Sc, Y, La-Lu, Rare Earth Elements: Compounds with Boron

289 Pages·1989·12.234 MB·English

by  Hiltrud Hein, Claus Koeppel, Ursula Vetter, Eberhard Warkentin (auth.), Dr. Hartmut Bergmann, Gerhard Czack, Hiltrud Hein, Sigrid Ruprecht, Ursula Vetter (eds.)

1
2 Hel 10 Ne I 18 Ar I 36 Kr I 54 Xe 1 86 Rn 1 H,23
I;
2 5 6 7 8 a
I H 9 F 17 CI 35 Br 53 1 85 8At
8 o 3 16 S 9 34 Se 10 52 Te 11 84 Po 12 71 Lu 103 Lr 71
7 N 4 15 P 16 33 As 17 51 Sb 18 83 Bi 19 70 Vb 102 No 71
I I 6 C 14 14 Si 15 32 45 Ge 50 Sn 46 82 Pb 47 69 Tm 101 Md 71
bers 5 B 13 13 AI 35 31 36 Ga 49 In 37 81 TI 38 68 Er 100 Fm 71
m Num 30 Zn 32 48 Cd 33 80 H34 g 67 Ho 99 Es 71
n Syste 29 Cu 60 47 Ag 61 79 Au 62 66 Dy 98 Cf 71
meli 57 65 68 71
e G 28 Ni 46 Pd 78 Pt 65 Tb 97 Bk
with th 27 Co 58 45 64 Rh 77 Ir 67 64 Gd 96 71 Cm
nts 59 63 66 71
me 26 Fe 44 Ru 76 Os 63 Eu 95 Am
the Ele I I! I : I I, , I 25 Mn 56 43 Tc 69 75 Re 70 62 Sm 94 Pu 71
Table of , , 24 Cr 52 42 M53 o 74 W 54 61 Pm 9371 Np
I
dic 48 49 50 71 5 5
erio 23 V 41 Nb 73 Ta 105 60 Nd 92 U
P
22 Ti 41 40 Zr 42 72 Hf 43 104 71 59 Pr 9151 Pa
21 Sc 39 39 V 39 57** La 39 89*** Ac 40 58 Ce 9044 Th
4 26 Be 12 M27 g 20 Ca 28 38 Sr 29 56 Ba 30 88 Ra 31 an ides 39 n ides
I H 2 3 20 Li 11 21 Na 19 * K 22 37 24 Rb 55 Cs 25 87 25a Fr *Lanth ** Acti
* "'
~ f ... " i" c;') i-s' .,. ~ 3 ur ... i' ~ :;. CI> i" it 1:1:1 ~ (") ~ ~
Gmelin Handbook of Inorganic Chemistry
8th Edition
Gmelin Handbook
of Inorganic Chemistry
8th Edition
Gmelin Handbuch der Anorganischen Chemie
Achte, völlig neu bearbeitete Auflage
Prepared Gmelin-Institut für Anorganische Chemie
and issued by der Max-Planck-Gesellschaft
zur Förderung 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 1990
Gmelin-Institut für Anorganische Chemie
der Max-Planck-Gesellschaft zur Förderung der Wissenschaften
ADVISORY BOARD
Dr. G. Breit, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (Philipps
Universität, Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grünewald
(Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, Frankfurt/Main-Höchst), Prof. Dr.
H. Nöth (Universität München), Prof. Dr. H. Offermanns (Degussa AG, Frankfurt/Main), Prof.
Dr. G. zu Putlitz (Universität Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-Institut für Fest
körperforschung, Stuttgart), Prof. Dr. A. Simon (Max-Planck-Institut für Festkörperforschung,
Stuttgart), Prof. Dr. Dr. A. H. Staab (Präsident der Max-Planck-Gesellschaft, München), Prof.
Dr. Dr. h.c. mult. G. Wilke (Max-Planck-Institut für Kohlenforschung, Mülheim/Ruhr)
DlRECTOR DEPUTY DIRECTOR
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EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E. h. Margot Becke
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CHIEF EDITORS
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dasch, Dr. W. HuisL, B. Jaeger, Dr. R. Jotter, Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem.
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STAFF
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M. Kunz, Dr. A. NebeL, Dipl.-Chem. R. NohL, Dr. B. Rempfer, Dr. K. Schücke, U. TöLLe, Dipl.-Ing.
H. Vanecek
Volumes published on "Rare Earth Elements" (8yst. No. 39)
A1 Introductory Review. History. Occurrence - 1938
A2 Scandium: History. Occurrence - 1973
A3 V, La to Lu: Cosmochemistry - 1980
A4 V, La to Lu: Crystal Chemistry - 1979
A5 V, La to Lu: Geochemistry - Total Earth. Magmatic Cycle - 1981
A6b V, La to Lu: Geochemistry - Hydrosphere. Atmosphere. Cosmo- and Geochemical
Cycles. Balance - 1988
"A7 V, La to Lu: Minerals (Excluding Silicates) - 1984
"AB V, La to Lu: Minerals (Silicates). Deposits. Mineral Index - 1984
081 Sc, V, La to Lu: History, Position in the Periodic System. Separation from Raw
Materials - 1976
82 Sc, V, La to Lu: Separation of the Rare Earth Elements from One Another. Preparation
of the Pure Metals. Uses. Toxicology - 1976
83 Sc, V, La to Lu: Physical Properties of the Metals - 1974
084 Sc, V, La to Lu: Nuclear, Atomic, and Molecular Properties - 1976
85 Sc, V, La to Lu: Preparation, Enrichment, and Separation of Isotopes (Sc, V, La to Sm)
-1978
86 Sc, V, La to Lu: Preparation, Enrichment, and Separation of Isotopes (Eu to Lu).
Detection and Determination of Isotopes. Chemical Reactions of the Elements -1978
87 Sc, V, La to Lu: Reactions of the Ions in Solution. Electrochemical Behavior - 1979
C1 Sc, V, La to Lu: Hydrides. Oxides - 1974
C2 Sc, V, La to Lu: Compounds with H+O, Alkali Metals+O, N, as weil as the Related
Alkali Double Salts - 1974
C 3 Sc, V, La to Lu: Fluorides, Fluoride Oxides, and the Related Alkali Double Salts -1976
"C 48 Sc, V, La to Lu: Chlorides. Comparative Data - 1982
" C 4 b Sc, V, La to Lu: Data on Individual Chlorides - 1982
C 5 Sc, V, La to Lu: Oxide Chlorides, Hydroxide Chlorides, Salts of Oxoacids of Chlorine,
and Alkali Chlorometallates - 1977
C 6 Sc, V, La to Lu: Bromides. Iodides, Corresponding Basic Halides. Salts of Halogen
Oxoacids and Alkali Double Salts - 1978
"C 7 Sc, V, La to Lu: Sulfides, Oxide Sulfides, Alkali Thiometallates - 1983
o C B Sc, V, La to Lu: Sulfide Halides. Sulfates, Salts of Other Sulfuric Acids and Corre-
sponding Alkali Double Compounds - 1981
"C 9 Sc, V, La to Lu: Compounds with Se - 1986
"C 10 Sc, V, La to Lu: Compounds with Te, Po - 1987
"C 118 Sc, V, La to Lu: Compounds with B - 1990 (present volume)
"01 Sc, V, La to Lu: Coordination Compounds 1 - 1980
" 02 Sc, V, La to Lu: Coordination Compounds 2 - 1982
"03 Sc, V, La to Lu: Coordination Compounds 3 - 1981
" 04 Sc, V, La to Lu: Coordination Compounds 4 - 1986
" 05 Sc, V, La to Lu: Carboxylates - 1984
" 06 Sc, V, La to Lu: Ion Exchange and Solvent Extraction Reactions. Organometallic
Compounds - 1983
" Completely or partly in English
0
Gmelin Handbook
of Inorganic Chemistry
8th Edition
Sc, Y, La-Lu
RARE EARTH ELEMENTS
C 11a
Compounds with Boron
With 88 illustrations
AUTHORS Hiltrud Hein, Claus Koeppel, Ursula Vetter,
Eberhard Warkentin
EDITORS Hartmut Bergmann, Gerhard Czack, Hiltrud Hein,
Sigrid Ruprecht, Ursula Vetter
CHIEF EDITOR Hartmut Bergmann
System Number 39
Springer-Verlag Berlin Heidelberg GmbH 1990
L1TERATURE CLOSING DATE: 1988
IN MANY CASES MORE RECENT DATA HAVE BEEN CONSIDERED
Library of Congress Catalog Card Number: Agr 25-1383
ISBN 978-3-662-07505-0 ISBN 978-3-662-07503-6 (eBook)
DOI 10.1007/978-3-662-07503-6
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Originally published by Springer-Verlag, Berlin· Heidelberg . New York· London . Paris· Tokyo in 1989
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Typesetting
Preface
The volume "Rare Earth Elements" C 11 deals with the compounds and systems of the rare
earth elements with boron, Le., borides, borates, and associated alkali double compounds. As
in all earlier volumes of "Rare Earth Elements" Se ries C ("Seltenerdelemente" Reihe Cl,
comparative data are presented in sections preceding treatment of the individual compounds
and systems.
Topics of the present volume C 11 aare the comparative data on the borides and the indi
vidual sections on the systems and borides containing Sc, Y, and La. The individual sections
for the systems and borides with Ce to Lu can be found in the following volume C 11 b together
with the borates, their alkali double compounds, and other compounds containing Ce to Lu,
boron and elements related by the Gmelin system.
The most extensively studied borides treated in the comparative sections are of the type
MBe. These rare earth hexaborides are refractory compounds and so me of them, especially
LaBe, are good thermionic emissive materials or exhibit other interesting physical properties.
For example, many data on mechanical, thermal, or electrical properties are presented in
tables and figures. In connection with these useful properties, the preparation of the sampIes
and their chemical and thermal stability play an important role. Interesting crystallographic
structures are presented in the comparative sections on MB4 and MBee, the latter formula gives
only an approximate composition for the most boron-rich compound in the M-B systems. Main
topics of these sections and those for the borides of the type MB and MB are also physical
2 12
properties. The most comprehensive chapter in the individual sections of volume C 11 adeals
with LaBe, which is a well-known thermionic material of great practical importance with high
electron emission efficiency and an excellent stability in the surface composition at high
temperatures. The effects of preparation conditions, composition, temperature, surface struc
tures, surface treatment, and of the atmosphere on the thermionic emission are studied
thoroughly. Another important item of the LaBe chapter is the electronic structure, which often
serves as an example for the other rare earth hexaborides. In the individual section on yttrium
borides, the thermionic properties and the electronic structure of YB4 and YBe are also
remarkable features.
Frankfurt am Main Hartmut Bergmann
November 1989
XI
fable of Contents
Page
32 Rare Earth Elements and Boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
32.1 Borides ............................................................ .
General Referenees ....................................................... .
32.1.1 Comparative Data tor MB2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
32.1.1.1 Preparation ....................................................... 2
32.1 .1.2 Crystallog raph ie Properties. Density .................................. 2
32.1.1.3 Thermal and Magnetie Properties. Eleetronie Strueture .................. 4
32.1.2 Comparative Data tor M2Bs ........................................... 6
32.1.3 Comparative Data tor "MB;' (x=3 to 4) ................................ 6
32.1.4 Comparative Data tor MB4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
32.1.4.1 Formation, Preparation ............................................. 6
32.1.4.2 Crystallographie Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
32.1.4.3 Valeney .......................................................... 12
32.1.4.4 Meehanieal and Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
32.1.4.5 Magnetie Properties ............ ......... ...... .... ................. 15
32.1.4.6 Eleetrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
32.1.4.7 Chemical and Eleetroehemical Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
32.1.5 Comparative Data for MBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
32.1.5.1 Existenee ........................................................ 21
32.1.5.2 Homogeneity Range ............................................... 22
32.1.5.3 Preparation ....................................................... 23
Preparation of Polyerystalline Sam pIes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Single-Crystal Growth ......................................... . . . . . . . . . . . . 28
Preparation of Films ...................................................... 31
32.1.5.4 Crystallographie Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
32.1.5.5 Lattiee Vibrations .................................................. 39
32.1.5.6 Nuclear Magnetic Resonanee ........................................ 42
32.1.5.7 Crystal Field Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
32.1.5.8 Mechanieal Properties .............................. . . . . . . . . . . . . . . . . 45
32.1.5.9 Thermal Properties ................................................ 49
32.1.5.10 Magnetie Properties .................. ............. ................ 55
Gmelin Handbook
e
RE Main Vol. 11a