Table Of Content2 l He 10 Ne I 18 Ar I 36 Kr I 54 Xe I 86 Rn I H,231
I~
2 5 6 7 8
I H 9 F 17 CI 35 Br 53 I 85 AI
3 9 10 II 12 71 -
8 o 16 S 34 Se 52 Te 84 Po 71 Lu 03Lr _
1
.
4 16 17 18 19 71
7 N 15 P 33 As 51 Sb 83 Bi 70 Yb 102No
ers I ! 5 6 B 13 C 14 13 14 AI 35 Si 15 31 32 45 Ga 36 Ge 49 50 Sn 46 In 37 81 82 TI 38 Pb 47 69 68 Er Tm 0010171 71 m Md
b 1F
m Num 3D Zn 32 48 Cd 33 80 34 HU 67 Ho 99 Es 71
ste : I 60 61 62 71
n Sy 29 Cu 47 AU 79 Au 66 Oy 98CI
e Gmeli 28 Hi 57 46 Pd 65 78 PI 68 65 Tb 9771 Bk
with th 27 Co 58 45 64 Rh 77 I r 67 64 Gd 96 71 Cm
s 9 3 6 1
nt 5 6 6 7
Table of the Eleme : I I I , I ! I ! I • ! 1 24 25 26 Cr 52 Mn 56 Fe 42 44 43 M53 Te 69 Ru o 74 75 76 W 54 Re 70 Os 62 61 63 Pm Sm Eu 93 94 95Np 71 Pu 71 Am
dic 48 49 50 71 55
erio 23 V 41 Nb 73 Ta IDS 60 Nd 92 U
P
22 Ti 41 40 Zr 42 72 HI 43 104 71 59 Pr 91 Pa 51
21 So 39 39 Y 39 57** La 39 89*** Ac 40 58 Ce 90 Th 44
iI I 4 26 Be 12 27 MU 20 Ca 28 38 Sr 29 56 Ba 3D 88 Ra 31 nides 39 des
I H 2 3 20 Li II 21 Ha 19 • K 22 37 24 Rb 55 Cs 25 87 Fr *Lantha **Actini
~ r " ~ ~ f f ,. i , ~ I ~ f
Gmelin Handbook of Inorganic Chemistry
8th Edition
Gmelin Handbook Volumes on "Silicon" (Syst. No. 15)
Silicon Main Volume B
Element and Compounds - 1959
Silicon Main Volume C
Organic Silicon Compounds - 1958
Silicon Suppl. Vol. B 1
Silicon and Noble Gases. Silicon and Hydrogen (including SiHn-Oxygen Compounds) -1982
Silicon Suppl. Vol. B 2
Properties of Crystalline Silicon Carbide. Diodes. Molecular Species in the Gas Phase.
Amorphous Silicon-Carbon Alloys - 1984
Silicon Suppl. Vol. B 3
System Si-C. SiC: Natural Occurrence. Preparation and Manufacturing Chemistry. Special
Forms. Manufacture. Electrochemical Properties. Chemical Reactions. Applications.
Ternary and Higher Systems with Si and C (present volume) - 1986
Gmelin Handbook
of Inorganic Chemistry
8th Edition
Gmelin Handbuch der Anorganischen Chemie
Achte, vollig neu bearbeitete Auflage
Prepared Gmelin-Institut fUr Anorganische Chemie
and issued by der Max-Planck-Gesellschaft
zur Forderung der Wissenschaften
Director: Ekkehard Fluck
Founded by Leopold Gmelin
8th Edition 8th Edition begun under the auspices of the
Deutsche Chemische Gesellschaft by R. J. Meyer
Continued by E. H. E. Pietsch and A. Kotowski, and by
Margot Becke-Goehring
Springer-Verlag Berlin Heidelberg GmbH 1986
Gmelin-Institut fUr Anorganische Chemie
der Max-Planck-Gesellschaft zur Forderung der Wissenschaften
ADVISORY BOARD
Dr. J. Schaafhausen, Chairman (Hoechst AG, Frankfurt/Main-Hochst), Dr. G. Breil (Ruhr
chemie AG, Oberhausen-Holten), Dr. G. Broja (Bayer AG, Leverkusen), Prof. Dr. G. Fritz
(Universitat Karlsruhe), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. R. Hoppe
(Universitat GieBen), Dr. H. Moell (BASF-Aktiengesellschaft, Ludwigshafen), Prof. Dr. H. Noth
(Universitat Munchen), Prof. Dr. G. zu Putlitz (Universitat Heidelberg), Prof. Dr. A. Rabenau
(Max-Planck-Institut fur Festkorperforschung, Stuttgart), Prof. Dr. Dr. H. A. Staab (Prasident
der Max-Planck-Gesellschaft, Munchen), Prof. Dr. Dr. h.c. mult. G. Wilke (Max-Planck-Institut
fUr Kohlenforschung, Mulheim/Ruhr)
DIRECTOR DEPUTY DIRECTOR
Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert
CHIEF EDITORS
Dr. K.-C. Buschbeck - Dr. H. Bergmann, F. Fussel, B. Heibel, Dr. H. Katscher, Dr. R. Keim, Dipl.
Phys. D. Koschel, Dr. U. Kruerke, Dr. H. K. Kugler, Dr. P. Merlet, Dr. E. Schleitzer-Rust, Dr.
A. Slawisch, Dr. F. Schroder, Dr. B. v. Tschirschnitz-Geibler, Dr. R. Warncke
STAFF
D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, Dr. L. Berg, Dipl.-Chem. E. Best, Dipl.-Ing. V. A.
Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, R. Dowideit, Dipl.
Chem. M. DroBmar, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, Dr. W.-D. Fleischmann,
V. Frick, Dr. R. Frobose, G. Funk, Dipl.-Ing. N. Gagel, E. Gerhardt, Dr. U. W. Gerwarth, M.-L.
Gerwien, Dipl.-Phys. D. Gras, C. Gorr, H. Hartwig, Dipl.-Min. H. Hein, G. Heinrich-Sterzel, H.-P.
Hente, H. W. Herold, U. Hettwer, Dr. I. Hinz, Dr. W. Hoffmann, Dipl.-Chem. K. Holzapfel, Dr.
S. Jager, Dr. J. von Jouanne, H.-G. Karrenberg, Dipl.-Phys. H. Keller-Rudek, Dr. L. KieBling,
Dipl.-Phys. E. Koch, Dr. E. Koch, Dipl.-Chem. K. Koeber, Dipl.-Chem. H. Kottelwesch, R. Kolb,
E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. P. Kuhn, Dr. W. Kurtz, M. Langer, Dr.
A. Leonard, Dipl.-Chem. H. List, H. Mathis, E. Meinhard, K. Meyer, Dr. M. Mirbach, Dr. U. Neu
Becker, K. Noring, Dipl.-Chem. R. Nohl, Dipl.-Min. U. Nohl, Dr. W. Petz, I. Rangnow, Dipl.-Phys.
H.-J. Richter-Ditten, Dipl.-Chem. H. Rieger, B. Riegert, E. Rieth, A. Rosenberger, Dr. B. Roth,
E. Rudolph, G. Rudolph, Dipl.-Chem. S. Ruprecht, Dr. R. C. Sangster, V. Schlicht, Dipl.-Chem.
D. Schneider, Dipl.-Min. P. Schubert, A. Schwarzel, Dipl.-Ing. H. M. Somer, E. Sommer,
M. Teichmann, Dr. W. Topper, Dipl.-Ing. H. Vanecek, Dipl.-Chem. P. Velie, Dipl.-Ing. U. Vetter,
H.-M. Wagner, Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. B. Wobke, K. Wolff,
U. Ziegler
CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF
Dr. J. R. Clark, Dr. D. B. Gerth, Dr. J. L. Grant, Dr. K. Rumpf, Dr. K. Swars, Dr. U. Trobisch,
Dr. B. Vance
EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E. h. Margot Becke
CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock
Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
Gmelin Handbook
of Inorganic Chemistry
8th Edition
Si
Silicon
Supplement Volume B 3
System Si-C. SiC: Natural Occurrence. Preparation
and Manufacturing Chemistry. Special Forms.
Manufacture. Electrochemical Properties. Chemical
Reactions. Applications. Ternary and Higher
Systems with Si and C
With 87 illustrations
AUTHORS Vera Haase, Gerhard Kirschstein, Hildegard List,
Sigrid Ruprecht, Raymond Sangster, Friedrich Schroder,
Wolfgang Topper, Hans Vanecek
Werner Heit, NUKEM GmbH, Hanau
Jurgen Schlichting (dec.), Universitat Karlsruhe
EDITORS Hartmut Katscher, Raymond Sangster, Friedrich Schroder
CHIEF EDITOR Friedrich Schroder
System Number 15
Springer-Verlag Berlin Heidelberg GmbH 1986
LlTERATURE CLOSING DATE: END OF 1983
IN VARIOUS CASES MORE RECENT DATA HAVE BEEN CONSIDERED
Library 01 Congress Catalog Card Number: Agr 25-1383
ISBN 978-3-662-06996-7 ISBN 978-3-662-06994-3 (eBook)
DOI 10.1007/978-3-662-06994-3
This work is subject to copyright. AII rights are reserved. whetherthe whole or part 01 the material is concerned. specilically those 01
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"Verwertungsgesellschaft Wort". Munich.
© by Springer-Verlag Berlin Heidelberg 1985
Originally published by Springer-Verlag Berlin Heidelberg New York Tokyo in 1985
Softcover reprint 01 the hardcover 8th edition 1985
The use 01 registered names. trademarks. etc .. in this publication does not imply. even in the absence 01 a specilic statemenl. that
such names are exempt lrom the relevant protective laws and regulations and therelore Iree lor general use.
Preface
This volume concludes the coverage of silicon carbide, SiC, begun in "Silicon" Supplement
Volume B 2, 1984, subtitled "Silicon Carbide - Part I". Part I described the physical properties
of SiC, SiC diodes, molecular species in the SiC-C gas phase, and amorphous silicon-carbon
alloys. The current Part II ("Silicon" Supplement Volume B 3,1986) covers in its initial chapter
the Si-C phase diagram and in the final chapters the higher order systems of Si and C with
additional elements through boron, arranged according to the Gmelin system. In between
some 95% of the volume focusses on SiC, beginning with its natural occurrence, preparation
and formation, and purification, continuing with its chemical analysis, manufacture of special
ized forms, electrochemistry, and chemical reactions, and concluding with descriptions of its
myriad applications. The final applications section covering electronic devices also describes
similar applications of the amorphous Si-C alloys. The successive chapters in this volume are
often closely interrelated, since it is often necessary to synthesize SiC directly in a form in
which it will be applied. SiC cannot be melted and cast, nor rolled nor drawn, nor is it easily
electroplated or sintered or purified.
Silicon carbide first became known to man when E. G. Acheson in 1891 used an electric
current to heat a mixture of clay and carbon to extremely high temperatures. From this initial
experiment evolved within a few years the commercial Acheson process for the manufacture
of SiC by the electrothermal reaction of sand and carbon. For details see "Silicon" Supplement
Volume A 1, 1984. Only a number of years later was SiC identified as naturally occurring in
meteorites, and only within very recent decades has it been recognized that it is also a
frequently occurring (but in great dilution) terrestrial mineral. The surprisingly voluminous
literature on its natural occurrence required 30-odd pages in the Handbook for its summariza
tion. The preparation, formation, and commerical production of SiC occupies nearly 45% of
this volume. The chemistry of its preparation and formation can be summarized quite
succinctly: Under sufficiently reducing conditions at sufficiently high temperatures, substan
tially any conceivable combination of carbonaceous and siliceous materials will yield SiC.
Silicon carbide is extremely hard and resistant to both thermal shock and high tempera
tures. It has a low density and a high thermal conductivity and mechanical properties unusual
for a nonmetallic substance. It is a very high band gap semiconductor readily doped both p
and n-type. Irradiation effects in both fission and fusion reactors are mild. It is under many
circumstances quite inert chemically, and under others so reactive that the largest single
application in terms of tonnage consumed is as a reactive additive in iron and steel production.
Thus the range of applications extends from metallurgical and chemical uses through abrasive
and abrasion-resistant forms to refractory and mechanical engineering materials to protective
coatings and applications in nuclear technology to electrical and electronic equipment, and
even in some 120 Handbook pages it has been possible only to highlight these applications
from a chemical point of view and to cite at some length the more relevant literature,
particularly the review papers and books where greater detail can be found.
Much of the initial material for both Gmelin volumes dealing with silicon carbide was
prepared by the late Dr. Jl.irgen Schlichting, Institut fUr Chemische Technik, Universitat
Karlsruhe.
Frankfurt am Main F. A. Schroder
November 1985
IX
Table of Contents
Page
The Si-C Phase Diagram ................................................ .
2 Silicon Carbide, SiC ..................................................... 6
2.1 Natural Occurrence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . 6
2.1.1 General. Nomenclatu re 6
2.1.2 Terrestrial Occurrence 7
Paragenesis ............................................................. 7
Genesis ................................................................ 16
Intergrowths and Inclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Compositional Analyses ................................................... 22
Crystal Form und Crystal Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Optical Properties ........................................................ 28
Other Physical Properties. Tests ............................................ 33
2.1.3 Extraterrestrial Occurrence ............................................ 34
2.2 Preparation and Formation ............................................. 36
2.2.1 Preparation and Manufacturing Chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
General Comments ....................................................... 36
Reactions of Si and C ..................................................... 40
Si(s)+C .............................................................. 40
Si(I)+C ............................................................... 41
Si(g)+C .............................................................. 44
Si(s, g) + C(g) .......................................................... 45
Si(soln) + C(soln) ....................................................... 46
Reactions of Si-C-O(-H) Materials ........................................... 46
Si(s, I), + C + HP or Si02 .••.................•.....••....••.•••..••.••.••• 46
Si(s, I, g) + CO or Phenolic Resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
SiO(g, s) + C ........................................................... 48
SiO(g) + CO or Hydrocarbons or Acetone ................................... 50
Si0 (s, I) + C ........................................................... 51
2
Basic Aspects of Reaction of Si0 and C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2
Acheson Process ..................................................... 53
ESK Process ......................................................... 62
Electric Arc Reaction of Si0 + C ........................................ 64
2
Other Manufacturing Processes with Si0 + C ............................. 65
2
Other Preparations of SiC from Si02 + C .................................. 70
Silicic Acid or Silica Gel + C .............................................. 72
Si02 + Hydrocarbons .................................................... 73
Silica Gel or Si02 + Other Organic Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Pyrolysis of Rice Wastes ................................................. 75
Pyrolysis of Oxygen-Containing Organosilicon Compounds or Polymers .. . . . . . . . 76
Carbon Reduction of Silicates ............................................ 77
CaC2 Reduction of Si02 or Silicates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Pyrolytic Reactions of Si-C-H Systems ....................................... 79
Equilibrium Considerations in the Si-C-H System ............................ 79
Gmelin Handbook
Silicon B 3
x
Page
Si(s, l, g) + Hydrocarbons ................................................. 80
Si(s) + CH4 ........................................................... 80
Si(l, g) + CH4 ......................................................... 81
Si(s) + C2H2 .......................................................... 81
Si(l, g) + C2H2 ........................................................ 82
Si(s, l, g) + CxHy(g), (CxHy = C2H4, C3Ha, C6HsCH3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
SiH4(g) + C or Hydrocarbons ............................................. 84
SiH4 +C ............................................................. 84
SiH4 + CH4 ........................................................... 84
SiH4 + C2H4 .......................................................... 85
SiH4 + C3Ha .......................................................... 86
SiH4 + CxHy(g), (CxHy = C3H6, C6HsCH3) .................................... 88
Pyrolysis of Si-C-H Organosilanes ......................................... 88
CH3SiH3 ............................................................. 88
(CH3)4Si ............................................................. 89
Other Alkyl, Alkenyl, or Aryl Silanes ...................................... 89
Si-C-H Organosilicon Polymers ......................................... 91
Pyrolytic Reactions of Si-C-Cl-H Systems .................................... 98
Basic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Si + C-Cl-H Systems ..................................................... 102
Si + C + Cl-Containing Atmospheres ..................................... 102
Si + CCl4 and CH2Cl2 .................................................. 102
SiH4 + C-Cl(-H) Materials ................................................. 103
SiCl4 + C or C-Cl(-H) Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 103
SiCl4+C ............................................................ 103
SiCl4 + CH4 .......................................................... 104
SiCl4 + C3Ha .......................................................... 106
SiCl4 + Unsaturated Aliphatic Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 107
SiCl4 + C6H6 .......................................................... 107
SiCl4 + C6H12 or C6H14 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108
SiCl4 + C6HSCH3 ...................................................... 108
SiCl4+CCl4 .......................................................... 110
SiCl4 + Other Chlorinated Hydrocarbons .................................. 114
Inorganic Chlorosilanes + C-Cl-H Materials ................................. 115
Si2Cl6 + CCl4, CHCl3, or C2HCl3 .......................................... 115
SiHCl3 + Carbonaceous Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 115
SiH2Cl2 + C3Ha ........................................................ 117
Pyrolysis of CH3SiCl3 .................................................... 117
Basic Aspects ........................................................ 117
CH3SiCl3 Pyrolysis Without Added H2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 121
CH3SiCl3+ H2 ........................................................ 123
CH3SiCl3+CH4 ....................................................... 128
CH3SiCl3 + C6HSCH3 (+ CCl4) ............................................ 128
Pyrolysis of Other Chloro(organo)silanes ................................... 129
(CH3hSiCl2 .......................................................... 129
(CH3hSiCl ........................................................... 132
CH3SiHCl2 ........................................................... 134
SiH3CHCl2 ........................................................... 136
Other Chlorosilanes ................................................... 136
Gmelin Handbook
Silicon B 3
