Boron and Refractory Borides

665 Pages·1977·17.157 MB·English

by  V. I. Matkovich (auth.), Dr. Vlado I. Matkovich (eds.)

Boronand
Refractory Borides
v.
Edited by I. Matkovich
Editorial Board
G. V. Samsonov P. Hagenmuller T. Lundstrom
With 271 Figures
Springer-Verlag Berlin Heidelberg New York 1977
Dr. VLADO I. MATKOVICH
The Carborundum Company
Niagara Falls, NY 14302/USA
Presently at:
Pall Corporation, 30 Sea Cliff Avenue,
Glen Cove, NY 115421USA
For explanation of the cover motive see legend to Fig. 2, page 80.
ISBN-13: 978-3-642-66622-3 e-ISBN-13: 978-3-642-66620-9
001: 10.1007/978-3-642-66620-9
Library of Congress Cataloging in Publication Data. Main entry under title. Boron and refractory borides. 1. Boron
compounds. 2. Borides. 3. Refractory materials. I. Matkovich, V. I., 1924-. QD181.BlB 66.546 '671'2. 77-5056.
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned,
specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying
machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law, where copies are
made for other than private use, a fee is payable to the publisher, the amount of the fee to be determined by
agreement with the publisher.
© by Springer-Verlag Berlin Heidelberg 1977.
Softcover reprint of the hardcover 1s t edition 1977
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific
statement, that such names are exempt from the relevant protective laws and regulations and therefore free for
general use.
2132/3130-543210
Contents
A. Introduction
V.I. MATKOVICH
B. Considerations of Theoretical Interest
I. The Electronic Structure of Boron Compounds
G. V. SAMSONOV and B.A. KOVENSKAYA ........................... 5
II. The Nature of the Chemical Bond in Borides
G.V. SAMSONOV and B.A. KOVENSKAYA ........................... 19
III. The Electronic Structures of the Hexaborides and the Diborides
P.G. PERKINS (With 15 Figures) .............................. 31
IV. Boron and Aluminum Dodecaboride as the Specific Type of Hopping
Conduction Materials
A.A. BEREZIN, O.A. GOLIKOVA, V.R. ZAITSEV, M.M. KAZANIN,
V.M. ORLOV, and E.N. TKALENKO (With 8 Figures) .............. 52
V. Electron Paramagnetic Resonance (EPR) in Boron Nitride, Boron
and Boron Carbide
D. GEIST (With 6 Figures) ................................... 65
VI. Structural Determinants in the Higher Borides
V.I. MATKOVICH and J. ECONOMY (With 11 Figures) ............. 78
VII. Crystal Chemistry of Higher Borides
V.I. MATKOVICH and J. ECONOMY (With 8 Figures) .............. 96
VIII. Tetragonal Boron-I and Its Derivatives
H.J. BECHER and R. MATTES (With 1 Figure) .................. 107
IX. Compounds Based on Octahedral B6 Units: Hexaborides and Tetra
borides
J. ETOURNEAU, J.-P. MERCURIO, and P. HAGENMULLER
(With 16 Figures) ......................................... 115
X. Crystal Chemistry of Boron and of Some Boron-Rich Phases; Prepa
ration of Boron Modifications
R. NASLAIN (With 28 Figures) ............................... 139
C. Preparations and Properties
I. Chemical Properties of Boron
J. CUEILLERON and F. THEVENOT .............................. 203
VI
II. Methods of Preparation of Amorphous Boron
A. F. ZHIGACH and D. C. STASINEVICH ......................... 214
III. Methods of Preparation of ~-Rhombohedral Boron
JA.A. UGAI and N.E. SOLOVIEV (With 7 Figures) ............. 227
IV. Characterization of Localized States in 8-Rhombohedral Boron
M. PRUDENZIATI (With 8 Figures) ........................... 241
V. Alkali Metal Borides
R. NASLAIN, J. ETOURNEAU, and P. HAGENMULLER
(With 19 Figures) ......................................... 262
VI. Ib and lIb Subgroup Borides
V.N. GURIN and M.M. KORSUKOVA (With 4 Figures) ............ 293
VII. Borides of the IVb Group
G.N. MAKARENKO (With 10 Figures) .......................... 310
VIII. Borides of Group Vlb Elements
G.L. GAL ' CHENKO, E.G. LAVUT, E.A. LAVUT, and L.M. VIDAVSKY. 331
IX. Transition Metal Borides
T. LUNDSTR(5M (With 7 Figures) ............................. 351
X. Single-Crystal Refractory Borides of Transition Metals
V.N. GURIN and V.S. SINELNIKOVA (With 1 Figure) ........... 377
XI. Properties and Uses of Diborides
J. CASTAING and P. COSTA (With 5 Figures) ................. 390
XII. Ternary Metal Borides
H. NOWOTNY and P. ROGL (With 6 Figures) ................... 413
XIII. Rare Earth-Boron Phase Equilibria
K.E. SPEAR (With 18 Figures) .............................. 439
XIV. Metallic Borides: Preparation of Solid Bodies-Sintering Methods
and Properties of Solid Bodies
H. PASTOR ..............•.................................. 457
XV. l-1agnetic Properties of Borides
K.H.J. BUSCHOW (With 11 Figures) .......................... 494
D. Special Applications
I. Chemical Vapor Deposition of Boron Filament
V. KRUKONIS (With 26 Figures) ...•......................... 517
II. Boron Carbide Fibers from Carbon Fibers
W.D. SMITH (With 7 Figures) ............................... 541
III. Boron Nitride Fibers
J. ECONOMY and R. LIN (With 9 Figures) .................... 552
IV. Reinforcing Properties of ALB2 Flakes
L.C. WOHRER and A.A. WOSILAIT (With 12 Figures) ........... 565
VII
V. Amorphous Boron Films
K. MOORJANI and C. FELDMAN (With 6 Figures) •.....•...•..••• 581
VI. Boride Coatings
A.P. EPIK (With 2 Figures) ..•.••....•........•..•.•........ 597
VII. Nuclear Applications of Boron and the Borides
D.E. MAHAGIN and R.E. DAHL (With 9 Figures) •••••.•.•••..... 613
VIII. Use of Boron Compounds in Lightweight Armor
M. L. WILKINS (With 11 Figures) ..•.•.......•.•.•..•.•.••.... 633
Subj ect Index ....•......•......•.•••.•••...••...••.....•.•••.••.. 649
List of Contributors
BECHER, H.J., Anorganisch-Chemisches Institut der Universitat Mlinster,
Gievenbecker Neg, 4400 Mlinster/Federal Republic of Germany
BEREZIN, A.A., Physico-Technical Institute im. Ioffe, Academy of
Sciences, Polytechnichescaya ul. 26, Leningrad/USSR
BUSCHOW, K.H.J., Bell Laboratories, 600 Mountain Avenue, Murray Hill,
N.J. 07974/USA
CASTAING, J., Office National d'Etudes et des Recherches Aerospaciales,
Paris/France
COSTA, P., Office National d'Etudes et des Recherches Aerospaciales,
Paris/France
CUEILLERON, J., Universite de Lyon 1, 43, boulevard du 11 novembre 1918,
69621 Villeurbanne/France
DAHL, R.E., Pacific Northwest Laboratory, Richland, WA/USA
ECONOMY, J., IBM Corporation, 5600 Cottle Rd., St. Jose, CA 95193/USA
EPIK, A.P., Institute of Material Problems, Academy of Sciences, Kiev
142, Krzhizhanovski St.3/USSR
ETOURNEAU, J., Universite de Bordeaux I, Laboratoire de Chimie Minerale
Structurale, 351, cours de la Liberation, 33405 Talence/France
FELDMAN, C., The Johns Hopkins University, Applied Physics Laboratories,
8621 Georgia Avenue, Silver Spring, MD 20910/USA
GAL'CHENKO, G.L., Lomonosov State University of Moscow, Chemical Fac
ulty, Moscow/USSR
GEIST, D.t, Institut flir Angewandte Physik der Techn. Hochschule Claus
thal, LeibnizstraBe, 3392 Clausthal-Zellerfeld/Federal Republic
of Germany
GOLIKOVA, O.A., Physico-Technical Institute im. Ioffe, Academy of Sci
ences, Polytechnichescaya ul. 26, Leningrad/USSR
GURIN, V.N., Physico-Chemical Institute, Academy of Sciences, Lenin
grad/USSR
HAGENMULLER, P., Universite de Bordeaux I, Laboratoire de Chimie Min
erale Structurale, 351, cours de la Liberation, 33405 Talence/
France
KAZANIN, M.M.,Physico-Technical Institute im. Ioffe, Academy of Sci
ences, Polytechnichescaya ul. 26, Leningrad/USSR
KORSUKOVA, M.M., Physico-Chemical Institute, Academy of Sciences,
Leningrad/USSR
KOVENSKAYA, B.A., Institute of Material Problems, 252142 Kiev 142,
Krzhizhanovski st. 3/USSR
KRUKONIS, V., Arthur D. Little, Inc., Acorn Park, Cambridge,
MA 02140/USA
LAVUT, E.A., Lomonsov State University of Moscow, Chemical Faculty,
Moscow/USSR
LAVUT, E.G., Lomonsov State University of Moscow, Chemical Faculty,
Moscow/USSR
LIN, R., The Carborundum Company, Niagara Falls, NY 14302/USA
LUNDSTROM, T., Uppsala Universitat, Kemiska Institutionen, Box 531
751 21, Uppsala 1/Sweden
MAHAGIN, D.E., Pacific Northwest Laboratory, Richland, WA/USA
MAKARENKO, G.N., Institute of Material Problems, Academy of Sciences,
252142 Kiev 142, Krzhizhanovski St. 3/USSR
MATKOVICH, V.I., The Carborundum Company, Niagara Falls, NY 14302/USA.
Presently at: Pall Corporation, 30 Sea Cliff Avenue, Glen Cove,
NY 11542/USA
MATTES, R., Institut fUr Angewandte Physik der Techn. Hochschule Claus
thal, LeibnizstraBe, 3392 Clausthal-Zellerfeld/Federal Republic of
Germany
MERCURIO, J.-P., Universite de Bordeaux I, Laboratoire de Chinie Minerale
Structurale, 351, cours de la Liberation, 33405 Talence/France
MOORJANI, K., The Johns Hopkins University, Applied Physics Laborato
ries, 8621 Georgia Avenue, Silver Spring, MD 20910/USA
NASLAIN, R., Universite de Bordeaux I, Laboratoire de Chimie Minerale
Structurale, 351, cours de la Liberation, 33405 Talence/France
NOWOTNY, H., Institut fUr Physikalische Chemie der Universitat Wien,
Wien/Austria
ORLOV, V.M., Physico-Technical Institute im. Ioffe, Academy of Sci
ences, Polytechnichescaya ul. 26, Leningrad/USSR
PASTOR, H., Central Laboratories, Ugine-Carbone, Grenoble/France
PERKINS, P.G., Department of Pure and Applien Chemistry, University
of Strathclyde, Glasgow, CL 1 XL/Scotiand
PRUDENZIATI, M., Laboratorio di Electtronica, Via Vivaldi 70, Modena/
Italy
ROGL, P., Institut fUr Physikalische Chemie der Universitat Wien,
Wien/Austria
SAMSONOV, G.V~, Institute of Material Problems, 252142 Kiev 142,
Krzhizhanovski St. 3/USSR
SINELNIKOVA, V.S., Institute of Material Problems, Academy of Sciences,
252142 Kiev 142, Krzhizhanovski St. 3/USSR
x
SMITH, W.O., Airco Spear, Carbon Graphite division, 4861 Packard Rd.,
Niagara Falls, NY 14302/USA
SOLOVIEV, N.E., Voronezh, University pl. 1, Voronezh State University/
USSR
SPEAR, K.E., Associate Professor of Ceramic Science, Material Sciences
Department, The Pennsylvania State University, University Park,
PA 16802/USA
STASINEVICH, D.C., Ministry of Chemical Industries, Kirov St. 20,
Moscow/USSR
THEVENOT, F., Ecole Nationale Superieure de Mines, 158, cours Fauriel,
42023 Saint-Etienne Cedex/France
TKALENKO, E.N., Physico-Technical Institute im. Ioffe, Academy of
Sciences, Polytechnichescaya ul. 26, Leningrad/USSR
UGAI, Ja.A., Voronezh, University pl. 1, Voronezh State University/
USSR
VIDAVSKY, L.M., Lomonsov State University of Moscow, Chemical Faculty,
Moscow/USSR
WILKINS, M.L., Lawrence Livermore Laboratory, University of Cali
fornia, Livermore, California/USA
WOHRER, L.C., The Carborundum Company, Niagara Falls, NY 14302/USA
WOSILAIT, A.A., The Carborundum Company, Niagara Falls, NY 14302/USA
ZAITSEV, V.R., Physico-Technical Institute im. Ioffe, Academy of Sci
ences, Polytechnichescaya ul. 26, Leningrad/USSR
ZHIGACH, A.F., Ministry of Chemical Industries, Kirov St. 20, Moscow/
USSR
A. Introduction
V. I. MATKOVICH
During the meeting of the International Symposium on Boron held in
October, 1972 in Tbilisi, U.S.S.R., the idea was proposed to assemble
a review of boron and refractory borides by the specialists present.
The advantages of such a work were immediately apparent. Such diverse
applications of borides as in protective armor, nuclear reactors, coat
ings, reinforcement, etc. can hardly all be presented in sufficient
detail by a single author. On the other hand it was also recognized
that with so much specialization, some areas of interest may not be
covered.
Within the last decade or two a number of areas have been developed in
which the use of refractory borides is growing and improvements are
being actively explored. Thus, a number of borides have considerable
potential as reinforcing material for plastics or light metals, though
only boron fibers have been firmly established up to the present. Ap
plication of flakes and films for two-dimensional reinforcement appears
attractive, although the high cost of materials and development repre
sents a considerable barrier.
A number of borides have been used to manufacture lightweight protec
tive armor. In this area relatively fast changes seem to be taking
place as improvements in performance and weight are made. Boron carbide
has found considerable use in this application and new developments
exploit the light weight of beryllium borides.
It should also be mentioned that refractory boron compounds have been
used extensively in nuclear applications. Boron is one of the very few
elements that can be used as neutron-absorber material in fission reac
tions. With the advent of fast breeder reactors and world energy short
ages, the use of boron for these applications should increase sUbstan
tially in the future.
It is hoped that further investigations of properties of various refrac
tory borides may lead to new interesting applications. One of such areas,
where a considerable amount of work is being done, is in electronic
properties related to purification of boron, crystal growth, stability
of various modifications, etc.
Difficulty in contamination control has traditionally been the biggest
single obstacle in the understanding of boron chemistry, particularly
of the higher borides. This problem is further complicated by the prob
lems in boron analysis, many of which, concerning composition and
stoichiometry of otherwise common borides always seem to recur. A few
examples are mentioned below.
When boron carbide was first discovered at the turn of the century,
Moissan assigned it the formula of B6C, Somewhat later a homogeneity
range was established with the composition of B~C representing its high
carbon-content limit. Furthermore, structure determinations all but
proved that this composition was stoichiometric. The unit cell contains
15 atoms, 12 grouped in the form of an icosahedron and three forming a