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Si Silicon: 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 PDF

562 Pages·1985·12.366 MB·English
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Preview Si Silicon: 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

2 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 translation. reprinting. reuse 01 illustrations. broadcasting. reproduction by photocopying machine or similar means. and storage in data banks. Under § 54 01 the German Copyright Law where copies are made lor other than private use. alee is payable to "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

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