Bovidés

current collector Weber N, Kummer J Τ 1967 Sodium-sulfur secondary

battery. In: Collins D Η (ed.) 1967 Proc. Annual Power
Sources Conf. US Army Signal Research and Develop-
insulated end cap - ment Laboratory, Fort Monmouth, NJ, pp. 37-9

sodium - R. Stevens
beta-alumina membrane - [ U n i v e r s i t y of Leeds, Leeds, U K ]
U m i qn 0 6
"^^'L. ^ ..!^'

Borides
A wide variety of elements in t h e p e r i o d i c table form
c o m p o u n d s with b o r o n , t e r m e d borides. This article
sulfur - impregnated - c o n c e n t r a t e s o n t h e b i n a r y m e t a l borides, a g r o u p of
graphite felt
m a t e r i a l s of g r o w i n g scientific a n d industrial interest,
Figure 4 since a n u m b e r of their p r o p e r t i e s such as h a r d n e s s ,
Diagram of a sodium-sulfur cell strength, w e a r resistance, high melting point, chemical
inertness a n d metallic c h a r a c t e r c a n be utilized t o
resolve m a n y technical p r o b l e m s .
b e t a - a l u m i n a m e m b r a n e , usually in t h e form of a
closed-end thin-walled t u b e . I n t h e design s h o w n , t h e
sulfur electrode is central; alternative designs in- 7. Properties
c o r p o r a t e t h e sulfur in t h e o u t e r c o m p a r t m e n t of t h e
cell. O n c o n n e c t i o n of t h e external circuit, t h e s o d i u m Borides d o n o t c o n f o r m t o t h e o r d i n a r y c o n c e p t s of
gives u p electrons; t h e s o d i u m ions formed t h e n dif- valency, either in s t o i c h i o m e t r y or in structure. T h e
fuse t h r o u g h t h e b e t a - a l u m i n a t o react with t h e sulfur s t o i c h i o m e t r y of m e t a l b o r i d e s ranges from c o m -
t o p r o d u c e t h e sulfide. T h e reverse r e a c t i o n occurs o n p o u n d s with low b o r o n c o n t e n t , such as M 5 B , to
recharging. c o m p o u n d s extremely rich in b o r o n , such as M B 6 6-
Usually, it is c o n v e n i e n t t o place t h e sulfur inside M B 9 9, w h e r e M represents a metal. W i t h i n this c o m -
t h e b e t a - a l u m i n a t u b e since t h e c e r a m i c h a s far s u p e - p o s i t i o n a l r a n g e t h e c r y s t a l l o g r a p h i c s t r u c t u r e of the
rior c o r r o s i o n resistance t o t h a t of t h e mild-steel o u t e r b o r i d e s c h a n g e s (see T a b l e 1). T h e spatial d i s t r i b u t i o n
case. T h i s a r r a n g e m e n t is considered t o offer sufficient of b o r o n a t o m s is characteristic for all these c o m -
a d v a n t a g e t o offset t h e slight decrease in p o w e r a n d p o u n d s , c h a n g i n g from isolated b o r o n a t o m s t o pairs,
energy density t h a t results. c h a i n s a n d t h r e e - d i m e n s i o n a l c o n n e c t e d n e t w o r k s in
I n a d d i t i o n t o practical a p p l i c a t i o n s , b e t a - a l u m i n a s t h e b o r o n - r i c h b o r i d e s , t h e n u m b e r of b o r o n - b o r o n
a r e also of c o n s i d e r a b l e research interest as t h e y i n t e r a c t i o n s increasing with increasing b o r o n c o n t e n t .
p r o v i d e o n e of t h e clearest e x a m p l e s of a solid w i t h a T h e covalent b o n d i n g of t h e b o r o n a t o m s c a n be
high ionic conductivity. A l t h o u g h t h e s o d i u m i o n c o n s i d e r e d as a r e a s o n for t h e c o m m o n l y observed
variety h a s received t h e m o s t a t t e n t i o n , d u e t o its high h a r d n e s s a n d high melting p o i n t s of t h e borides
a p p l i c a t i o n in t h e s o d i u m - s u l f u r b a t t e r y , t h e r e is n o w (see T a b l e 2).
a r a n g e of m a t e r i a l s in which t h e s o d i u m ion is T r a n s i t i o n m e t a l s of g r o u p s I l i a t o VIII form
replaced by o t h e r alkali m e t a l ions, silver ions o r b o r i d e s . In general, i s o m o r p h o u s b o r i d e s c o n s t i t u t e a
h y d r o x o n i u m ions. T h e b e h a v i o r of these m a t e r i a l s c o n t i n u o u s series of solid s o l u t i o n s within specific
closely parallels t h a t of t h e s o d i u m ion variety. r a d i u s r a t i o s of t h e m e t a l a t o m s . T h e m a n y b i n a r y a n d
t e r n a r y b o r i d e s of t h e t r a n s i t i o n m e t a l s a r e of metallic
See also: Aluminum Oxide Ceramics c h a r a c t e r ; with s o m e limitations, this is also t r u e of the
b o r i d e s of the l a n t h a n i d e s a n d actinides. Besides g o o d
electrical c o n d u c t i v i t y (Table 2), t h e electron emission
of t h e r a r e - e a r t h b o r i d e s is o u t s t a n d i n g . L a B 6 , for
Bibliography e x a m p l e , h a s a w o r k function of 2.68 eV a n d a
4 - 1 _ 1
R i c h a r d s o n c o n s t a n t of 73 χ 1 0 A m K .
Dell R M, Moseley Ρ Τ 1981 Beta-alumina electrolyte for
Borides a r e resistant t o m o s t chemical reagents, b u t
use in sodium-sulfur batteries, part 1: Fundamental prop-
erties. J. Power Sources 6: 143-60 like B 4 C they a r e soluble in fused alkali. D i b o r i d e s ,
Kummer J Τ 1972 ^-alumina electrolytes. Prog. Solid State especially T i B 2 , s h o w excellent wettability a n d sta-
Chem. 7: 141-75 bility in liquid m e t a l s (e.g., a l u m i n u m ) . T h e o x i d a t i o n
Stevens R, Binner J Ρ G 1984 Structure, properties and resistance of b o r i d e s is only m o d e r a t e ; a b o v e 1200 Κ
production of 0-alumina. J. Mater. Sei. 19: 695-715 (927 °C) in air, m a r k e d oxide f o r m a t i o n is observed at

35
Bondes

Table 1
Crystallographic characteristics of some metal borides (after Schwetz et al. 1981)

Crystal system and

Formula Metal structural type Arrangement of boron atoms

M 4B Pd, Pt cubic, Pt 4B type isolated atoms

M 2B Ta, Cr, Mo, W, Fe, Ni, Co tetragonal, CuAl 2 type isolated atoms
M 5B 3 Cr tetragonal, Cr 5B 3 type
M 3B 2 V, Nb, Ta, Mo tetragonal, U 3S i 2 type isolated pairs
MB V, Nb, Ta, Mo, Cr, W, Ni rhombic, CrB type single chains
MB Mo, W tetragonal, MoB type
MB Ti, Hf, Fe, Co rhombic, FeB type
M 3B 4 V, Nb, Ta, Cr rhombic, T a 3B 4 type double chains
MB 2 Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, hexagonal, A1B2 type two-dimensional hexagonal
U, Pu, Al network
M 2B 5 Mo, W hexagonal, M o 2 B 5 type
MB 4 Y, lanthanides, actinides tetragonal, U B 4 type three-dimensional network
MB 6 Y, lanthanides, actinides cubic, CaB 6 type connected B 6 octahedrons
M B 12 Se, Y, Zr, Mo, W, lanthanides, actinides cubic, U B 1 2 type 24 cross-linked boron atoms
surround a central metal
atom
M B 66 Y, Pu, lanthanides Y B 66 type three-dimensional network of
B 1 2 clusters

Table 2
Physical properties of some refractory borides (after Schwetz et al. 1981)

Melting Knoop
Density
3 3
point Electrical8 resistivity hardness,
Boride (10 k g m ' ) ÎK) (10~ Qm) 1 Ν load

TiB 2 4.52 3470 9-15 2600

ZrB 2 6.09 3520 7-10 1830
ZrB 12 3.61 2520 60-80 2580
HfB 2 11.2 3650 10-12 2160
VB 2 5.10 2670 16-38 2110
NbB 2 7.21 3270 12-65 2130
TaB 2 12.60 3370 14-68 2500
CrB 2 5.20 2170 21-56 1100
M o 2B 5 7.48 2370 18-45 2180
W 2B 5 13.1 2470 21-56 2500
Fe 2B 7.32 1663 1800
FeB 7.15 1820 30 1900
CoB 7.32 1535 26 2350
NiB 7.39 1325 23
LaB 6 5.76 2985 7-15 2010
EuB 6 4.91 2890 80-170 1840
UB4 9.38 2768 30 1850
U B 12 5.65 2500 22 2630
CaB 6 2.46 2540 160 5 1650
SiB 6 2.43 2140 2 χ 107 2140
B 4C 2.52 2720 1 0 M120 3000
ß-B 2.35 2420 10 2600

the surface. (Exceptions are the silicon b o r i d e s S i B 4 a n t s t a t e m e n t s c a n be m a d e . As is typical for h a r d

a n d S i B 6 , b u t these are usually r e g a r d e d as b o r o n materials, the elastic m o d u l i are high a n d the general
suicides.) p e r f o r m a n c e is brittle at low t e m p e r a t u r e s . T h e
T h e m e c h a n i c a l properties of the borides h a v e n o t s t r e n g t h of the borides c a n be considered t o be
been intensively investigated; however, s o m e i m p o r t - m o d e r a t e t o high. Actual m e a s u r e m e n t s are always

36
 Borides

influenced by the grain s t r u c t u r e , p o r o s i t y a n d t h e from t h e v a p o r p h a s e by a halide reaction (see

presence of second p h a s e s . T a b l e 3). T h i s process c a n also be used t o form surface
c o a t i n g s by chemical v a p o r d e p o s i t i o n .
Since refractory b o r i d e s in general a r e h a r d a n d
2. Production
brittle, m a c h i n i n g of b o r i d e p a r t s needs special p r o -
T a b l e 3 s h o w s t h e r e a c t i o n schemes of s o m e tech- cesses. D i a m o n d g r i n d i n g is possible a n d a high sur-
nically interesting p r e p a r a t i o n processes for m e t a l face finish c a n be achieved. Since s o m e b o r i d e s s h o w a
borides. high electric c o n d u c t i v i t y , electric-spark c u t t i n g p r o -
In the direct r e a c t i o n of t h e m e t a l with b o r o n , cedures c a n be used in these cases.
b o r i d e f o r m a t i o n s t a r t s a t a b o u t 1200 Κ (927 °C) a n d
is a c c o m p a n i e d b y a n e x o t h e r m i c reaction. Very p u r e
c o m p o u n d s c a n be o b t a i n e d either by a r c fusion o r 3. Applications
reaction-sintering techniques.
In c o n t r a s t t o this small-scale process, t h e car- T h e h a r d n e s s a n d w e a r resistance of the m e t a l borides
b o t h e r m i c r e d u c t i o n of oxides is suitable for large- a r e t h e m o s t c o m m o n p r o p e r t i e s utilized in technical
scale p r o d u c t i o n . T h e r e a c t i o n p r o d u c t s a r e of a p p l i c a t i o n s . In the b o r o n i z i n g process (using B 4 C as
technical p u r i t y a n d , o w i n g t o t h e very high process t h e b o r o n d o n o r ) , b o r i d e layers a r e formed o n the
t e m p e r a t u r e s ( > 2600 Κ (2327 °C)), c o a r s e - g r a i n e d surface of m e t a l p a r t s o r h a r d m e t a l - c u t t i n g tools
materials are o b t a i n e d . d u r i n g heat t r e a t m e n t , t h u s i m p r o v i n g lifetime a n d
T h e r e d u c t i o n of m e t a l oxides with b o r o n c a r b i d e service p e r f o r m a n c e u n d e r w e a r c o n d i t i o n s . A 1 B 1 2
(and if necessary c a r b o n ) d o e s n o t d e m a n d such high a n d T i B 2 a r e used as m a t r i x m a t e r i a l s in h a r d m e t a l -
t e m p e r a t u r e s , 2100 Κ (1827 °C) being typical; as a c u t t i n g tools. B o r i d e surface layers c a n also be
consequence, t h e w h o l e process c a n be b e t t e r c o n - p r o d u c e d by p l a s m a spraying. C o m p o s i t e s based o n
trolled. Boride f o r m a t i o n p r o c e e d s via solid-state pressureless sintered T i B 2 - T i C - F e m i x t u r e s s h o w
reactions u n d e r v a c u u m o r inert gases. M a s s p r o - excellent p e r f o r m a n c e as c u t t i n g tools for a l u m i n u m
d u c t i o n is possible. alloys. Sintered T i B 2 c a n be used as a n efficient a r m o r
A suitable m e t h o d for t h e p r e p a r a t i o n of very p u r e m a t e r i a l against projectiles of u l t r a h i g h velocity.
b o r i d e s is the electrolysis of fused salts c o n t a i n i n g a T h e chemical stability of d i b o r i d e s , especially T i B 2
m e t a l oxide a n d b o r o n oxide. T h i s p r o c e s s is being a n d Z r B 2 , in t h e e n v i r o n m e n t of a H a l l - H é r o u l t cell
used for t h e p r o d u c t i o n of small q u a n t i t i e s of for a l u m i n u m p r o d u c t i o n , t o g e t h e r with their wet-
borides. tability by liquid a l u m i n u m a n d their high electric
T h e processes m e n t i o n e d a b o v e give b u l k y b o r i d e conductivity, h a s suggested a p r o m i s i n g d e v e l o p m e n t .
m a t e r i a l s o r h a r d aggregates of b o r i d e particles. In By replacing the c o n v e n t i o n a l g r a p h i t e c a t h o d e a n d
o r d e r to fabricate dense, s h a p e d bodies, p o w d e r m e t - lowering the a n o d e - c a t h o d e d i s t a n c e in t h e cryolite
allurgical p r o c e d u r e s h a v e t o be applied. T h e first step b a t h , energy savings of u p t o 2 5 % seem t o be possible
is always t h e p r e p a r a t i o n of sintering p o w d e r s , a in t h e electrolysis of a l u m i n u m . D i b o r i d e s c a n be
process which n o r m a l l y includes intensive milling favorably used in crucibles for t h e h a n d l i n g of liquid
with t h e d r a w b a c k of i m p u r i t y p i c k u p . T h e consolid- m e t a l s such as a l u m i n u m , c o p p e r , silver, gold, zinc,
a t i o n of p o w d e r s d u r i n g sintering c a n be achieved c a d m i u m , m a g n e s i u m , g e r m a n i u m , lead, b i s m u t h a n d
with a n d w i t h o u t pressure. As a c o n s e q u e n c e of t h e c h r o m i u m . M a n y t o n n e s of T i B 2 p o w d e r g o i n t o the
high melting p o i n t s of m o s t b o r i d e s , high t e m p e r - p r o d u c t i o n of v a c u u m metallizing b o a t s ( T i B 2 , A1N,
a t u r e s h a v e t o be used for sintering. Pressureless B N composite). T h e y are resistance-heated t o a b o u t
sintering t e c h n i q u e s h a v e been successfully applied for 1700 Κ (1427 °C) a n d used for t h e c o n t i n u o u s e v a p o -
very fine ( s u b m i c r o m e t e r ) p o w d e r s . Such p o w d e r s , r a t i o n of a l u m i n u m t o p r o d u c e thin m e t a l films, for
which are p y r o p h o r i c in air, c a n be m a n u f a c t u r e d e x a m p l e , o n c a p a c i t o r foils.

Table 3
Some processes for the synthesis of metal borides

Process Reaction scheme

Direct reaction of the metal with boron by fusion and reaction

sintering M + B->MB
Carbothermic reduction of oxides MO + B 2 0 3 + C - MB + CO
Reaction of metal oxide with boron carbide (and carbon) MO + B 4C ( + C) - MB + CO
M g
Electrolysis of fused salts containing metal and boron oxides MO + B 2 0 3 ° ) MB + O .
2 0
MgF2 2
Deposition from the vapor phase
M-halide + B-halide + H 2 MB
+ H-halide

37
Borides

T h e metallurgical i n d u s t r y is the greatest c o n s u m e r Hoard J L, Hughes R Ε 1967 Elemental boron and com-
of borides. T h e a p p l i c a t i o n of borides in the form of pounds of high boron content: Structure, properties and
welding metals ( N i - C r - B - S i alloys) is well k n o w n ; polymorphism. In: Muetterties Ε (ed.) 1967 The Chemistry
these alloys are m a i n l y used t o p r o d u c e c o r r o s i o n - of Boron and its Compounds. Wiley, New York, pp. 25-154
a n d wear-resistant surface coatings. I m p o r t a n t r a w Kuwabara Κ 1987 ZrB 2 based composite ceramics. In:
Werheit Η (ed.) 1987 Boron and Borides, Proc. 9th Int.
m a t e r i a l s for the h a r d b o r i d e alloys a r e C r B , C r B 2 ,
Symp., University of Duisburg, pp. 444-5
N i B a n d F e B . F e r r o b o r o n is k n o w n as a grain-refining Matkovich V I (ed.) 1977 Boron and Refractory Borides.
a d d i t i o n in steelmaking. T h e s a m e effect is achieved Springer, Berlin
with small T i B 2 a d d i t i o n s for t h e p r o d u c t i o n of fine- Moskowitz D 1983 Method of making and using a TiB 2
grained a l u m i n u m . Very small a m o u n t s of b o r o n o r comprising body. World Patent No. PCT-WO 84/04713
borides ( 5 0 - 2 0 0 p p m ) also cause a m a r k e d grain- Pastor H, Thevenot F 1978 Applications industrielles des
refining effect in high-melting m e t a l s such as m o l y b - composés du bore. Inf. Chim. 178: 151-73
denum, tungsten, tantalum, vanadium and uranium. Samsonov G V, Serebryakova Τ J, Neronov V A 1975
T h e m e c h a n i c a l properties, deformability a n d weld- Boridy. Atomizdat, Moscow
ability of m o l y b d e n u m alloys are also c o n s i d e r a b l y Schwetz Κ A, Lipp A 1985 Boron carbide, boron nitride and
metal borides. Ullmanrfs Encyclopedia of Industrial Chem-
improved. N e w Z r B 2 - b a s e d composite materials (e.g.,
istry. VCH Publishers, Deerfield Beach, FL, pp. 295-307
Z r B 2 - S i C , Z r B 2 - S i C - B 4 C ) h a v e been d e v e l o p e d for Schwetz Κ A, Reinmuth K, Lipp A 1981 Herstellung und
w e a r : r e s i s t a n t a p p l i c a t i o n s in the h a n d l i n g of m o l t e n industrielle Anwendung refraktärer Borverbindungen.
metals or slags. Radex Rundsch. 3: 568-85
C a B 6 is a s t r o n g a n d effective deoxidizing a n d Spear Κ Ε 1976 Phase behavior and related properties of
fluxing agent for n o n f e r r o u s metals. C o p p e r , deoxi- rare-earth borides. In: Alper A M (ed.) 1976 Phase Dia-
dized with C a B 6 , h a s a high electrical conductivity, grams: Materials Science and Technology, Vol. 4. Aca-
since the m a x i m u m solubility of b o r o n in c o p p e r demic Press, New York, pp. 91-159
Telle R 1988 Borides—A new hard material generation?
(0.05%) d o e s n o t m a r k e d l y influence t h e conductivity.
Chemie Zeit 22(3): 93-9
In a d d i t i o n , the s t r e n g t h of such deoxidized c o p p e r Thompson R 1965 Borides: Their Chemistry and Appli-
can be c o n s i d e r a b l y increased (relative t o the s t r e n g t h cations. The Royal Institute of Chemistry, London
of p u r e c a t h o d e c o p p e r ) by t h e r m o m e c h a n i c a l
treatment. H. K n o c h
H e x a b o r i d e s of t h e a l k a l i n e - e a r t h m e t a l s a n d r a r e - [Elektroschmelzwerk Kempten, Kempten, G e r m a n y ]
e a r t h metals are v a l u a b l e c a t h o d e m a t e r i a l s for
electron emission. Very high c u r r e n t densities c a n be
achieved at r a t h e r low emission t e m p e r a t u r e s c o m -
p a r e d with m e t a l electrodes. L a B 6 is the preferred
material in c o m m e r c i a l electron devices, b u t o t h e r Boron Carbide
h e x a b o r i d e s , such as Y B 6 , G d B 6 , T h B 6 , B a B 6 , a n d
L a B 6 - B a B 6 solid solutions, seem t o be p r o m i s i n g for B o r o n c a r b i d e ( B 4 C ) is the m o s t p r o m i n e n t c o m -
this a p p l i c a t i o n . p o u n d in t h e b o r o n - c a r b o n system. It h a s m a n y
All m e t a l b o r i d e s c a n be used as n e u t r o n - a b s o r b i n g i m p o r t a n t uses, p a r t i c u l a r l y as a r a w m a t e r i a l for the
materials. If m e t a l s are c h o s e n for b o r i d e f o r m a t i o n f o r m a t i o n of o t h e r b o r i d e s a n d in the w h o l e field of
which possess a n even higher c a p t u r e cross section for b o r o n chemistry.
n e u t r o n s t h a n b o r o n itself (e.g., lanthanides), t h e n
materials are o b t a i n e d with extremely high m a c r o -
1. Properties
scopic c a p t u r e cross sections a n d excellent refractory
properties. R a r e - e a r t h h e x a b o r i d e s , a n d especially B 4 C crystallizes with a r h o m b o h e d r a l lattice, t h e lat-
E u B 6 , are being tested as n e u t r o n - a b s o r b i n g pellets in tice c o n s t a n t s in t h e h e x a g o n a l a r r a n g e m e n t being
c o n t r o l r o d s for fast-flux n u c l e a r r e a c t o r s . T h e effici- a0 = 0.560 n m a n d c 0 = 1.212 n m . T h e formula B 1 2C 3
ency of borides for nuclear a p p l i c a t i o n s c a n be influ- c a n be a t t r i b u t e d t o t h e unit cell, w h e r e C 3 c h a i n s a n d
1 0
enced over a wide r a n g e by enriching t h e reacting B B 1 2 i c o s a h e d r o n s are a r r a n g e d a l o n g t h e space dia-
i s o t o p e from t h e 19.9 a t . % found in n a t u r a l b o r o n u p g o n a l of a c u b e . B 4 C is b l a c k a n d melts at 2720 Κ
3
to a c o n t e n t higher t h a n 90 a t . % . (2447 °C); its density is 2510 k g m ~ .
After d i a m o n d , c u b i c b o r o n nitride a n d B 6 0 , B 4 C
See also: Boron Carbide
exhibits t h e highest h a r d n e s s of a n y k n o w n m a t e r i a l ,
possessing a K n o o p h a r d n e s s of a r o u n d 3000. T h e
r o o m - t e m p e r a t u r e b e n d s t r e n g t h of dense polycrystal-
Bibliography 2 2
line B 4 C r a n g e s from 350 M N m " t o 500 M N m ~ ,
Benesovsky F 1975 Metallboride. In: Bartholome Ε, Beikert a n d in n o n o x i d i z i n g a t m o s p h e r e s a n excellent
Ε. Hellmann Η, Ley Η, Weigert W, Weise Ε (eds.) 1975 s t r e n g t h r e t e n t i o n is o b s e r v e d u p t o 1750 Κ (1473 °C).
UIlmanns Enzyklopädie der Technischen Chemie, Vol. 8. The Young's modulus, shear modulus and Poisson's
2
Verlag Chemie, Weinheim, pp. 657-62 ratio at r o o m temperature are 441GNm~ ,

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