BORON CARBONITRIDE -A HIGH-TEMPERATURE

ELECTRIC INSULATING AND REFRACTORY MATERIAL

G. V. Samsonov, A. I. Eroshenko, UDC 669.162.212

V. I. Ostroverkhov, V. A. Krat,
and T. V. Dubovik

The R e f r a c t o r y M a t e r i a l s Section of the Institute of M a t e r i a l s Science, Academy of Sciences of the

Ukrainian SSR and the B r o v a r y Powder M e t a l l u r g y F a c t o r y have jointly developed a method for the p r o -
duction of l a r g e - s i z e d , 100-300 m m in d i a m e t e r , b o r o n c a r b o n i t r i d e p a r t s . L a r g e - s i z e d b o r o n c a r b o n l -
t r i d e blanks a r e p r e s s e d f r o m a m i x t u r e of b o r o n nitride and c a r b i d e powders in the weight ratio 1 : 1 in a
200-ton hydraulic p r e s s under a p r e s s u r e of 1.5 t o n s / c m 2. To i m p r o v e the p r e s s i n g b e h a v i o r of the pow-
d e r s , the m i x t u r e is p l a s t i c i z e d with a 3% solution of synthetic r u b b e r in benzine. P r e s s e d blanks a r e
s i n t e r e d for 1 h at 1950~ in a h i g h - f r e q u e n c y induction furnace provided with a p r o c e s s i n g a t m o s p h e r e
containing 81-82% N2, up to 11% CO2, 3-4% H20 , and up to 2% O2, using 700-ram o.d. x 600-ram i.d. x 300-
m m high c r u c i b l e s .
B o r o n c a r b o n i t r i d e is an excellent e l e c t r i c insulating m a t e r i a l which also exhibits high t h e r m a l shock
r e s i s t a n c e and withstands the action of molten m e t a l s , alloys, s l a g s , and s a l t s . The p r o p e r t i e s of b o r o n
c a r b o n i t r i d e a r e s u m m a r i z e d in T a b l e 1 [1, 2]. The e l e c t r i c insulating p r o p e r t i e s of b o r o n c a r b o n i t r i d e in
the t e m p e r a t u r e r a n g e 20-2000~ a r e s u p e r i o r to those of such o x y g e n - f r e e r e f r a c t o r y compounds as boron,
a l u m i n u m , and silicon n i t r i d e s and also of the r e f r a c t o r y oxides ZrO2, A1203, MgO, and ThO 2. The high
e l e c t r i c insulating p r o p e r t i e s of b o r o n c a r b o n i t r i d e a r e linked with the c h a r a c t e r of the c h e m i c a l bond b e -
tween its components, which is effected by s and p e l e c t r o n s , with the f o r m a t i o n of the stable sp 3 configura-
tions by all its a t o m s .

Boron c a r b o n i t r i d e p o s s e s s e s high r e f r a c t o r y p r o p e r t i e s : it is r e s i s t a n t to the action of silicon-

b o r o n alloys at a t e m p e r a t u r e of the o r d e r of 2000~ m o l t e n s i l i c i d e s , nickel and cobalt b a s e alloys, and
molten c h r o m i u m , m a n g a n e s e , gold, c o p p e r , and h i g h - b a s i c i t y slags at t e m p e r a t u r e s of 1300-1700~
c r y o l i t e - a l u m i n a m e l t s and liquid a l u m i n u m at 1000~ molten m i x t u r e s of chlorides, fluorides, and p o t a s -
s i u m fluoborate at 900~ molten m i x t u r e s of antimony and sodium and p o t a s s i u m chlorides at 800~ Bo-
ron c a r b o n i t r i d e does not r e a c t with m o l y b d e n u m at t e m p e r a t u r e s of up to 1500~ with niobium up to
1600~ and with tungsten up to 1300~ On heating to t e m p e r a t u r e s of 1500-2300~ it shows no r e a c t i o n
with s uch r e f r a c t o r y compounds as b o r i d e s , c a r b i d e s , aluminides, s ulfides, s elenides, and g e r m a n i d e s .
Boron c a r b o n i t r i d e can o p e r a t e s a t i s f a c t o r i l y at t e m p e r a t u r e s of up to 1400-1500~ in a i r , up to 2500-
2600~ in argon, hydrogen, and c a r b o n monoxide, and up to 3000~ in nitrogen.
Single- and twin-channel e l e c t r i c insulating sheaths m a d e of b o r o n c a r b o n i t r i d e a r e nowadays ex-
t e n s i v e l y used for the p r o t e c t i o n of m e t a l l i c t h e r m o c o u p l e s at high t e m p e r a t u r e s [1]. B o r o n c a r b o n i t r i d e
has found its applications as an e l e c t r i c insulating m a t e r i a l in v a c u u m a p p a r a t u s f o r t h e deposition of
m e t a l s on cloths and films and also in h i g h - t e m p e r a t u r e and high-voltage ion s o u r c e s ; unlike other insu-
lating m a t e r i a l s , s u c h as alundum, s t e a t i t e , porcelain, and the like, which begin to fuse under t h e s e condi-
tions a f t e r 2 h, b o r o n c a r b o n i t r i d e o p e r a t e s s a t i s f a c t o r i l y in such s o u r c e s for hundreds of hours at a t e m -
p e r a t u r e of 2500~ and a voltage of 300 V. The use of b o r o n c a r b o n i t r i d e as an e l e c t r i c insulating m a t e r i a l
has enabled e l e m e n t s to be c o n s t r u c t e d for heating g a s e s to high t e m p e r a t u r e s (up to 2000~

Institute of M a t e r i a l s Science, A c a d e m y of Sciences of the Ukrainian SSR. B r o v a r y Powder M e t a l -

lurgy F a c t o r y . T r a n s l a t e d f r o m P o r o s h k o v a y a Metallurgiya, No. 12 0.20), pp. 46-48, D e c e m b e r , 1972.
Original a r t i c l e submitted April 11, 1972.

9 1973 Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New York,
N. Y. 10011. All rights reserved. This article cannot be reproduced for any purpose whatsoever without
permission of the publisher. A copy of this article is available from the publisher for $15.00.

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 T A B L E 1. Properties of Boron Carbonitride

Tempera- Tempera-
Property Property
ture, *C ture, ~
Electrical resistivity, Eva~oorationrate,
-cm g/cm 2- sec
20 >I0 is 1515 6,78.10 -9
750 2.101~ 1580 1,60.10 -8
!000 5.106 1650 4,34.10-8
1220 3- 106 1760 2,46.10 -7
1400 5.10 ~ 1881 2,67.10 -6
1600 3.104 1927 4,43. 10-6
2000 2" 104
Compression strength,
Thermal conductivity, kg/mm 2
W/m- *C 20 1,59
300 27.0 1000 1,63
500 20,8 1200 1,71
700 15,9 1400 1,90
900 13,4 1640 2,66
1150 12,2 1820 3,76
1300 11,0 1930 4,12
1500 10,5 2020 4,75
1800 10,1
20O0 9,8 Bend strength,
Coeffo of thermal ex- kg/mm2
20 I, 80
pressionx I0-8, 1/*C
20-- 300 O, 77 Modulus of normal elas-
300--1000 1,9--4,3 ticity, kg/cm2
1000--2000 4,4--4,6 2O 138300
Dielectric permeability at 220 135600
X = 4.6 cm 890 130800
20 1,9--2,1 1175 127700
1800 12250O
Tangent of dielectric loss
angle at X = 4.6 cm
20 O, 017--0,04

In s p e c i a l s e r v i c e t e s t s on s i t a l l s , * o x i d e s , g r a p h i t e , a n d n o n m e t a l l i c r e f a c t o r y c o m p o u n d s , b o r o n
c a r b o n i t r i d e w a s found to e x h i b i t t h e h i g h e s t r e s i s t a n c e to c h e m i c a l a t t a c k b y f u s e d b o r a x a t 950~ The
m e a n r a t e o f a t t a c k b y b o r a x on b o r o n c a r b o n i t r i d e a t t h i s t e m p e r a t u r e o v e r a p e r i o d of 1000 h w a s 0.0062
m m / h w i t h o u t e l e c t r o l y s i s a n d 0.0003 m m / h w i t h e l e c t r o l y s i s . T h e a v a i l a b i l i t y of a n o n m e t a l l i c m a t e r i a l
c a p a b l e o f o p e r a t i n g f o r a long p e r i o d of t i m e in f u s e d b o r a x s h o u l d now m a k e it p o s s i b l e to c o n s t r u c t
e l e c t r o l y t i c b o r o n i z i n g i n s t a l l a t i o n s of a l m o s t a n y c o n f i g u r a t i o n o r s i z e [3].

T h e o u t s t a n d i n g p h y s i c . t e c h n i c a l p r o p e r t i e s o f b o r o n c a r b o n i t r i d e e n a b l e t h i s c o m p o u n d to b e r e c -
o m m e n d e d f o r u s e a s a r e f r a c t o r y a n d e l e c t r i c i n s u l a t i n g m a t e r i a l in m a n y new f i e l d s of t e c h n o l o g y , f o r
e x a m p l e , in c r u c i b l e s , t a n k s , a n d t u b e s f o r p u m p i n g m o l t e n m e t a l s a n d m i x t u r e s of s l a g a n d s a l t m e l t s ,
thermocouple sheaths, lining plates, and high-temperature electric insulators operating at temperatures of
up to 2000-2500~ [4, 5].

LITERATURE CITED
T . V. D u b o v i k a n d L . I. S t r u k , P o r o s h k o v a y a M e t . , No. 5 , 1 0 7 (1966).
2. T . V. D u b o v i k , T . V. A n d r e e v a , a n d V. K . K a z a k o v , in: H e t e r o g e n e o u s D i e l e c t r i c s [Ln R u s s i a n ] ,
U k r N I I N T I , K i e v (1967), p. 58.
3. M. E . G u t m a n , L . A. M i k h a i l o v , et a l . , P o r o s h k o v a y a M e t . , No. 8, 60 (1968).
4. G. V. S a m s o n . v , N o n m e t a l l i c N i t r i d e s [in R u s s i a n ] , M e t a l l u r g i y a , M o s c o w (1969).
5. T . V. D u b o v i k a n d T . V. A n d r e e v a , in: D i e l e c t r i c s [in R u s s i a n ] , I z d . KGU, K i e v (1971), p. 82.

* Microcrystalline glasses such as Pyroceram - Translator.

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