsaturated
molecular organic compounds such as allenes or alkynes is being intensively
investigated in several laboratories.
Figure 8. Hypothetical allene structure of carbon postulated earlier [41,75]. First published in [I521
and reproduced with permission.
LIX
Fullerenes
It has been shown that fullerenes or their derivatives can exhibit very interesting
chemical, electrical, magnetic, and mechanical properties. Besides, for example,
the superconductivity, which has been experimentally verified for the alkali metal
fullerides M 3 C 6 0 with M = K or Rb [77], fullerenes can serve as a starting material
for diamond synthesis [78,79] and may exhibit high hardness themselves under high
pressure conditions [go].
In 1992 M. Regueiro et al. reported on the transformation of c 6 0 molecules into
polycrystalline diamond by nonhydrostatic compression at room temperature [78]:
& c60
P > 20 GPa/20"C
' Cdiarnond.
In contrast c 6 0 withstands hydrostatic pressure up to 20 GPa [81]. However, the

football molecules seem to be unstable towards uniaxial or shear stresses whereas
they are stable under isotropic stress where the spherical molecules are homogeneously deformed. In a dense arrangement of c 6 0 spheroids, 48 of the 60
carbon atoms have a quasi-tetrahedral coordination which is required in the
diamond structure. Only small structural rearrangements are then necessary for
the transformation into diamond [78].
R. S. Ruoff and A. L. Ruoff proposed that c 6 0 is stiffer than diamond [go]. This
result has been estimated from the calculated bulk modulus of individual c 6 0
molecules. The calculations revealed a bulk modulus B = 843 GPa which is nearly
twice the experimental value of 441 GPa determined for diamond. Since solid c 6 0
forms a van der Waals crystal with f.c.c. lattice and the distance between the
single c 6 0 molecules is about l.Onm, B would be relatively small under normal
conditions. However, when the individual carbon spheres are compressed until
they touch each other, the bulk modulus of the crystal would become in the range
of that of the molecule. Taking into account a volume filling factor of 74% valid for
the f.c.c. structure, B is calculated to be 624 GPa using the volume fraction rule [80].
Therefore, diamond might be outranked by the hardness of c 6 0 crystals. This result
is of great fundamental interest, despite the fact that the extraordinary hardness
value will be only achieved at high pressures (20 GPa).
Carbon Nitride (C3N4)

Theoretical predictions that covalent solids comprised of carbon and nitrogen are
excellent candidates for extraordinary hardness [82,83] lead to a strong interest in
the scientific community which resulted in hundreds of theoretical and experimental
studies on this system. In this chapter we only depict some results on C-N compounds without an attempt to be exhaustive.
The first of such predicted structures, namely PC3N4the structural analogue of
the well-known hexagonal PSi3N4, was suggested almost 10 years ago [12]. A
number of other structures of C3N4 were proposed later: graphite-like (P-6m2)
and cubic defect-zincblende (P-43m) [84], the hexagonal analogue of aSi3N4
LX
(P31c), pseudocubic (P-42m), and cubic (I-43d) [13]. Bulk moduli (and hardness) of
most of these compounds were predicted to be comparable with and the last one
even to exceed that of diamond.
The hardness of the hypothetical carbon nitride, pC3N4, has been comprehensively discussed by A. Liu and M. Cohen [12,83]. In the case of &N4, the bulk
modulus is estimated to be higher than that of diamond (483 GPa) by semi-empirical
methods using Eq. (4) with a bond length d = 0.147 nm and an ionicity factor of
X = 0.5. From ab initio calculations of the total structural energy of C3N4 using
the first principles pseudopotential total energy method, a somewhat lower value
of 427GPa for B is derived. This finding can be attributed to the structural
difference between this material and the completely tetrahedrally coordinated zinc
blende structure from which the scaling law (Eq. (4)) was developed [12,83]. In
contrast, the compound pC3N4 is considered to have the pSi3N4 structure and is
only a partially tetrahedrally coordinated structure. The pSi3N4structure is related
to the well known hexagonal structure of the beryllium silicate Be2Si04.Therefore,
the unit cell of PC3N4 is hexagonal and contains two formula units (Fig. 9). The
carbon atoms are sp3 hybridized and tetrahedrally surrounded by N atoms, whereas
nitrogen has a planar trigonal coordination (sp3 hybridization). The overall structure can be described by a network of CN4 tetrahedra and NC3 sites.
Teter and Hemley suggested the cubic high pressure phase of Zn2Si04denoted as
willemite-I1 as another possible structure of a superhard C3N4[13]. This suggestion
was based on the fact that the structure of the zero-pressure phase of Zn2Si04
(willemite-I) is isomorphous with the structure of Be2Si04. Using first principles
pseudopotential total energy techniques they calculated energetics, structure, and
some physical properties of the cubic willemite-I1 structure as well as of four
other candidate structures of C3N4. They found that aC3N4 (the analogue of
aSi3N4) is energetically favorable at zero-pressure and the cubic willemite-I1
structure might be a high pressure phase of C3N4. The predicted transition pressure
from a-to the cubic willemite-I1phase was 68 GPa. The calculated bulk modulus of
this cubic C3N4was 496 GPa, which is significantly higher than the measured bulk
modulus of diamond (442 GPa) or predicted moduli of a- and pC3N4 (425 GPa and
450 GPa, respectively). This result suggested that the hardness of cubic C3N4with
willemite-I1 structure may exceed that of diamond [13]. However, in his later
work Teter revised this conclusion to the contrary according to the almost linear
relation he has found between shear moduli of polycrystalline compounds and
their hardness [17]. The calculated shear moduli of the polycrystalline p- or cubic
C3N4 are only 60% of the shear modulus of diamond and smaller than that of
cubic BN. Accordingly the hardness of these carbon nitrides (once synthesized)
will probably not exceed that of cubic BN [17]. Further discussion of possible structures of C3N4can be found in Part I in the chapter of J. E. Lowther.
Synthesis of carbon nitrides has been attempted for example by the pyrolysis of
organic nitrogen-containing compounds such as melamine-formaldehyde resin
and subsequent shock compression of the obtained residues [85]. However, no tetrahedral carbon nitride could be detected in the reaction products. In a similar
approach, L. Maya et al. obtained a carbon nitride with trigonally coordinated
carbon by the pyrolysis of organic compounds at 700C and 225 MPa pressure
LXI
a)
Figure 9. Theoretically suggested crystal structures of carbon nitride C3N4(filled circles represent
the carbon atoms): (a) Hexagonal structure corresponding to that of PSi3N4or phenacite, Be2Si04.
(b) Cubic structure corresponding to that of willemite-11, the high-pressure phase of Zn2Si04[ 131.
First published in [ 1521 and reproduced with permission.
[86]. Plasma decomposition of CH4 and N2 provided amorphous solids containing

C, N, and H, exclusively [87]. High pressure pyrolysis of tetracyanoethylene,
(CN)2C=C(CN)2, gave C4.66Nwith graphitic structure [88]. Similarly, the gas
phase decomposition of pyridine in the presence of chlorine at 800C provided
the carbon nitride C5N with a hexagonal sheet structure [89].
Martin-Gil et al. reported on the synthesis of cubic carbon nitride with the zinc
blende structure by pyrolysis of N,N-diethyl- 1,4-phenylene-diarnmoniumsulphate
at 800C in an N2 atmosphere using Se02 as a catalyst [90]. The material obtained
contained both an amorphous matrix and polycrystalline regions with crystallites of
5-50nm in size. The sample as whole had a composition CN, with 0.2 < x < 0.5.
The composition of the embedded crystallites was estimated using EELS (electron
energy loss spectroscopy) data to be C,N,,, with x and y between 3 and 4. The
LXII
Introducfion: Novel Ultrahard Matericils
cubic zinc blende structure of the crystallites was derived from TEM measurements
and confirmed by extended energy loss fine structure analysis [90].
Besides the preparation of polycrystalline C- and N-containing thin films by using
direct current magnetron sputtering with nitrogen as the sputtering gas [ 141, the
synthesis of C3N4 was experimentally verified in the work of C. Niu et a/. [15]. In
this paper, the preparation of the carbon nitride was realized by pulsed laser
ablation of graphite targets in the presence of a nitrogen source. The C-N films
deposited on Si (001) and on polycrystalline Ni were characterized by Rutherford
backscattering (RBS). photoelectron spectroscopy (XPS, ESCA), and electron
diffraction measurements in the TEM mode. The analysis of the diffraction data
(convergent beam electron diffraction) clearly showed that the reflections were in
accord with that expected for the PC3N4 structure. Furthermore, the spectroscopic
analyses revealed the presence of C and N in the deposited films. The bonding in
these solids is covalent. The analysis of the chemical composition of the films determined by RBS exhibited nitrogen contents of up to 45% which is the highest amount
measured in any binary C-N solids to that time. The nitrogen content did not
decrease after thermal annealing in flowing N2 up to 800C indicating the relative
stability of the C-N material. Preliminary investigations of the hardness showed
that the films could not be scratched by hard metals [15].
Thin carbon nitride films containing small crystals were deposited by Yu e t a / . on
Si wafers in the (100) orientation using R F diode sputtering of graphite target with
pure N2 [91]. The films were about 1 pm thick with a nominal composition of
Co6N0.300.1
and contained polycrystalline grains of 0.5-1 pm in size with higher
nitrogen content. Many of the lattice spacings obtained from the ring patterns
measured with TEM matched those of the theoretically predicted PC3N4 [91].
Analogous results were reported by Fernandez et al. who used a dual ion beam
sputtering system to deposit C-N films with a nitrogen content of about 44% on
KCI substrates [92].
Preparation of crystalline carbon nitrides was reported to be possible by use of
chemical vapor deposition techniques. Films containing a-,PC3N4 and an unknown
C-N phase were obtained on nickel substrates from the gas mixture of nitrogen and
methane in a hot-filament CVD apparatus [93]. The composition of the grown films
close to the stoichiometric value N / C = I .33 was measured using energy-dispersive
X-ray analysis and Auger electron spectroscopy. The lattice constants of synthesized
SI- and (jC3N4agreed with the theoretically predicted values. The authors have not
observed bands of diamond or graphite in Raman spectra of the synthesized films.
Presence of amorphous C-N compounds was ruled out after analysis of the films
morphology [93]. Plasma enhanced CDV process was applied by He and Chang for
synthesis of PC3N4 on a silicon wafer as a substrate [94]. As a precursor they used a
mixture of methane, hydrogen, and nitrogen. The nitrogen concentration was varied
between 0 and almost 75%. The strongest evidence for synthesis of BC3N4 at the
highest N2 content was obtained from the TEM measurements. The lattice spacings
calculated from the powder diffraction rings agreed with the theoretically predicted dspacings of PC3N4. However, contamination of the deposited carbon nitride by
iron carbide or nitride most probably in amorphous form and possible presence of
amorphous CH, double bounds C=C or C=N was also reported [94].
LXIII
According to the theoretical calculations, the synthesis of dense C3N4structures

should be possible by applying high pressures and temperatures [12]. The simplest
possible starting materials for synthesis of carbon nitrides are elementary carbon
and nitrogen. Nguyen and Jeanloz used different forms of carbon (graphite,
amorphous carbon, and c 6 0 fullerene) and nitrogen for their high pressure synthesis
experiments where the samples were heated by an Nd :YAG laser [95]. After heating
of the c 6 0 N2 mixture at 30 GPa to 200CL2500 K they obtained a crystalline
material at ambient conditions, the X-ray powder diffraction pattern of which did
not match any of the known carbon phases, the carbon nitrides prepared by deposition techniques, or the theoretically predicted PC3N4.The measured d-spacings can
be better described by a cubic cell with lattice parameter a = 0.77 nm. Similar results
were obtained with the use of other carbon precursors. Presence of more than one
phases was not excluded. The chemical composition of the synthesized material was
not determined [95].
Molecular precursors containing carbon and nitrogen were used for synthesis
experiments in the Nd :YLF laser heated diamond cell. Tetracyanoethylene
(TCNE) with the stoichiometry C6N4 was investigated to 42 GPa [96,97]. EDX
and EELS measurements showed increase of the nitrogen content in the treated
sample with pressure: After heating at 20GPa the nitrogen content was 24%
and by 42GPa the nitrogen content reached 38%, which is the composition of
the starting material. However, at all pressures crystalline carbon was formed in
addition to the amorphous sp2-bonded carbon nitride. It was also found that
the amount of carbon increases with the heating time [96,97], indicating need of
higher pressure for synthesis of single phase carbon nitrides. Such experiment
was performed on a mixture of TCNE (C6N4) and cyanuric triazide (C3N12)
with a nominal composition C3N4 at 119GPa and 2500C [97]. X-ray powder
diffraction spectra showed six new lines, which were indexed to a tetragonal cell
with a = 0.7815 nm and c = 0.6219 nm. The stability of another carbon nitride
precursor material paracyanogen (pCN) at high pressures and temperatures has
been investigated in detail [98]: The decomposition temperature of the precursor
was found to increase with pressure from 550C at 3GPa to 750C at 20GPa.
This work demonstrated that there is a well defined line for decomposition of
pCN and the decomposition temperatures are moderate. It was likely that the
carbon in pCN retained sp2 hybridization to the highest pressure of the work.
Additionally, above the decomposition temperature the authors obtained crystalline graphite even in a region of the carbon phase diagram where diamond was
stable. Thus the pCN precursor, with sp2 carbon bonding, favors the formation
of the carbon phase with sp2-bonded atoms instead of thermodynamically favored
sp3-bonding [98].
Successful synthesis of a bulk crystalline carbon nitrogen was reported by use of
an organic precursor containing carbon, nitrogen, and hydrogen in [99]. After heating this precursor to 400C at 6 GPa the author obtained a three phase-agglomerate
consisting of poorly ordered graphite, a-carbyne and a hexagonal phase with lattice
spacings close to that of the predicted PC3N4.
The most significant problems in almost all experiments on synthesis of carbon
nitrides are as follows:
LXIV
(i) The samples contain many phases often with different chemical composition.
(ii) Crystalline carbon nitrides have been obtained in small amounts and mostly Xray or electron powder diffraction data were presented. Such data do not
always allow unambiguous determination of the structure especially when
other phases were not identified.
(iii) Small sample amounts and presence of other phases is a serious hindrance for
accurate determination of chemical composition of the obtained crystalline
carbon nitrides.
Improvements in the synthesis techniques and analytic equipment may help to solve
these problems. It also has to be mentioned here that the stability of some of the
predicted carbon nitrides was questioned in a number of studies based on chemical
and thermodynamical grounds. A recent discussion of this subject and further
references can be found elsewhere [ 171.
Boron-based Hard Materials

Carbon-based materials such as diamond or diamond-like carbon have several
disadvantages. Among them, the low oxidation resistance of diamond is one of
the most important drawbacks for its technological applications. Boron-based
hard materials of the binary or ternary systems B-C, B-N, B-0, or B-C-N might
improve this property significantly. For example, diamond can be used up to about
600C in air environment, whereas cubic boron nitride (cBN) withstands oxidation
up to 1100C [loo, 1011. Elemental boron itself is a hard material. The high microhardness of boron of 27 GPa [lo21 is related to the low molar volume of 5 cm3 and
the covalent bonding of the rhombohedral crystal structure comprised of B12-icosahedra which are linked together by multiple-center bonds.
Besides diamond and cBN, the well known boron carbide B4C is among the
hardest materials and has been comprehensively reviewed by F. Thkvenot [1031.
In the present chapter, the latest developments concerning the binary and ternary
systems B-N, boron carbide nitrides (B-C-N), and boron suboxides are discussed.
Other hard materials based on boron are described by R. Telle et al. in Part 111.
Boron Nitrides
Boron nitride is isoelectronic with elemental carbon and is, therefore, found in
similar crystal structures:
-
the hexagonal (hBN) [lo41

the cubic zinc blende (cBN) [2,3]
the wurtzitic (wBN) [lo51
the rhombohedral (rBN) [lo61 structure
In contrast to rhombohedral carbon, rBN has been synthesized in significant

amounts by several methods and is well investigated [107,108]. In contrast to
LXV
Figure 10. P,Tphase diagram of boron nitride: (a) catalytic conversion of hBN into cBN; (b) metastable region for the vapor phase formation of cBN. An alternative phase diagram of BN suggested
previously [I 1I] is shown by dashed lines.
graphite, the hexagons of hBN are arranged on top of each other, while the
structures of cBN and wBN completely correspond to diamond and lonsdaleite,
respectively. The zinc blende polymorph of BN is also known as sphalerite or
PBN. Cubic boron nitride is the second hardest material and is produced conventionally at high pressures and temperatures, analogous to those methods developed
for the fabrication of synthetic diamond. It has been commercially available since
1969 [loo]. Hot-pressed monolithic and polycrystalline BN, comprised of both the
cubic and the wurtzitic polymorphs, is already used in cutting tool devices [log].
The generally accepted P,T phase diagram of BN shown in Fig. 10 is based on the
work of Wentorf and colleagues, in which melting temperatures of hBN and the
phase boundary h B N - + c B N at high pressures were measured. This phase
boundary extrapolated to room temperature by analogy with the carbon phase
diagram intersects the pressure axis [110], thus implying that hBN is the most
stable modification at ambient conditions. In contrast, it was suggested in some
recent publications [l 1 I] that cBN is stable at ambient pressure at temperatures
up to 1300C. This suggestion is based on measurements of the thermodynamic
properties of all modifications of BN, where the difference of enthalpies of formation of cubic and hexagonal BN was found to be negative [l l l]:
AHFBN(298K)- AHfhBN(298K)= -16kJmol-'.

Using these thermodynamic data an alternative phase diagram of BN (also shown in
Fig. 10) was developed.
The technological applications of cBN are similar to those of diamond. However,
because of improved oxidation resistance, cBN allows high-speed cutting or
LXVI
grinding of steel-based materials which cannot be machined with diamond. The

discovery of diamond synthesis within the metastable regime of the carbon
phase diagram depicted in Fig. 5 resulted in an increased effort for the deposition
of cBN films under similar conditions. The main processes developed are given
below.
(i) Deposition of cBN by electron cyclotron resonance plasma using NH3 and BF3
as the reactant gases. The films were grown on single crystal Si (100) wafers at a
substrate temperature of 675C and were characterized by infrared and Auger
spectroscopy. The film thickness was 100400 nm, the average growth rate was
10 nm min-' [I 121.
(ii) Formation of cBN by activated reactive evaporation of H3B03in the presence
of NH,. Cubic BN could be deposited on different substrate materials such
as steel, silicon, glass, or NaCl crystal with a rate of 150 nmmin-' at 450C
substrate temperature [113].
(iii) Synthesis of cBN by R F plasma CVD under low pressure conditions and
negative self-bias. B2H6 and N2 were applied as the reactants. The cBN films
were obtained on single crystal Si wafers heated at 600C with a deposition
rate of 6 nm min-' . Cubic BN was verified by transmission electron diffraction
(TED) and microscopy (TEM). The TEM investigations revealed crystallite
sizes of 10-20 nm [ 1141.
(iv) Plasma enhanced CVD from BC13 + NH3 + H2 Ar under irradiation of an
ArF excimer laser at 193 nm. The cBN films deposited were heteroepitaxially
grown on Si (100) surfaces at 500-900C substrate temperatures. Molecular
orbital calculations of the cBN growth mechanism indicate an important role
of atomic chlorine formed during the deposition [I 151.
(v) Finally, cBN was synthesized in the form of films by the dual ion beam deposition technique. In this process, boron atoms are sputtered from a boron target
by an Ar' ion beam and subsequently deposited on a substrate (Si wafer) simultaneously bombarded by N i ions. The deposition rate is 2 .2 4 .6 nm min-' and
film thicknesses of up to 300nm could be achieved [116].
However, besides the formation of cBN, hexagonal hBN is also found in the
deposited films prepared by all of the different methods mentioned above. Vapordeposition of cBN films is reviewed in Part I1 by K. Bewilogua and F. Richter.
Additionally, it is also worth mentioning that cBN has been obtained by the
pressure pyrolysis of borazine, B3N3H6, in a hydrothermal apparatus at 25100 MPa and 250-700C followed by a high temperature treatment at 6.5 GPa
pressure in a girdle type apparatus [117]. The decomposition of magnesium boron
nitride (Mg3BN3) in the presence of water and under high pressure ( P > 4GPa)
and high temperature (1400C) conditions according to the reaction equation
Mg3BN3
+ 3H20 * 3 Mg 0 + cBN + 2NH3
also provided cBN [117]. Magnesium boron nitride is a compound known in the
pseudobinary system BN-Mg3N2 and is synthesized from a mixture of hBN and
Mg3N2 at 4GPa and 800C. The morphology of the cBN crystals formed is
strongly dependent on the temperature and pressure applied. In the case of the
LXVII
decomposition at 1400C and 4 GPa pressure, tetrahedral crystals 10 mm in

diameter were isolated [ 1 181.
By analogy to the body-centered tetragonal carbon, J. Corkill et al. postulated
also a b.c.t.-4 phase of BN with alternating B and N atoms (Fig. 6a) which has
been calculated by the pseudopotential total energy method [119]. While the
calculations for b.c.t.-4 carbon showed a reduced stability with respect to diamond
due to the occupation of antibonding states at the Fermi level, the structure of
b.c.t.4 BN has a small density of states at the Fermi level. Consequently,
b.c.t.-4 BN is estimated to have higher stabilization compared to b.c.t.-4
carbon. The calculated bulk modulus B (268GPa) of b.c.t.-4 BN is significantly
lower than that of the cBN structure (367GPa) owing to the relative openness
of the b.c.t.-4 phase.
Boron-rich Boron Nitrides

Crystalline boron-rich boron nitrides of the compositions B25N up to B53N as
well as amorphous phases of the composition B3N and B5N have also been
synthesized by CVD methods [120,121]. The formation of a rhombohedral structure of the boron-rich nitride, B4N, is described in [122]. The films deposited at
1200C on hBN substrates by a tungsten hot filament assisted vapor-phase
reaction
x>l
were characterized by Raman and photoelectron spectroscopy as well as by X-ray
diffraction. The spectroscopic measurements indicate the presence of a B4N phase
with a crystal structure analogous to that of rhombohedral B4C, a compound
which also belongs to ultrahard materials. In this crystal structure, B l l N icosahedra are linked by N-B-N chains as shown in Fig. 11 [122]. Due to this
Figure 11. Model of the unit cell of the B4N structure. The atoms marked in black represent the
nitrogen atoms within the N-B-N-chain. First published in [152] and reproduced with permission.
LXVIII
structural feature, the new BN phase can be expected to exhibit interesting hardness properties.
Nitrogen-rich Boron Nitride

Existence of a nitrogen-rich boron nitride denoted as hBN was suggested by Yo0
et al., who observed appearance of a low-density hexagonal compound after laser
heating of boron in excess of nitrogen in a diamond cell [123]. This compound
was synthesized both in the stability fields of conventional hBN (2 GPa, 1300 K)
and of cubic BN (15 GPa, 1800 K). hBN is highly transparent and can be recovered
as white polycrystals, which do not convert to other forms of boron nitride at
ambient conditions [ 1231. Unfortunately, chemical composition of the compound
obtained was not determined quantitatively.
Boron Carbonitrides (B,C,N,)

In addition to diamond and the compounds found in the binary phase diagrams of
C-N, B-C, and B-N (Fig. I), materials of the extended ternary system containing
boron, carbon and nitrogen can be also considered as potential candidates with
advanced hardness properties. These compounds are of broad interest because
hexagonal (BN),C, can be considered for applications as high temperature semiconductors, especially if they can be altered by doping or structural changes [ 1241.
Moreover, it is expected that the cubic form of ternary compounds or solid solution
with the general formula (BN),C, might exhibit hardness approaching that of
diamond, but will remain strong for steel cutting and withstand oxidation at
higher temperatures than diamond.
Low density B,C,N,, with hexagonal or turbostratic structure can be synthesized
in three different ways:
-
nitriding of solid -phase precursors at high temperatures

using CVD technique
by pyrolysis of inorganic polymers containing boron, carbon, and nitrogen.
Boron carbonitrides of the general composition B,C,N, were first synthesized by

Kosolapova using the reaction of lampblack and amorphous boron in N2 atmosphere
at 1800-2000C [ 1251. Most recently, B,CyN, with hexagonal graphite-like sheet
structure was obtained by CVD methods providing thin films at lower temperatures
(1000-1400C). Typically, BC13/HC=CH/NH3 or BC13/NH3/CH4/H2gas mixtures
are used for the deposition of B-C-N films [124,126-1301. Boron carbonitride powders could be synthesized in high amounts by the pyrolysis of amine-borane derived
inorganic polymers [ 131, 1321. The molecular amine-boranes, pyridine-borane
(C5H5N BH3) and piperazine-borane (C4H10N2)BH3, form highly cross-linked
polymers by annealing at moderate temperatures (100-200C) with or without solvents [1331. Subsequently, the polymeric materials can be thermally decomposed
LXIX
Buron-bused Hard Materials

r!
I
c-c,
A
H
C N - i - H
110 OC
Figure 12. Schematic representation of the decomposition of pyridine-borane into turbostratic

boron carbonitride, BC4N, with graphite like sheet structure. In the graphitic structure on the
right, only the sp2 o-bonds are shown. First published in [I521 and reproduced with permission.
giving boron carbonitrides, B,C,N2, with different carbon contents. The following
simplified equations represent the overall pyrolysis reactions providing BC4N and
BC2N (Fig. l), respectively:
CN-B.3
NH
N-BH3
U
1050"C/Ar
1050"C/Ar
BC4N
BC2N
+ CH4 + 2H2,
+ 2CH4 + NH3 + H2.
Powder diffraction as well as photoelectron spectroscopy (XPS), electron energy

loss spectroscopy (EELS), and solid state NMR investigations of the synthesized
BC2N and BC4N revealed a graphite-like sheet structure with carbon substituted
for boron and nitrogen and with little sheet-to-sheet registry (turbostratic boron
carbonitride). The pyrolytic conversion of pyridine-borane to turbostratic B-C-N
via the formation of an intermediate polymeric compound is shown schematically
in Fig. 12. These boron carbonitride materials can be considered as solid solutions
of C and BN and are thermally stable up to 1800C in an Ar atmosphere. At higher
temperatures, phase separation providing crystalline hBN, B4C, and elemental C is
observed (see Fig. 1) [ 1331. Microstructural investigation of the synthesized BC4N
by means of TEM showed also the presence of small amounts of isolated crystals
with cubic symmetry as determined by electron diffraction data [ 132,1341. The diffraction data of the cubic crystals do not correspond to those of diamond or cBN.
Therefore, a cubic boron carbonitride phase is assumed for those single crystals
embedded in a turbostratic BC4N matrix. The most difficult issue in the synthesis
of hexagonal B,C,NZ compounds is proving of a single phase content. Indeed
there is no direct method of distinguishing between hexagonal B. C ,Nz, hBN and
..J
graphite, if all are turbostratically distorted. Andreev and Lundstrom pointed out
that in some of the above described work the available data are insufficient to
make unambiguous conclusions about single phase content [1351. They prepared
hexagonal B,C,N, materials by nitration of boron carbide B4C powder at 2100C
LXX
at different partial nitrogen pressures and found in all cases at least two coexisting
phases. For example, samples prepared at partial nitrogen pressures between 30 and
100% contained a carbon-poor three-dimensionally ordered phase and a carbonrich turbostratic phase [135]. Synthesis of ceramic materials from polymers is discussed in Part I1 by G. D. Soraru and P. Colombo.
The high-pressure and high-temperature formation of crystalline boron carbonitride with a cubic lattice was reported in 1977 by various Russian authors using
hBN + C, hBN + B4C, or cBN + C as the reacting species [136,137]. High microhardness values in the range between 60 and 80 GPa have been measured for these
cubic phase E C - N materials. High-pressure synthesis of the cubic B,C,N, phases
from the starting graphite-like (BN),C1-,x (with x = 0.15, 0.26 and 0.6) prepared
by CVD-method was performed at 14GPa and above 3300K [124]. Although
detailed chemical analysis was not performed, it was assumed that the obtained
material was a solid solution of cubic BN and diamond. X-ray powder diffraction
data suggested that this cubic material exhibits ideal mixing according to the Vegards
law and has the same composition as the starting hexagonal material. However, the
author also observed reflexes allowed only for cBN, which he explained by ordering of
materials. Additionthe B-N pairs in the lattice of the synthesized cubic (BN),C1 -,
ally, the author always observed the presence of graphite-like phases in a heat-treated
charge and small amounts of B4C in a few samples [124]. Ideal mixing in the cubic
(BN),C, compounds synthesized in this way was also reported 15 years later by
Kagi et al. [138]. In contrast, measurement of molar volume and of the bulk modulus
of cubic (BN),C1 --x phases synthesized in the YAG-laser heated diamond cell at pressures of 30-50 GPa and temperatures of 2000-2500 K showed strong deviation from
ideal mixing [139]. According to these studies the molar volumes of cubic (BN),yCl
at ambient conditions are larger than that of the ideal solid solution and cubic
(BN),C1_, phases with x < 0.5 have a bulk modulus smaller than that of endmember cBN [139]. If the first observation holds at pressures and temperatures of
synthesis then a mechanical mixture of diamond and cBN will appear at equilibrium
conditions. This is because high pressures favor formation of denser materials [ 1401.
It follows that this cubic (BN),C1 --x should be a metastable intermediate product of
to the mixture of diamond and cBN.
transformation from hexagonal (BN),C, -,
The second observation suggests that the hardness of cubic (BN),C, phases with
x < 0.5 should be smaller than that of cBN, if the systematic approach of Liu
and Cohen [12] is applied. The conclusion of nonideal mixing made earlier [139]
can be called in question because hexagonal materials did not transform completely
into the cubic phases and quantitative chemical analysis of the synthesized cubic
phases was not performed. Nevertheless, metastability of cubic (BN),CI
is
supported by the following results of Japanese authors. Sasaki et al. observed
crystallization of hexagonal BC2N in diamond and cBN in the presence of a Co
catalyst at relatively low pressures and temperatures (5.5 GPa and 1400-1600 K)
[141]. Nakano found that upon phase separation of metastable cubic BC2N to
diamond and cBN the composition of residual cubic (BN),C1 -,
did not change
(x = 0.33). Accordingly, no other stable phases of type (BN),C, except diamond
and cBN exist at the temperature and pressure conditions of the work (7.7 GPa,
2300-2400C) [142].
Silicon-based Materials
LXXI
Because formation of cubic boron carbonitride is of great fundamental interest

with respect to superhard materials much additional effort is needed to succeed in
the preferential synthesis of the cubic B-C-N phase. As follows from the above
results the most promising way would be synthesis under nonequilibrium conditions
such as flash-heating at static pressures or shock-wave compression [ 1401. Successful
synthesis of cubic BC2,5Nsolid solution in 18% yield by shock-compression of
hexagonal BC2,5Nhas been reported [143]. The material obtained was a single
cubic BC2.5N phase with a diamond-like structure and crystals between 5 and
20 nm in size.
Boron Suboxides
In 1988, A. R. Badzian reported that boron suboxides exhibit exceptional high
hardness values [144]. The suboxides with compositions between B 2 0 and B220
were synthesized by the solid state reaction of elemental boron with B2O3 at
1600-2000C. Subsequent melting of the reaction product under Ar provides
boron containing 4-5 at.% oxygen corresponding to B I 8 0and BZ20,respectively.
The crystal structure of the boron rich boron suboxides is related to that of arhombohedra1 boron. The microhardness of boron suboxides was determined to
be between 31 GPa and 59 GPa, which is rather close to the hardness of cubic BN
[144, 1451.
Application of high pressure and high temperature allows synthesis of boron
suboxides with the high degree of crystallinity needed for studying the properties
of these compounds. For example, only fine powders with some secondary
amorphous products were obtained in the synthesis of boron suboxide with a
nominal composition B 6 0 at ambient pressure. Additionally, the synthesized
compounds were nonstoichiometric with compositions varying from B600,72to
B600.86.Hubert et al. showed that by reduction of B2O3 by boron at 1700C and
5.5 GPa a highly crystalline material consisting of multiply twinned particles with
icosahedral symmetry can be obtained. The size of these icosahedral particles was
up to 20-30pm. The measured molar oxygen content was 0.96 f 0.08 (B600.96)
thus approximating the ideal value of 1 [146,147].
The a-rhombohedra1 structure of elemental boron has an electron deficiency that
can be reduced by the incorporation of interstitial atoms in structural voids. Filling
these voids with atoms can result in cross-linking of the boron icosahedra which is
realized for example in the structures of B4C (B12C3), B12P2, B4N, or boron rich
boron suboxides (see Fig. 11) and can contribute to a significant increase of the
rigidity of the solid state structure.
Silicon-based Materials
This section deals with high pressure phases of two silicon based compounds Si02
and Si3N4,which previously did not belong to the family of superhard materials.
LXXII
While the a- and p-phases of silicon nitride were known for a long time as hard
materials, the common phases of Si02 (e.g. quartz) lie much further down the
hardness scale (Table 1). The high pressure phase of Si02 with the rutile structure
(stishovite) was first reported in 1961 [148]. Si02-stishovite is stable at pressures
above 11 GPa and persists metastably at ambient conditions. Its density
(4.287gcmP3) is almost 62% higher than that of the ambient pressure quartz
phase (2.648 g ~ m - [149].
~ ) The bulk modulus of Si02-stishovite (298 GPa) exceeds
that of B4C (200 GPa) which hardness is comparable with that of cubic BN 141. Such
a strong increase in density and bulk modulus is due to an increase of the coordination number of Si-atoms from four to six. Recently LCger et al. measured
the Knoop hardness of polycrystalline single phase Si02-stishovite to be between
31 and 35GPa, which exceeds the literature values of 30GPa for B4C and B 6 0
[4]. However, one has to bear in mind that the measured hardness values depend
strongly on the state of the sample and on the specific test method used. Thus to
make reliable comparisons hardnesses of the materials have to be measured using
the same method and taking into account the above mentioned peculiarities.
A change to six-fold coordination of Si-atoms occurs upon transformation of
hexagonal c1- and pSi3N4 to the high pressure cubic phase with spinel structure
observed in the laser heated diamond cell at 15GPa [5]. The technique of C02laser heating in a diamond cell is described in Part I by Zerr et al. The density of
the cubic Si3N4is 23% above that of a- or p-phases. According to first-principles
calculations, the elastic bulk and shear moduli of cSi3N4exceed that of Si02-stishovite. Consequently, the hardness of the cubic silicon nitride can be comparable to
that of Si02-stishovite [5]. Detailed discussion of silicon nitride based materials is
given in Part 111 by M. Herrmann.
These results on the high pressure phases of two silicon based materials show a
strong potential of the high pressure techniques in synthesis of new materials with
promising mechanical properties. Furthermore, there are many unexplored paths
for future work, even if some of these ways seem on first glance to be completely
worked out, as for the case of Si02-stishovite.
Concluding Remarks
The experimental and theoretical research activities in the field of materials with hardness comparable to or higher than diamond have been stimulated in recent years by the
discovery and postulation of novel carbon allotropes and novel carbon- and boronbased materials. Comparison of the experimental and theoretical results obtained in
the past shows that first principles quantum mechanical and semi-empirical calculations are very useful for the screening of the structural and electronic properties of
new materials. The fascinating variety of new possible carbon allotropes which have
been calculated to be stable relative to diamond or can be stabilized for kinetic reasons
reflects the high potential and the topicality of modern carbon chemistry. Novel
carbon allotropes and carbon and silicon nitrides are subjects of discussion in Part I
in the chapter written by G. Jungnickel et al. and J. E. Lowther.
However, the experimental evidence for the synthesis and structure of dense
superhard C3N4 phases reported in the literature is not unambiguous. Thus,
future research should be focused on the synthesis of sufficient amounts of these
new superhard materials and on their structural characterization. The structures
of all C3N4-polymorphsreported so far still remain to be verified by single crystal
X-ray or electron diffraction. Furthermore, the difficulties in the determination of
reliable hardness values of these new materials not only at room temperature but also
at elevated temperatures have to be overcome. Diamond will not lose its reputation
as the hardest material until the newly developed phases and compounds have been
characterized in detail and can be produced in reasonable amounts.
Acknowledgement
The authors thank J. Nicolich for preparation of crystal structure plots. This work
was supported by the Deutsche Forschungsgemeinschaft under the contract number
Ri 510/14-1.
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Introduccion A Mat Ceramicos

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Handbook of Ceramic Hard Materials

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Ralf Riedel (Editor)

Library of Congress Card No. Applied for

C WILEY-VCH Verlag GmbH, D-69469 Weinheiin (Federal Republic of Germany), 2000

This book is dedicate to

Ute, Vincent, Lorenz and Marlene

One of the clearest hierarchies in materials science and engineering is provided by

List of Contributors XXVII

Structures and Properties

Structural Chemistry of Hard Materials

Phase Transitions and Material Synthesis using the C02-Laser

Mechanical Properties and their Relation to Microstructure

Nanostructured Superhard Materials

Corrosion of Hard Materials

Corrosive Media 140

Interrelations Between the Influences of Indentation Size, Surface

Transition Metal Carbides, Nitrides, and Carbonitrides

New Superhard Materials: Carbon and Silicon Nitrides

Relative Stability 263

Effective Doping in Novel sp2 Bonded Carbon Allotropes

Synthesis and Processing

Directed Metal Oxidation

Historical Background 289

Corrosion of Directed Metal Oxidation Composites 3 16

Self-propagating High-Temperature Synthesis of Hard Materials

Hydrothermal Synthesis of Diamond

Chemical Vapor Deposition of Diamond Films

Reactive Species in Diamond Chemical Vapor Deposition, the Role

Vapor Phase Deposition of Cubic Boron Nitride Films

Polymer to Ceramic Transformation: Processing of Ceramic Bodies

Materials and Applications

Diamond Materials and their Applications

Superabrasive tools: A Brief Introduction 479

Polycrystalline Cubic Boron Nitride 5 18

Applications of Diamond Synthesized by Chemical Vapor Deposition

Chemical Vapor Deposited Diamond Dressers 616

Diamond-like Carbon Films

Ceramics Based on Alumina: Increasing the Hardness for Tool

Recent Trends in the Application of Ceramic Tool Materials 648

Carbide Reinforced Composite Ceramics Based on A1203 669

Silicon Carbide Based Hard Materials

Silicon Nitride Based Hard Materials

Boride-Based Hard Materials

The Hardness of Tungsten Carbidecobalt Hardmetal 946

Relationship between Hardness and Toughness 962

Data Collection of Properties of Hard Materials

Facility for Advanced Combustion

radius of radial crack

strain energy release rate

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adiabatic combustion temperature

energy-dispersive analysis of X-rays

X-ray absorption near edge structure

Introduction: Novel Ultrahard Materials

Introduction: Novel Ultrahurd Materials

Synthetic material or natural mineral.

Scratching methods (Mohs, Martens),

Introduction: Novel Ultrahard Materials

where d is the diagonal of the square-based diamond pyramid of the Vickers

74.3/unit cell (calc)

(N,.) (1971 - 220X)