ALUMINUM VAPORIZERS MADE OF MATERIALS BASED

ON BORON NITRIDE AND TITANIUM DIBORIDE

V. I. Mogilenskii, V. M. Gropyanov, UDC 621.66.049.1 : 669.71

A. N. Zhunda, A. G. Zeberin,
and G. V. Egorova

Composite m a t e r i a l s based on boron nitride and titanium diboride show g r e a t p r o m i s e for the m a n u -
f a c t u r e of c o r r o s i o n r e s i s t a n t elements of installations for the vacuum vaporization of aluminum [1-4]. Yet
suitable techniques f o r the production of such m a t e r i a l s and t h e i r p r o p e r t i e s have up to now r e c e i v e d v e r y
little investigation, and it is t h e r e f o r e impossible rationally to choose the best compositions and methods
of m a n u f a c t u r e of parts for industrial s e r v i c e . In view of this, the p r e s e n t work was c a r r i e d out with the
aim of studying the reactions of b o r o n nitride with molten aluminum and some p r o p e r t i e s of B N - T i B 2 c o m -
posite m a t e r i a l s , and also of developing, on the basis of r e s u l t s obtained, a p r o c e s s for the production of
p a r t s having the r e q u i r e d c h a r a c t e r i s t i c s .
The existing view that boron nitride and aluminum do not react chemically with each other [5, 6] is
based on the fact that molten aluminum does not wet a boron nitride support plate. However, a t h e r m o -
dynamic calculation of the reaction BN +A1 =A1N +B shows that the reaction can in fact take place. The
standard i s o b a r i c - i s o t h e r m a l potential of this reaction, calculated using Ulich's f i r s t approximation, is
AG~T = 15,800-0.37 T, while its equilibrium constant is K s = 0 . 7 - 102 at 1800~
B e c a u s e of the intense vaporization of aluminum and appreciable dissociation of boron nitride at high
t e m p e r a t u r e s , our experimental investigation of the reactions between these m a t e r i a l s was conducted on
specimens p r e p a r e d by the method of hot p r e s s i n g at 1800-2000~ X - r a y diffraction p i c t u r e s of h o t - p r e s s e d
boron nitride with an addition of 20% (by weight) of aluminum have v e r y distinct diffraction m a x i m a c h a r -
a c t e r i s t i c of aluminum nitride (Table 1). Aluminum nitride can be uniquely identified also in other s p e c i -
mens, p r e p a r e d f r o m m i x t u r e s consisting of titanium diboride, boron nitride, and metallic aluminum.

T A B L E 1. D a t a Y i e l d e d b y D i f f r a c t i o n Pictures of R e a c t i o n Products
of Boron Nitride and Aluminum
!BN+ A1 BN A1N ]BN+ A1 BN A1N
Specimen ~andard [7] standard [7] ~spemmen ~tandard[7] standard [7]
No. . . - -- No. ] - --
I din I d~n ] 1 d/n ] I din ' din 1 d/n
I
1 4 3,71 I 2 3,74 I 13 18 1,67 26 1,67 I
2 00 3,26 100 3,25 14 17 1.56 100 t,56
3 2 2f5 [ 2 2,94 15 15 1,42 100 1,42
4 30 2,71 I 90 2,70 16 i 8 1,35 40 1,35
5 18 2,49 I 69 2,4~ 17 15 1=32 [ 7 1,32
6 27 2.36 ] 90 2,26 18 6 1,31 ] 70 1,31
7 9 2,26 I 19 6 1,25 9 1,25
8 2(17 ] 24 2,18 20 8 1,19 8 1,19
9 6 2,(8 I 9 2,09 7 1,17 '14 1,17
10 3 11~6 I 22 2 1,13 20 1,13
1I 18 1,82 1 2~ 1,83 23 2 1,11 3 1,11
12 2 1,73 I , 1,73 24 1 1 C8 2 1, C8
I0 1 ,C'5 83 1,05

All-Union Institute of Refractories. Translated from Poroshkovaya Metallurgiya, No. 3 (111), pp.
42-47, March, 1972. Original article submitted July 15, 1970.

9 1972 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.

203
 Fig. 1. M i c r o s t r u c t u r e of h o t - p r e s s e d Fig. 2. M i c r o s t r u c t u r e of zone of con-
specimen: 1) TiB2; 2) AlE; 3 ) B N . tact of specimen with aluminum.
x 300.

bO

,0

Ck,
,r~ ~ ~.,.x.X" 30
3
~700 26

22
/MO x/x -
/8

,,00 */ ~'~- D~,80 /4

t300 / " j
1200~_ .x-x/ ____ Bbt3

//00 -<.x~x.~ "xr D:t2okg/cm

z
r i i J

0BA/,vol. ~ 40 50 60 70 Time, rain

Fig. 3 Fig. 4
Fig. 3. Properties of hot-pressed materials based on BIN-TiB2 with aluminum addition: 1)
apparent density; 2) electrical resistivity; 3) open porosity.
Fig. 4. Variation of die t e m p e r a t u r e (1) and specimen shrinkage (2) with time in hot p r e s s i n g .

TABLE 2. Chemical Metallographic examinations confirmed that aluminum nitride does

Composition of Reaction f o r m during the reaction of BN with aluminum. F i g u r e 1 illustrates the
Products of B N - T i B 2 m i c r o s t r u c t u r e of a s p e c i m e n p r e p a r e d f r o m a mixture containing 45.1 BN,
Composite and Aluminum 45.7 TiB2, and 9.2 wt. % A1. After hot p r e s s i n g at 1800~ t h r e e phases,
white, light g r a y , and dark, can be distinguished in such a specimen. The
compo- initial Comp.of
nent comp., hot-pressed white grains, ranging in size f r o m 5 to 30 /~, are titanium diboride, with a
wt. % specimen, m i c r o h a r d n e s s of 2800 k g / m m 2. The light g r a y c r y s t a l s , judging f r o m t h e i r
wt. %
m i c r o h a r d n e s s (1000 kg/mm2), m a y be identified as aluminum nitride. The
TiB~ 45,7 47,7 p o r e s and boron nitride, which is difficult to polish b e c a u s e of its low h a r d -
BN 45,1 39,0 n e s s , appear in m i e r o g r a p h s as dark a r e a s . The c h e m i c a l compositions of
A1 9,2 3,1
A1N -- 10,4
the specimen b e f o r e and after hot p r e s s i n g a r e given in Table 2.

204
 TABLE 3. Service C h a r a c t e r i s t i c s of TiB 2 and BN +TiB 2
Vaporizing Elements
Vaporizing Vaporizing Vapor - Vaporizing vaporized Amt. of A!
element Life, h rate, izing 2 rate,
material g/rain area,cm g/cm~_min per cycle,
g/cm2
TiB~ 0,75--I,0 I 5,0 15,6 0,320 14,5--192
(limiting) (maximum)
BN-I-TIB~ 2,0 7,0 14,8 0,470 57--60

B.10/~ -ore
]
20. I
A 4r

2,0

r
.~~

20o
l
400 600 800 lOOP : 1200 14~0 T,~
Fig. 5. Variation of e l e c t r i c a l r e s i s t i v i t y of specimens
with t e m p e r a t u r e : 1) 60% BN, 30% TiB2, 10% A1; 2) 50%
BN, 40% TiB2, 10% A1; 3) m a t e r i a l made by Heraeus
Company; 4) 50% BN, 50% TiB2; 5) 25% BN, 75% TiB 2.

Thus, on the basis of data yielded by t h e r m o d y n a m i c , x - r a y diffraction, metallographic, and chemical

studies, it was established that, during hot pressing, boron nitride r e a c t s with aluminum, resulting in the
f o r m a t i o n of aluminum nitride. The r e a c t i o n p r e s u m a b l y takes place according to the f o r m u l a BN +A1 =
A1N +B, although no amorphous boron could be detected by x - r a y diffraction in the r e a c t i o n products. It is
conceivable that the r e a c t i o n yields aluminum borides, which cannot readily be identified in such complex
mixtures.
In spite of the r e l a t i v e l y intense reaction of boron nitride with aluminum, m a t e r i a l s based on B N - T i B 2
c o m p o s i t e s exhibit good c o r r o s i o n r e s i s t a n c e when exposed to molten aluminum owing to the formation of a
p r o t e c t i v e s u r f a c e l a y e r of aluminum nitride. F i g u r e 2 shows the m i c r o s t r u c t u r e of the zone of contact of
a specimen with molten aluminum after holding in a vacuum of 1 " 10 -3 m m Hg at 1000~ for 25 h. In a s u r -
face zone 0.2-0.5 m m deep, the boron nitride r e a c t s with the aluminum, and the resultant aluminum nitride,
b e c a u s e of an i n c r e a s e in specific volume, fills the p o r e s . The nonporous s u r f a c e l a y e r produced in this
m a n n e r , composed of the starting titanium diboride and aluminum nitride, protects the m a t e r i a l against
f u r t h e r attack, b e c a u s e both these compounds a r e r e s i s t a n t to molten aluminum.

205
 In o r d e r to evolve a p r o c e s s f o r the m a n u f a c t u r e of v a p o r i z i n g e l e m e n t s , e x p e r i m e n t s w e r e c a r r i e d
out on the sintering of s p e c i m e n s f r o m m i x t u r e s containing v a r i o u s p r o p o r t i o n s of b o r o n nitride and titanium
diboride. It was found that high-density s p e c i m e n s cannot be produced by sintering in a vacuum o r a n i t r o -
gen a t m o s p h e r e at boron nitride contents in e x c e s s of 20-30%. Raising the sintering t e m p e r a t u r e and the
b o r o n nitride content c a u s e s s p e c i m e n s to expand owing to d i s s o c i a t i v e v a p o r i z a t i o n of the BN.
Much b e t t e r r e s u l t s w e r e obtained in the hot p r e s s i n g of m i x t u r e s containing s m a l l additions of m e -
tallic aluminum. The p r e s e n c e of 10% aluminum by volume i m p r o v e s the s i n t e r a b i l i t y of B N - T i B 2 c o m -
p o s i t e s , enabling s p e c i m e n s of 4-5% p o r o s i t y to be obtained f r o m m i x t u r e s containing up to 50% b o r o n ni-
t r i d e (Fig. 3). The simultaneous action of p r e s s u r e and t e m p e r a t u r e c a u s e s , as noted above, the r e s u l t a n t
aluminum nitride to fill the pores between the p a r t i c l e s of the m a t r i x m a t e r i a l , which p r o m o t e s d e n s i f i c a -
tion. An aluminum addition also a c t i v a t e s sintering through the f o r m a t i o n of a liquid phase. Dense p a r t s
can be obtained at r e l a t i v e l y low t e m p e r a t u r e s (1700-1800~ F i g u r e 4 i l l u s t r a t e s a typical h o t - p r e s s i n g
schedule employed in the p r e p a r a t i o n of t e s t s p e c i m e n s .
The e l e c t r i c a l r e s i s t i v i t y of B N - T i B 2 b a s e m a t e r i a l s with an aluminum addition is a function of t h e i r
p o r o s i t y (Fig. 3). The e l e c t r i c a l r e s i s t i v i t y of m a t e r i a l s p r e p a r e d f r o m m i x t u r e s containing 40-52 vol. %
b o r o n nitride is 1000-4000/A2-cm at r o o m t e m p e r a t u r e , i n c r e a s i n g only slightly when the t e m p e r a t u r e is
r a i s e d to 1600~ (Fig. 5).
The m e c h a n i c a l strength of all h o t - p r e s s e d s p e c i m e n s was found to lie in the r a n g e 850-900 k g / c m 2,
and it is thus evident that such c o m p o s i t e s can be employed as c o n s t r u c t i o n a l m a t e r i a l s in p r o c e s s e s f o r
the v a c u u m deposition of aluminum coatings. H o t - p r e s s e d c o m p o s i t e s a r e a m e n a b l e to machining with h a r d
alloy tools, enabling p a r t s of the r e q u i r e d configuration to be obtained f r o m c y l i n d r i c a l blanks.
Finally, an e x p e r i m e n t a l batch of v a p o r i z i n g e l e m e n t s of a s t a n d a r d industrial s i z e was produced by
machining blanks 200 m m in d i a m e t e r and up to 60 m m high, hot p r e s s e d in a 500-kW, 100-ton p r e s s . The
v a p o r i z i n g e l e m e n t s w e r e subjected to t e s t s at the Special Vacuum Deposition Design Bureau, State Planning
C o m m i s s i o n of the Latvian SSR. T e s t i n g was p e r f o r m e d in a UV-29 v a c u u m installation, and involved h e a t -
ing the e l e m e n t s by the d i r e c t P a s s a g e of c u r r e n t at a t e m p e r a t u r e of 1500-1600~ and a r e s i d u a l p r e s s u r e
of 5" 10 -4 m m Hg. After 2 hours operation, the e l e m e n t s w e r e still fit f o r f u r t h e r s e r v i c e . When f r a c t u r e d ,
the s p e c i m e n s investigated w e r e found to have a zone of s t r u c t u r a l changes extending up to about o n e - t h i r d
of the v a p o r i z e r height, but the depth of the r u p t u r e zone did not exceed one-tenth of the height.
The r e s u l t s yielded by t h e s e t e s t s lead to the conclusion that the life of B N - T i B 2 vaporizing e l e m e n t s
is a p p r e c i a b l y longer than that of e l e m e n t s c u r r e n t l y being produced at the B r o v a r y Powder Metallurgy
F a c t o r y . This is vividly i l l u s t r a t e d by the data in T a b l e 3. As can be seen, p a r t s produced f r o m B N - T i B 2
m i x t u r e s s a t i s f y the r e q u i r e m e n t s of this application and a r e t h r e e to four t i m e s m o r e efficient than TiB 2
e l e m e n t s . In o r d e r to decide whether u s e of B N - T i B 2 v a p o r i z e r s is justified on e c o n o m i c grounds, a c o m -
p a r a t i v e evaluation m u s t be m a d e of the costs involved in the technique d e s c r i b e d above and the existing
process.

LITERATURE CITED
1. US Patent No. 2888355.
2. US Patent No. 2872327.
3. F r e n c h Patent No. 1252283.
4. B r i t i s h Patent No. 943698.
5. G . A . Y a s i n s k a y a , P o r o s h k o v a y a Met., No. 7, 53 (1966).
6. G . V . Samsonov, Nonmetallic Nitrides [in Russian], Metallurgiya, Moscow (1969}.
7. G. B r a u e r , Z. Anorg. Chem., 242, 15 (1939}.

206