HANDBOOK OF REFRACTORY
`CARBIDES AND NITRIDES
`
`Properties, Characteristics,
`Processing and Applications
`
`bi‘
`
`Hugh 0. Pierson
`
`Consultant and Sandia National Laboratories (retired)
`Albuquerque, New Mexico
`
`NOYES PUBLICATIONS
`Westwood, New Jersey. LI.S.A.
`
`Micron Technology, Inc. et aI., Petitioners - Ex. 1045
`_
`MICFOFI Technology, Inc. and Micron Memory Japan, Inc. v. Massachusetts Institute of Technology
`IPRZD15-D1087
`1
`
`

`
`
`
`
`Copyright 0 I996 by Noyes Publications
`No part ofthis book ml)’ be reproduced or utilized
`In my Forrn or by any means, ciectmnic or
`mechanical, including photocopying, recording or
`by any information storage unit retrieval syserrl.
`without permission in writing from the Publisher.
`Library urcongxess Catalog Card Number: 915-1257:
`ISBN: 0-8155-1392-5
`
`2
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`Mcflam
`HANFJE
`
`Printed in the United States
`
`Published in the United States of America by
`Noyes Publications
`
`169 Fnimew Avenue. Westwooii. New Jersey 07675
`I098765432]
`
`.
`.
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`Lrhrurjr L:-ft’_"ongre55 Catalogingin-Puhllcallon Data
`
`Pierson, llugh 0,
`Handbook of refractory l:.1.l'hidc5 and nitrides : prupmiei.
`chara:1erisl1'cs_ processing, and applicaliuns -" by Ilugjl U. Pierson.
`p_ ml
`
`ISBN 0-8155-1392-5
`Includes bibliographical references and index.
`1 Refractory transition metal compounds--Melallograpliy
`2. Carbidcs. 3. Nitridcs
`I. ‘ram
`
`T.\:l5‘fl3.T7PS4
`66 .12-vdclfl
`
`I996
`
`I
`9!:-I25?!
`CU’
`
`

`
`
`
`ds. Arthur Mullondorc.
`
`:k Sliglich, formcrly of
`thorough review of the
`I friend. George Narita.
`olp and patience in the
`
`Hugh 0. Pierson
`
`Contents
`
`this publication is
`13' responsibility or
`or consequences
`d Foririfonnational
`.1mun:ia| products
`tion for use by the
`of any informal Ion
`the manner ofthal
`:
`ICCOlT1I‘I‘|<.‘T1d that
`on of materials or
`.5:|[i.*J_\ himsclfas
`:Iic.'1hIc szifcty and
`
`................................... .. l
`Introduction .. ............
`1.0 HISTORICAL PERSPECTIVE AND PRESENT STATUS OF
`REFRACTORY CARBIDES AND NITRIDES .................... ..
`2.0 (IARBIDES AND NITRJDES AS REFRACTORY
`
`1
`
`3.0 BOOK OBJECTIVES .......................................................... .. 3
`4.0 BOOK ORGANIZATION ..................................................... __ :1
`5.0 GLOSSARY AND METRIC CONVERSION GUIDE .......... .. 5
`6.0 BACKGROUND
`6.1 GeneraIRcfcrc-nces
`6.2 Periodicals
`..................................................................... .. 6
`6.3 Conferences
`7
`
`The Refractory Carbide-s.... .................................... 8
`1.0
`8
`2.0 DEFINITION AND CLASSIFICATION OF CARBIDES
`2.1 Classification ................................................................... .. 9
`2.2 Refractory Qualifications .....................
`...................... .. .9
`2.3 Factors Controlling Carbide Formation .......................... .. 9
`3.0 CARBIDE FORMATION AND ELECTRONEGATIVITY
`9
`
`3.1 Definition of Electroncgativity ........................................ .. 9
`3.2 Comparison of Electroncgativity
`10
`
`ix
`
`

`
`x
`
`Contents
`
`11
`4.0 CARBIDE FORMATION AND ATOM
`II
`4.1 Atomic
`12
`4.2 Carbide Fonnation and Ratio of'Atomic
`12
`5.0 THE ATOMIC BONDING OF CARBIDES
`[2
`5.1 Ionic Bond
`13
`5.2 Covalent
`[4
`5.3 Metallic
`6.0 GENERAL CHARACTERISTICS OF CARBIDES ____________ .. I4
`6.1 Interstitial Carbides
`14
`6.2 Covalent Carbides ......................................................... _. 14
`6.3 Intermediate Carbides
`15
`6.4 Salt-Like Carbidcs ......................................................... .. 15
`REFERENCES
`................................................................... .. 16
`
`17
`
`Interstitial Ca rbides, Structure and Composition
`1.0 DEFINITION AND GENERAL CHARACTERISTICS OF
`1?
`INTERSTITIAL CARBIDES
`1.1 Definition
`.................................................................. .. 17
`1.2 General Characteristics
`18
`2.0 ELECTRONIC STRUCTURE OF CARBON
`18
`2.1 Nucleus and Electronic Configuration of die Carbon"Atom”.r. 19
`2.2 Hybridization oftlie CarbonAtom 22
`2.3 Thc.rp3
`24
`3.0 THE EARLY TRANSITION METALS
`25
`3.1 Definition ofTransition Elements
`25
`
`3.2 Electronic Configuration of Early Transition Metals 26
`4.0 CRYSTAL STRUCTURES .
`. . . . . . .
`. . .
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`. .. 27
`
`2?
`
`4.1 Close-Packed Crystalline Structures
`4.2 Hexagonal C lose-Packed (hep) and Face-Centered
`Cubic Close-Packed (fcc) Structures .............................. .. 23
`4.3 Body-Centered Cubic {bcc) and Simple Hexagonal
`31
`Structures
`4.4 Crystal Structures 3l
`5.0 ATOMIC STRUCTURE OF INTERSTITIAL CARBIDES
`34
`5.1 Definition of Interstitial Structures ................................. .. 34
`5.2 Atomic-Radii
`34
`5.3 Interstitial
`34
`
`5.4 The Chromium Carbide Exception
`6.0 CRYSTALLINE STRUCTURE AND COMPOSITION OF
`36
`INTERSTITIAL CARBIDES
`36
`6| Crystalline
`6.2 Composition and Structure ............................................. .. 37
`
`36
`
`
`
`_.-*.v_t-'-;‘-
`
`6.3 Metal-to-I
`
`6.4 Density C.
`7.0 ATOMIC B0]
`7.1 Complexit
`7,2 Overall Er
`7.3 Thermal P
`7.4 Ionic Bond
`7.5 Covalent E
`7.6 Bondinga:-.
`7.? Metallic B:
`7.8 Band Strut:
`8.0 INTERSTITIA
`3.1 Vacancies
`
`8.2 Ordering of
`9.0 GENERAL RE
`INTERSTITIAJ
`9.1 Variations i.
`9.2 General Ch.’-
`REFERENCES
`
`Carbides ofGr
`Hafniuni Carbi
`[.0 GENERAL Cl-I}
`GROUP IV CAI"-
`2.0 PHYSICAL AN]
`GROUP IV CAR
`2.] Density and l
`2.2 Thennal Pro}
`2.3 Thcnnodynal
`2.4 Thermal Con.
`
`2.5 Tl-tennal Exp:
`3.0 ELECTRICAL P.
`3.] Electrical Cor
`3.2 Hall Effect
`..
`4.0 MECHANICALI
`4.] Property Vari:
`4.2 Summary of l
`4.3 Failure Media
`4.4 Ductile-Brittle
`4.5 Hardness
`..
`4.6 Transverse Ru
`
`
`
`

`
`
`
`Contents
`
`xi
`
`6.3 Metal-to-Carbide Structural Switching ........................... .. 39
`64 Density Considerations
`40
`7.0 ATOMIC BONDING OF INTERSTITIAL CARBIDES ..... .. 4]
`2.! Complexity offlonding System
`41
`2.2 Overall Bonding Scheme ................................................ .. 42
`2.3 Tltennal Properties Considerations ................................. .. 42
`7.4 Ionic Bonding and Elcctronegativity ............................... .. 46
`7.5 Covalent Bonding in Interstitial Monocarbidcs
`46
`7.6 Bonding and Atomic Spacing ......................................... .. 47
`2.? Metallic Bonding .......................................................... .. 48
`7.8 Band Structure
`48
`8.0 INTERSTITIAL CARBIDES AS DEFECT STRUCTURES 48
`
`8.2 Ordering ofthc Carbon Atoms .................................... .
`9.0 GENERAL REVIEW OF THE PROPERTIES OF
`INTERSTITIAL CARBIDES
`
`.
`
`. 50
`
`. St
`
`. 5|
`..
`9.1 Variations in Properties and Composition ...................
`.....5l
`9.2 GeneralCharacteristics..,._.........................................
`REFERENCES
`.................................................................. .. 52
`
`XTOM
`
`1:
`
`iii}ii6££ii&"Iii:'is'i':::::i.:..I.i:IZZ 12
`ARBIDES.......................... 12
`
`-"s"oi'E;i'iiii'io'iis'I§.ifffiif 14
`
`re and Composition
`CHARACTERISTICS OF
`
`12
`
`IP18
`,uration oftlic Carbon Atom 19
`Atom
`22
`
`25
`ETALS
`ICIIIS .................................. .. 25
`Early Transition Metals 26
`.
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`. .. 2?
`uctures ............................... .. 22
`p} and Face-Centered
`uctures .............................. .. 28
`nd Simple Hexagonal
`3|
`.... ..
`"ransilion Metals ................ .. 3l
`FERSTITIAL CARBIDES
`34
`crures
`34
`34
`........................................... .. 34
`
`:ption ................................ .. 36
`AND COMPOSITION OF
`
`Carbides of Group IV: Titanium, Zirconium, and
`Hafnium Carbides ..............
`............
`.............. .. 55
`L0 GENERAL CHARACTERISTICS OF
`GROUP IV CARBIDES .................................................... .. 55
`2.0 PHYSICAL AND THERMAL PROPERTIES OF
`GROUP IV CARBIDES
`2.1 Density and Melting Point ......................... ..
`2.2 Thermal Properties
`2.3 'I'hcrn1odynamic Functions
`2.4 Tl1en'nal Conductivity
`2.5 Thcmial Expansion.
`3.0 ELECTRICAL PROPERTIES OF GROUP IV CARBIDES ..
`3.1 Electrical Conductivity .................................................. ..
`3.2 Hall Effect
`................................................................ .. 64
`4.0 MECHANICAL PROPERTIES OF GROUP IV CARBIDES 64
`4.1 Property Variables ...................................................... .. .64
`4.2 Summary of Mechanical Properties
`65
`4.3 Failure Mechanism .................................................... .
`. 65
`4.4 Ductile~Britt|c Transition
`.. 66
`4.5 Hardness
`.......... ..66
`
`O\O'\O'\U\\I.nL.r-IJ-Lb
`
`I‘-Jb-JI-00%--.l$G'\
`
`..
`
`4.6 Transverse Rupture Strength .......................................... .. 66
`
`

`
`xii
`
`Contents
`
`‘_
`
`1
`
`5.0 CHEMICAL PROPERTIES OF GROUP Iv CAREIDES
`68
`1
`5.t Mutual Solubilitics ........................................................ .. 68
`52 Chemical
`68
`I
`6.0 CHARACTERISTICS AND PROPERTIES OF
`?
`TITANIUM 68
`i
`6.1 Summary of Propcnics .................................................. .. 68
`'
`6.2 Phase Diagram72 F
`6.3 Summary of Fabricatiun
`72
`T
`6.4 Surnmary of Applications and Industrial Importance ...... .. 72
`it
`7.0 CHARACTERISTICS AND PROPERTIES OF
`.
`ZIRCONIUM
`‘
`7.1 Summary ofPropcItics ................................................. .. 73
`7.2
`74
`7.3 Surnmaryof Fabrication
`74
`7.4 Summary of Applications and Industrial Importance
`M
`8.0 EIENRAJCNTERAIEEISE AND PROPERTIES OF
`8.1 Summary ofPropcrtics ................................................ .. 76
`3.2 Ph:1scDiagram77
`3.3 Summary of Fabrication Processes ................................. .. 78
`Tu.-§:‘.‘II§.IEI’E:"IE‘§”“ °”“""'°‘”‘.‘.'.“.’.”.i“..?‘f7??.?.T'f*???T.’T??3_7T?‘?5’.TT?‘7fTf5;:g 33
`
`:_
`
`I
`
`I.
`;
`
`S Carbidcs of Grqup V: Vanadium, Niobium and
`Tantalum CarbIdes_............................................... 81
`10 GENERAL CHARACTERISTICS OF
`GROUP v CAREIDES ..................................................... .. 81
`2.0 PHYSICAL AND THERMAL PROPERTIES OF
`32
`GROUP VCARBIDES .............................................. ,,
`82
`2.1 Density and Melting
`83
`2.2 Thcrrnal Properties
`87
`3.0 ELECTRICAL PROPERTIES OF GROUP v CARDIDES
`4.0 MECHANICAL PROPERTIES OF GROUP v CARDIDES . an
`5.0 CHEMICAL PROPERTIES or GROUP v CARBIDES
`39
`5.: Mulualsolubilities
`89
`5.2 Chemical Propcrtics ______________________________________________________ ,, 39
`6.0 CHARACTERISTICS AND PROPERTIES OF
`VANADIUM CARBIDE
`6.1 Summary Of'PrOpertiI:s
`6.2 Phase Diagram ......................................................... ..
`6.3 Summary of Fabrication
`6.4 Summary OfApplicatior1s and Irtdttstrial Itnponancc .
`
`\o\D\ca-oneP~J(\-3|--'\D\D
`
`.
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`.
`
`i
`i
`-
`5
`
`5
`I‘,
`.
`
`-
`
`7.0 CHARACTERIS1
`NIOBIUM CARE.
`7.: Summary OFP
`7.2 Phase Diagrarr
`7.3 SummaryofF-
`7.4 Summary PM
`3.0 CHARACTERJST
`TANTALUM CM
`3.1 Summary of PI
`3.2 Phase Diagram
`3.3 Summar.vofFe
`3-4 5Um"13"Y Of AI
`REFERENCES
`
`6 Ca rbides of Grou
`and Tungsten ca.
`"0 GENERAL CHAR‘
`GROUPWC-‘RB’
`Egglflfglnlffilfiz
`2-0 PHYSICAL ANPI
`GROUP PI CARBI
`gfigifiilaggolggfl
`33 ELECTRICAL PR[
`4.0 MECHANICAL PR‘
`5.0 CHEMICAL PROP.
`5.1 Mutual Solubilit
`5.2 Chemical Proper
`6.0 CHARACTERISTII
`CHROMIUM CARI
`6.1 Summary of Pro:
`6.2 Phase Diagram .
`6.3 S1Immz1I')' of Fab
`6.4 Summaryofflpr
`7.0 CHARACTERJSTIC
`MOLYBDENUM CI
`7.! Summary ofPro}
`7.2 Phase Diagrztrn ..
`7.3 Summary of Pror.
`7.4 Summary of App
`
`
`
`

`
`
`
`Contents
`
`xiii
`
`7.0 CHARACTERISTICS AND PROPERTIES OF
`NIOBIUM CARBIDE
`
`'I.I Summary ofProperties
`'.-‘.2 PhaseDiagram
`7.3 Summary of Fabrication
`7.4 Summary of Applications and Industrial Importance
`8.0 CHARACTERISTICS AND PROPERTIES OF
`TANTALUM CARBIDE ..................................................... ..
`
`3.l Summary ofPropetties .................................................. ..
`
`
`
`‘Ct-D~D\D\-Dx-D\D-«D»D
`
`
`
`an--av-U-'J-<.nr~...tt~...tr~...t
`
`8.3 Summar_v0fFabrication
`3.4 Surmnary of Applications and Industrial Importance ______ .. 93
`
`UP IV CARBIDES
`
`68
`
`................................. ..68
`
`................................. __68
`................................. __68
`
`striallmportancc ...... .. 72
`TIES OF
`
`............................... ..73
`.....74
`
`strial Importance ...... .. ‘I4
`TIES OF
`
`.....?6
`
`. ............................ ..'i'}'
`............................. ..78
`
`strlal Importance ..... .. 78
`................................ .. 78
`
`, Niobium and
`................
`
`81
`
`RTIESOF
`..................... ..82
`.............................. ..32
`.
`..
`......... ..83
`)UP V CARBIDES
`8?
`DUI’ V CARBIDES . 88
`IPVCARBIDES .... ..89
`.
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`. ..
`.
`............. ..89
`............................... ..89
`
`............................... _.89
`.... ..
`89
`. ............................ ..9l
`
`trial Importance ...... .. 92
`
`Carbides of Group VI: Chromium, Molybdenum,
`and Tungsten Carbides
`100
`[.0 GENERAL CHARACTERISTICS OF
`GROUP VI CARBIDES
`
`I00
`
`I00
`[.1 Common Features of Group VI Carbides .................... ,.
`[.2 Refractory Characteristics ....................................... .. 101
`2.0 PHYSICAL AND THERMAL PROPERTIES OF
`GROUP VI CARBIDES .............................................. ..
`
`. IOI
`
`102
`2.1 Density and Melting
`102
`2.2 Themtal Properties
`3.0 ELECTRICAL PROPERTIES OF GROUP VI CARBIDES 104
`4.0 MECHANICAL PROPERTIES OF GROUP VI CARBIDES . 106
`5.0 CHEMICAL PROPERTIES OF GROUP VI CARBIDES
`10?
`5.1 Mutual Solubilities ..................................................... .. 10?
`
`5.2 Chemical Properties .................................................... .. 10?
`6.0 CHARACTERISTICS AND PROPERTIES OF
`CHROMIUM CARBIDE .................................................. .. 10?
`
`6.1 Summaryof'Properties ............................................. .. 107
`6.2 Phase Diagram ................................................... ..
`.
`10?
`6.3 Summary of Fabrication Processes ..............................
`I 10
`6.4 Summary of Applications and Industrial Importance
`I II’!
`7.0 CHARACTERISTICS AND PROPERTIES OF
`MOLYBDENUM CARBIDE
`
`III}
`
`..
`
`7.1 Summary oI'Propertics ............................................... .. 110
`7.2 Phase Diagram
`110
`7.3 Summary of Production Processes ............................... ..
`I 12
`7.4 Summary of Applications and Industrial Importance .... ..
`I I2
`3*:
`
`
`
`

`
`xiv Contents
`
`8.0 CHARACTERISTICS AND PROPERTIES OF
`TUNGSTEN
`
`ll3
`
`I l3
`3.1 Summary ofPropcrties
`8.2 Phase Diagram ............................................................ .. II4
`3.3 Suuunary of Production Processes IIS
`8.4 Summary ofApplications and Industrial Importance
`l l6
`
`Covalent Carbides: Structure and Composition. 118
`1.0 GENERAL CHARACTERISTICS or COVALENT
`
`2.0 ATOMIC STRUCTURE OF CARBON, BORON, AND
`
`2.! Electronic Configuration................................................ II9
`2.2 Hybridized States
`I20
`3 .0 STRUCTURE AND COMPOSITION OF
`SILICON CARBIDE ........................................................ ..
`
`I2l
`
`3.] The Carbon-Siiicen Crystal Unit Cell ........................... .. 121
`3.2 Co\':1lcnt:1ndlonic Bonding
`.. 122
`3.3 Beta Silicon Carbide
`123
`
`123
`3.4 Alpha Silicon Carbide and Polytypes
`3.5 Summary of Structural Data ........................................ .. 124
`3.6 Structural Correlation
`I27
`3.? Phase Diagram
`I27
`40 STRUCTURE AND COMPOSITION OF
`I28
`BORON
`128
`4.I'Il1e Boron
`130
`4.2 The Structure of Boron Carbide
`I32
`4.3 Composition
`4.4 The Boron-Carbon Bond ............................................. .. I32
`4.5 Summary of Stru-:tur:1l Data for Boron Carbide ........... .. 132
`4.6 Phase Diagram ...........................
`.
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`. . .. 134
`REFERENCES
`I35
`
`.
`
`Characteristics and Properties of Silicon Carbide
`and Boron Carbide . .......................................... .. 137
`l.0 INTRODUCTION...
`I3?
`2.0 CHARACTERISTICS AND PROPERTIES OF
`SILICON 137
`
`2.] Historical Background and Present Status
`2.2 Summary of Properties ........................ ..
`
`[37
`. .................... .. [38
`
`3.0 CHARACTERISTII
`BORON CARBIDE
`3.I Historical Back;
`3.2 Summary-ot'Prc
`4.0 PHYSICAL AND T
`COVALENT CARE
`4.] Discussion nndl
`4.2 Physical Propen
`4.3 Thermal Propen
`5.0 ELECTRICAL ANI
`
`5.! Electrical Propu:
`5.2 Semiconductor}
`5.3 Boron Carbide a
`6.0 MECHANICAL FR
`
`6.1 Property Variab
`6.2 Summary of Me
`6 3 Strength
`6.4 Hardness
`7.0 NUCLEAR PROPE
`8.0 SUMMARY OF FA
`8.1 Silicon Carbide.
`3.2 Boron Carbide ..
`9.0 SUMMARY OF AP
`INDUSTRIAL IMPI
`9.] Silicon Carbide
`9.2 Boron Carbide ..
`REFERENCES
`
`The Refractory Ni
`1.0 INTRODUCTION ..
`2.0 GENERAL CHARA
`2.] Definition and C
`
`2.2 Rct‘raetoryQua|
`3.0 FACTORS CONTR
`3.l Nitride Formatio
`3.2 Nitride Formatic
`3.3 The Electronic [3
`4.0 GENERAL CHARA
`4.1 Interstitial Nitrid
`4.2 Covalent Nitride
`4.3 Intenncdiatc Nit:
`4.4 Salt-Like Nitride
`REFERENCES
`
`
`
`

`
`
`
`Corirenrs
`
`xv
`
`3.0 CHARACTERISTICS AND PROPERTIES OF
`BORON CARBIDE .......................................................... ..142
`3.1 Historical Background and Present Status
`142
`3.2 Summary of'Properties
`142
`4.0 PHYSICAL AND THERMAL PROPERTIES OF THE
`
`COVALENT CARBIDES ................................................ .. 144
`4.1 Discussion and Comparison............................
`......... ..144
`4.2 Physical Properties ................................................. .. 145
`4.3 Thermal Properties
`...................... ..
`. ........................ .. 146
`5.0 ELECTRICAL AND SEMICONDUCTOR PROPERTIES . 147
`5.1 Electrical Properties..............
`147
`5.2 Semiconductor Properties
`147
`5.3 Boron Carbide as a Thermoelectric Material ................ .. 149
`6.0 MECHANICAL
`149
`
`149
`6.1 Pr0P%rty
`6.2 Summary ofMechanieal Properties.............................___ 149
`6.3 Strength
`.
`149
`6.4 Hardness
`150
`?'.0 NUCLEAR PROPERTIES
`151
`30 SUMMARY OF FABRICATION PROCESSES
`151
`8.1 Silicon
`151
`...................................... ..
`8.2 Boron Carbide .................
`. 152
`90 SUMMARY OF APPLICATIONS AND
`. 152
`INDUSTRIAL IMPORTANCE ....................................... ..
`9.1 Silicon Carbide ........................................................... .. 152
`9.2 Boron Carbide ............................................................ .. 153
`REFERENCES
`154
`
`9 The Refractory Nitrides .....................................156
`1.0
`156
`2.0 GENERAL CHARACTERISTICS OF NITRIDES
`156
`.
`. ..
`.
`.
`.
`2.1 Definition and Classification .
`.
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`156
`2.2 Refractory Qualifications............_.._.........._.................... 158
`3.0 FACTORS CONTROLLING NITRIDE FORMATION .... .. I58
`
`158
`3.l Nitride Fonnation and Elcctronegativity
`3.2 Nitride Fonnation and Atom Size ................................ .. I59
`3.3 The Electronic Bonding ofNitrides . ....................... .. I59
`4.0 GENERAL CHARACTERISTICS or NITRIDES .......... .. 159
`4.1 Interstitial Nitrides
`[59
`
`4.3 Intermediate Nitridcs .................................................... .. 161
`4.4 Salt-Likehlitrides
`161
`REFERENCES
`................................................................ .. 162
`'71
`
`
`
`
`
`............_._.-.__..._.1 L—
`
`_=
`i
`
`1 1
`
`ERTIES OF
`
`113
`113
`114
`:5 ............................... .. IIS
`
`iustrial Importance .... .. 116
`....................... .. 116
`
`and Composition. 118
`H: COVAI ENT
`
`)N, BORON, AND
`
`I19
`I19
`
`\10F
`................................ ..121
`Cell .......................... .. I2]
`.
`.
`.
`.
`.
`I22
`
`pes ........................... ..123
`................................. ..124
`................................ .. 127
`............................. .. 12?
`JOF
`................................ .. 128
`
`132
`Ioron Carbide 132
`. ..................... .. 134
`................... ..
`135
`
`ofSiliconCarbide
`
`{TIES OF
`
`Ismms
`
`137
`.. 137
`
`.. 137
`
`137
`~- 138
`
`___1_.
`
`

`
`
`
`xvi Contents
`
`10 Interstitial Nitrides: Structure and Composition 163
`1.0 DEFINITION AND GENERAL CHARACTERISTICS OF
`INTERSTITIALNITRJDES
`.. . 163
`[.l Definition
`................................................................ .. I63
`I.2 General Characteristics
`164
`2.0 ATOMIC STRUCTURE OF NITROGEN........................... 165
`2.1 Nucleus and Electronic Configuration of‘
`t‘
`the NitrogenAtom 165
`2.2 Bonding and Hybridization
`166
`3.0 ATOMIC STRUCTURE OF TNTERSTITIAL NITRJDES .. I63
`3.] AtomicRadii .. 163
`3.2 Interstitial Sites.......
`..
`I69
`4.0 COMPOSITION AND CRYSTALLmiststtuctottstbrt
`I69
`INTERSTITIAL NITRIDES
`4.! Composition and Structure ........................................... .. I69
`4.2 Composition
`I7]
`4 3 Summary of Characteristics ......................................... .. 172
`4.4 Metal-to-Nitride Structural Switching .................. ..
`172
`4.5 Density Considerations
`174
`5.0 ATOMIC BONDING OF INTERSTITIAI. NITRIDES
`I74
`5.] Overall Bonding
`. 174
`5.2 Thermal Properties Considerations ............................... .. I76
`5.3 Ionic Bonding and Eleetronegatiyity ............................. .. 179
`REFERENCES
`.. I80
`
`11 Interstitial Nitritles: Properties and General
`Characteristics .............................
`.................. .. 181
`1.0 GENERAL PROPERTIES OF INTERSTITIAL NITRIDES ISI
`2.0 PHYSICAL AND THERMAL PROPERTIES OF
`INTERSTITIAL NITRIDES
`. ................................... .. ISI
`2.! Composition and Stoichiometry ............................
`I82
`2.2 Density and Melting
`I82
`2.3 Thermal Properties ...................................................... ..
`I83
`2.4 Thermal Conductivity
`134
`2.5 Thennal
`.135
`3.0 ELECTRICAL PROPERTIES OF INTERSTITIAL
`
`4.0 MECHANICAL PROPERTIES OF INTERSTITIAL
`NITRIDES
`4.] Summary of Mechanical Properties.........._..................
`4.2 Hardness
`..
`
`I88
`.. 189
`.. I39
`
`5.0 CHEMICAL PRO
`5.1 Mutual Solub
`
`5.2 Chcnucal Pro;
`6.0 TITANIUM NITI
`6.1 Summary of}
`6.2 Isomorphism.
`6.3 Phase Diagra:
`6.4 Summary of}
`6.5 Summary of!
`7.0 ZIRCONIUM NY
`7.1 Sununary 0H
`7.2 Isomorphism.
`7.3 Phase Diagrat
`7.4 Summary ofI
`7.5 Summary of!
`8.0 HAFNIUM NITR
`
`8.] Summary of}
`8.2 Isom0t'pI1i5!'I1.
`3.3 Phase Dlngrar
`8_4 Summary of}
`8.5 Summary of!
`9.0 VANADIUM N11
`9.1 SummaryofF
`9.2 Isomorphism.
`9.3 Phase Diagrar
`9.4 Summaryoff
`9.5 Summary offi
`10.0 NIOBIUM NITRJ
`
`10.1 Summary ofl’
`I02 isomorphism
`10.3 Phase Diagrar
`[(1.4 Summary oil‘
`l0.5 Summary offi
`I 1.0 TANTALUM N['|
`ll.l Summary oI'P
`lI.2 Isomorphism.
`I [.3 Phase Diagran
`ll.4 Summary of F
`I 1.5 Summary ofA
`REFERENCES
`
`
`
`10
`
`

`
`
`
`e and Composition 163
`-IARACTERJSTICS or
`
`163
`163
`
`OGEN _________________________ __ 165
`ration of
`____________________________________ .. 165
`
`1ST1TlAl..NI'I'RIDES.. 168
`
`JNE STRUCTURE OF
`
`169
`169
`1?l
`
`ching
`
`...I72
`
`124
`‘ITIALNITRIDES .
`................................... .. 1'14
`ns ............................. .. I76
`
`........................ .. 179
`.
`rity
`................................ .. 180
`
`s and General
`181
`......................
`IRSTITIAL NITRIDES 181
`’ERTIES OF
`
`I81
`182
`182
`183
`
`................................ .. 185
`ITERSTITIAL
`.............................. .. 18?
`NTERSTITIAL
`. . . . . .. 188
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`:3. ............................. .. 189
`....
`139
`
`Contents
`
`xvii
`
`5.0 CHEMICAL PROPERTIES OF INFERSTTIIAI. NITRIDES 191
`5.] Mutual Soiubilitics
`191
`
`5.2 Chcmica|192
`6.0 TITANIUM NITRJDE: SUMMARY OF PROPERTIES
`193
`6.1 SummaryofPropcrties
`193
`6.2 Isomorphism ................................................................ .. 194
`6.3 Phase Diagram
`194
`6.4 Summary ofFabrication Proccsscs ............................... .. 195
`6.5 Summary of'Applications and Industrial Importance .... .. 195
`7.0 ZIRCONIUM NITRIDE: SUMMARY OF PROPERTIES . 195
`7.1 Summary ofPrope11ics ................................................ .. 195
`T2 lsornorphism ................................................................ .. 195
`71.3 Phase Diagram ........................................................... .. 195
`7.4 Summary of Fabrication Processes .............................. .. 197
`7.5 Summary of Applications and Industrial Importance .... .. 197
`8.0 I-IAFNIUM NITRIDE. SUMMARY OF PROPERTIES
`198
`
`198
`8.1 Summary ofPropcr1ics
`8.2 Isomorphism .............................................................. .. 199
`8.3 Phase Diagram ................................ .
`.. .................. .. 199
`. _
`8.4 Summary of Fabrication Processes .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. . .
`.
`.
`.
`.
`.
`. . .. 200
`8.5 Summary of Applications and Industrial Importance
`. 200
`9.0 VANADIUM NITRIDE: SUMMARY OF PROPERTIES
`200
`
`9.1 Summary of Properties ............................................... .. 200
`9.2
`200
`9.3 Phase Diagram ........................................................ .. 200
`9.4 Summary of Fabrication Proccsscs................................. 200
`9.5 Summary of Applications and Industrial Importance .... .. 202
`10.0 NIOBIUM NITRIDE: SUMMARY OF PROPERTIES .... .. 202
`10.] Summary of Properties . . .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. _
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. . .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. .. 202
`10.2 Isomorphism...................__..........
`. 204
`10.3 Phase Diagram ......................................................... ..
`10.4 Summary of Fabrication Proccsscs ............................... .. 204
`10.5 Summary ofApplications and Industrial Importance .... .. 205
`11.0 TANTALUM NITRIDE. SUMMARY OF PROPERTIES .. 205
`
`205
`11.1 Summary ofPropcrtics
`1 1.2 isomorphism ........................................................... .. 205
`11.3 Phase Diagram
`205
`11.4 Summary of Fabrication Proccsscs .......................... ..
`205
`11.5 Summary of Applications and Industrial Importance .... .. 205
`REFERENCES
`. . . . .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. . . .
`. .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`. ..
`. 207
`
`
`
`11
`
`

`
`.rvi'r'i' Conrents
`
`209
`
`12 Covalent Nitrides: Composition and Structure . 209
`1.0 GENERAL CHARACTERISTICS OF
`COVALENT
`2.0 ATOMIC STRUCTURE OF NITROGEN, BORON,
`ALUMINUM, AND SILICON .......................................... .. 210
`2.] Electronic Configuration
`210
`2.2 Characteristics of the Elements Forming
`Covalent Nitrides ......................................................... .. 211
`3.0 COMPOSITION AND STRUCTURE OF
`211
`BORON NITRIDE
`211
`3.] Composition
`3.2 The Two Major Structures oi'Boron Nitride................... 212
`3.3 Structure of Hexagonal Boron Nitride .......................... .. 213
`3.4 Structure ofCubic Boron Nitride 214
`3.5 Other Boron Nitride Structures .................................... .. 216
`3.6 Summary ofstructural Data ofBoron Nitride
`216
`4.0 COMPOSITION AND STRUCTURE OF
`217
`ALUMINUM NITRIDE
`4.! Composition . ......................................................... .. 21?
`4.2 Structure
`2 17
`4.3 Bonding
`.. 218
`4.4 Summary of StruetiirizillData.o1;AIuriiiriu.rii.Niiilide-iii1:11.. 213
`5.0 COMPOSITION AND STRUCTURE or
`SILICON NITRIDE
`5.1 Composition
`5.2 Structure
`5.3 Bonding
`5.4 Surruuary of Structural Data of Silicon Nitride ............. .. 221
`
`219
`219
`................................................................. .. 219
`
`13 Covalent Nitrides: Properties and General
`223
`Characteristics .........
`.................
`..............
`1.0 INTRODUCTION ............................................................. .. 223
`2.0 PHYSICAL PROPERTIES OF THE
`COVALENT NITRIDES ................................................... .. 223
`2.1 Discussion and Comparison
`223
`2.2 Physical Properties ...................................................... .. 224
`3.0 THERMAL AND ELECTRICAL PROPERTIES OF
`225
`COVALENT NITRIDES.
`..
`3.1 Thermal Properties ................................................... .. 225
`3.2 Electrical
`227
`
`4.0 MECHANICK
`COVALENT IN
`
`4.} Property V:
`4.2 Summary o
`4.3 Strength an-
`4.4 Hardness
`5.0 CHEMICAL P]
`6.0 CHARACTER}
`BORON NITR]
`6.1 Historical E
`
`6.2 Hexagonal J
`6.3 Phase Diagi
`6.4 CVD Boron
`6.5 Cubic Bore:
`6.6 Chemical R-
`'.-‘.0 CHARACTER]
`ALUMINUM IN"
`7.1 Historical B
`
`7.2 Summary-'o:
`7.3 Phase Diagr
`7.4 Chemical R:
`8.0 CHARACTERI
`SILICON NITR
`11.1 Historical B
`
`8.2 Summar_\-‘oi
`3.3 Phase Diagr
`11.4 Chemical R:
`8.5 Siaions
`9.0 SUMMARY OF
`9.1 Boron Nitric
`9.2 Aluminum 1'‘
`9.3 Silicon Nitriu
`10.0 SUMMARY OF
`IMPORTANCE
`10.1 Boron Nitrid
`10.2 Aluminum 1*
`10.3 Silicon Nilri
`REFERENCES
`
`14 Processing of R
`(Powder, Bulk,
`1.0 INTRODUCTIC
`1.1 Synthesis Cl’.
`
`
`
`12
`
`

`
`
`
`Contents
`
`xix
`
`nd Structure . 209
`
`............................ ..209
`N.BORON,
`............................ .,2l0
`........
`210
`
`2ll
`
`Nitride................... 212
`
`............................ .. 216
`nNitridc .............. .. 216
`'I-'
`........................... .. 2]?
`............................ .. 2]?‘
`............................ .. 21?
`............................ .. 213
`1inumNitridc _______ .. 213
`F
`
`ZI9
`219
`219
`
`221
`....222
`
`in Nitridc.
`
`..
`
`I General
`. .................... .. 223
`
`'ERTlES OF
`............................ ..225
`....
`225
`22?
`
`. ____ ..
`
`.. 23?
`237
`23?
`.. 237
`.'.iiiii'.'... 23?
`
`5:};-'.'o'i."i§:'i't'}i;iéiIICiI'..iIjjif
`
`4.0 MECHANICAL PROPERTIES OF
`COVALENT NITRIDES ................................................. .. 228
`.228
`4.1 Property Variables
`fiéiiiégiifII.j[i§Iififffi'.i.f.. 229
`4.2 Summary of Mechanical Pro
`229
`43 Strength and Modulus
`232
`4.4 Hardness
`EiIili1:ll~1iSiliiiFiiCCliel2ilii[i1iili1i"i itililiiiiiiiiiésiii 232
`5.0 CHEMICAL prtoii
`6.0 CHARACTERISTICS AND PROPERTIES OF
`232
`BORON NITRIDE ......................................................... ..
`232
`6.1 I-listorical Background and Present Status
`.. 232
`6.2 Hexagonal Boron Nitridc
`234
`6.3 Phase Diagram
`6.4 CVD Boron Nitride ..................................................... .. 234
`_. 235
`6.5 Cubic Boron Nitride.
`236
`6.6 Chemical Resistance ofBoron Nitridc............... .
`7.0 CHARACTERISTICS AND PROPERTIES OF
`ALUMINUM NITRIDE. .
`?.l Historical Background and Present Status
`7.2 Summary ofPr0pertics
`7.3 Phase Diagram
`7.4 Chemical Resistancco
`r}{iLii§iii{t}}i'iiii}'i'aE‘fIIIIIifi
`3.0 CHARACTERISTICS AND PROPERTIES OF
`SILICON NITRIDE ......................................................... .. 239
`8.1 Historical Background and Present Status ................... .. 239
`240
`3.2 Summary0fPropcrtics
`.. 240
`8.3 Phase Diagram
`i..'.'.iii..2=:z)
`8,4 Chemical Resistance of
`243
`8.5 Sialons
`9:0 SUMMARY or"i5}iié“iéiC}i.'riEiiéi'iiii6Ciéé's'és'Ifi[.iIjjjifif 243
`243
`9.1 Boron Nitride
`9.2 Aluminum Nitride ............................................ .ii.i.'.... 243
`9.3 Silicon Nitride ............................................................. .. 244
`10.0 SUMMARY OF APPLICATIONS AND INDUSTRIAL
`
`244
`................... .. 244
`10.1 Boron Nitride .................................... .
`10.2 Aluminum Nitride ....................................................... .. 245
`10.3 Silicon Nitride ......................................................... .
`.
`. 24‘?
`REFERENCES
`.. 245
`
`14 Processing of Refractory Carbides and Nitrides
`248
`(Powder, Bulk, and Fibers) ......................
`1.0 INTRODUCTION ............................................................. .. 248
`.
`.
`.
`.
`.
`.
`. .. 248
`l.l Synthesis Characteristics
`.
`....................... ..
`
`13
`
`

`
`xx
`
`Canton is
`
`1.2 Forms and Processing of Refractory Carbides
`and Nitrides
`2.0 PRODUCTION OF REFRACTORY CARBIDE AND
`NITRIDE POWDERS ....................................................... .. 250
`2.1 General Considerations
`250
`2.2 Chemical Preparation
`250
`2.3 Vapor-Phase Chemical Reactions ................................. .. 253
`2.4 RF Plasma
`254
`
`249
`
`254
`. 256
`
`2.5 Self-Propagating High-Temperature Synthesis (SHS)
`2.6 Sol-Gel
`..
`3.0 PRODUCTION oiieiuilkfiioiixioiiiiiiieisiiibitiésoi?”
`REFRACTORY CARBIDES AND NITRIDES
`3.] Powder Pressing
`3.2'Sintering
`262
`4.0 FIBER PRODUCTION
`4.] State ofttie Art _________________________________________________ ..J.‘ _______ .. 262
`4.2 Refractory-Carbide and Nitride Fibers by Sol-Gel
`265
`4.3 Silicon-Carbide Fibers by Chemical-Vapor Deposition
`(CVDJI
`................................................................. .. 268
`4.4 Other Refractory-Fiber Materials ................................. .. 270
`5.0 WI-IISKER
`2?]
`5.1 Silicon Carbide
`27]
`5.2 Other W'hiskerMaterials 272
`
`256
`25?
`
`IS Processing of Refractory Carbidcs and Nitrides
`(Coatings) .......................................................... .. 276
`1.0 COATING PROCESSES .................................................. .. 276
`
`276
`278
`
`1.] Composite Nature ofCoatings
`1.2 Major Coating Processes
`2.0 GENERAL CHARACTERISTICS OF CHEMICAL
`VAPOR DEPOSITION (CVD) .......................................... .. 279
`2.1 The CW) Process ........................................................ .. 279
`2.2 General Characteristics
`280
`3.0 THE CVD OF REFRACTORY CARBIDES
`280
`3.] Titanium
`280
`3.2 The CVD of Other Interstitial-Metal Carbides
`284
`3.3 The CVD of Silicon Carbide ........................................ .. 286
`3.4 The CV!) of Boron Carbide ......................................... .. 286
`4.0 THE CVD OF REFRACTORY NITRIDES ...................... .. 287
`4.1 The CVD ofTitanium Nitride
`28?‘
`4.2 The CVD ofOther Interstitial Nitrides
`283
`
`4.3 The CVD of.
`4.4 The CVD of:
`4.5.The