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GLASS-FORMING TENDENCY OF
Pb-CONTAINING MULTICOMPONENT CHLORIDE AND BROMIDE MELTS
M. Yamane, S. Inoue, A. Nakamura
To cite this version:
M. Yamane, S. Inoue, A. Nakamura. GLASS-FORMING TENDENCY OF Pb-CONTAINING MUL-
TICOMPONENT CHLORIDE AND BROMIDE MELTS. Journal de Physique Colloques, 1982, 43
(C9), pp.C9-239-C9-242. �10.1051/jphyscol:1982943�. �jpa-00222472�
GLASS-FORMING TENDENCY OF Pb-CONTAINING MULTICOMPONENT C H L O R I D E AND BROMIDE MELTS
M. Y a m a n e , S . I n o u e and A . N a k a m u r a
Tokyo I n s t i t u t e of Technology, Meguro-ku, Tokyo
Resum&.- L ' a n t i t u d e 2 l a v i t r i f i c a t i o n d e s m6langes fondus d e s c h l o r u r e s e t bromures c o n t e n a n t Pb a 6 t 6 6 t u d i 6 e . Les e x p s r i e n c e s o n t 6 t 6 & t e n d u e s 2 p a r t i r d e s com?ositions e u t e c t i q u e s b i n a i r e s c o n t e n a n t PbC12 aux syst5mes t e r n a i r e s e t q u a t e r n a i r e s c o n t e n a n t d e s compos6s q u i o n t montr6 une t e n d a n c e f a v o r a b l e S donner l e s v e r r e s d a n s l e s p r e m i e r s e s s a i s . Le m6lange fondu PbC12-AgC1- CsC1-CdC1 a montr6 l a m e i l l e u r e a p t i t u d e 2 l a v i t r i f i c a t i o n p a r - m i l e s s y s t s m e s de c h l o r u r e s 6 t u d i 6 s . Les m6langes PbBr2-AgBr- 2 CsBr-CdBr 2 o n t montr6 une m e i l l e u r e a p t i t u d e a u e l e s s p s t s m e s de c h l o r u r e s c o r r e s p o n d a n t s . On d i s c u t e l a correspondance e n t r e l a tendance 2 l a v i t r i f i c a t i o n e t l a t e m p 6 r a t u r e de f u s i o n .
A b s t r a c t .
-
The g l a s s - f o r m i n g tendency o f P b - c o n t a i n i n g m u l t i -component c h l o r i d e and bromide m e l t s h a s been i n v e s t i g a t e d . The e x p e r i m e n t was e x t e n d e d from b i n a r y e u t e c t i c compositions c o n t a i n i n g PbC12 t o t e r n a r y and q u a t e r n a r y systems c o n t a i n i n g t h e components which gave t h e good g l a s s - f o r m i n g tendency i n t h e f i r s t t e s t . The m e l t of PbC12-Agc1-cs~1-CdC12 system showed t h e h i g h e s t q l a s s - f o r m i n g tendency among c h l o r i d e systems s t u d i e d . The m e l t o f PbBr2-AgBr-CsBr-CdBr2 system had h i g h e r g l a s s - f o r m i n g tendency t h a n c h l o r i d e c o n t a i n i n g t h e same c a t i o n s . The c o r r e l a - t i o n between g l a s s - f o r m i n g tendency and m e l t i n g t e m p e r a t u r e was d i s c u s s e d .1. I n t r o d u c t i o n
C r i t e r i a a p p l i e d t o t h e g l a s s - f o r m i n g a b i l i t y o f o x i d e s [ l - 4 1 do n o t always h o l d t r u e i n t h e s l a s s f o r m a t i o n of h a l i d e s . Althouah p o u l a i n [ 5 ] - p r o p o s e d t h e c r i t e r i o n p r e d i c t i n g new i o n i c g l a s s - f o r m i n g s y s t e m s , o u r e x p e r i e n c e t h a t t h e g l a s s - f o r m i n g r e g i o n i s o f t e n found i n t h e v i c i n i t y o f e u t e c t i c composition i s s t i l l an i m p o r t a n t g u i d e t o t h e i n v e s t i g a t i o n on new s y s t e m s . I n t h e p r e s e n t s t u d y , t h e c o r r e - l a t i o n between glass-forming tendency and m e l t i n g t e m p e r a t u r e was examined f i r s t on Pb c o n t a i n i n g b i n a r y c h l o r i d e systems h a v i n g e u t e c - t i c c o m p o s i t i o n s . The i n v e s t i g a t i o n c o n c e r n i n g t h e g l a s s - f o r m i n g r e - g i o n s o f t h e t e r n a r y and q u a t e r n a r y systems was t h e n made on t h e s y s tems c o n t a i n i n g components which gave good g l a s s - f o r m i n g tendency i n t h e f i r s t e x p e r i m e n t . The e f f e c t o f t h e s u b s t i t u t i o n o f bromides f o r c h l o r i d e s on t h e g l a s s f o r m a t i o n was a l s o i n v e s t i g a t e d .
2. Experiment
5g o f b a t c h m i x t u r e o f PbCl? c o n t a i n i n q b i n a r y e u t e c t i c composi- t i o n was melted i n a Pyrex g l a s s - c r u c i b l e a f tempe;atures a b o u t 3 0 0 ~ above t h e e u t e c t i c p o i n t f o r 30m. The m e l t was t h e n quenched t o form p l a t e l e t o f a b o u t 0.lrnrn t h i c k by d r o p p i n g it on a m e t a l p l a t e u s i n g a s y r i n g e from a b o u t 80cm h i g h , f o l l o w e d by b e i n g examined whether t h e p l a t e l e t s were g l a s s o r c r y s t a l . The g l a s s - f o r m i n g tendency o f t h e t e r n a r y and q u a t e r n a r y systems was determined by measuring t h e maximum Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1982943
C9-240 JOURNAL DE PHYSIQUE
t h i c k n e s s o f t h e g l a s s y p l a t e l e t o b t a i n e d by dropping t h e m e l t s on a m e t a l p l a t e from v a r i o u s h e i g h t s . The v i s c o s i t y o f t h e multi-component m e l t s o f v a r i o u s compositions was measured by t h e method o f r o t a t i n g c y l i n d e r .
3. R e s u l t and d i s c u s s i o n
3.1. Glass-forming tendency o f PbCl -MeCln b i n a r y m e l t s
The g l a s s - f o r m i n g tendency o f 6bc12-decln b i n a r y m e l t s o f e u t e c - t i c composition a r e shown i n T a b l e 1 a l o n g w i t h e u t e c t i c t e m p e r a t u r e s
[61. The p l a t e l e t o b t a i n e d from t h e m e l t o f PbC12-BiC13 was g l a s s y , a l t h o u g h i t was h y g r o s c o p i c . Those from PbC12-AgC1 and PbC12-CdC12 systems were p a r t l y g l a s s y and p a r t l y c r y s t a l l i z e d . The p l a t e l e t from PbC12-CdC12 system was c r y s t a l l i z e d t o l a r g e r e x t e n t . A l l t h e m e l t s h a v i n g t h e i r e u t e c t i c p o i n t s above 400°C were d e v i t r i f i e d by t h e quenching p r e s c r i b e d i n t h e above.
3.2. Glass-forming tendency o f PbC12-AgC1-CdC12 s y s t e m The g l a s s - f o r m i n g tendency o f t h e m e l t o f PbC12-AgCl s y s t e m was improved by t h e i n t r o d u c t i o n of C s C l o r CdC12 a s t h e t h i r d compo- n e n t . I n t h e s y s t e m PbC12;AgC1 -CdC12, t h e c o m p o s i t i o n g l v i n g t h e g l a s s y p a r t i n t h e p l a t e l e t was found i n t h e v i c i n i t y o f t h e b i n a r y e u t e c t i c c u r v e s o f t h e phase d i a - gram o f t h i s s y s t e m [ 7 ] a s i t i s shown i n Fig.1. The p l a t e l e t ob- t a i n e d from t h e m e l t o f a composi- t i o n n e a r t h e t e r n a r y e u t e c t i c p o i n t had g l a s s y p a r t t o t h e l a r g e - s t e x t e n t .
T a b l e 1 Glass-forming tendency o f PbC12-MeC1, b i n a r y m e i t s o f e u t e c t i c composition System T e ( O C )
*
Appearance-
PbC12-LiC1 4 1 0 c r y s t a l
PbC12-NaC1 410
,
PbC12-MgC12 460
PbC1,-CaC1, 460
~ b ~ l ; - ~ i ~ l ; 210 G l a s s PbC12-MnC12 410 C r y s t a l
* ) E u t e c t i c p o i n t , (Ref. [ 6 ] )
3.3. Glass-forming tendency o f PbX2 CdC 1 2
-AgX-CsX ( X = C 1 , B r ) systems The g l a s s - f o r m i n g r e g i o n s o f PbX2-AgX-CsX ( X = C l , B r ) systems a r e shown i n F i g . 2 . The composition g i v i n g t h e h i g h e s t g l a s s - f o r m i n g tendency i n c h l o r i d e system was 48PbC12 38AgC1 1 4 C s C 1 mol%. The c o r r e l a t i o n between g l a s s - f o r m i n g tendency and l i q u i d u s t e m p e r a t u r e , however, i s n o t known b e c a u s e o f t h e absence o f p h a s e diagram. Suc- c e s s i v e s u b s t i t u t i o n of bromine f o r c h l o r i n e i n t h e composition 48PbC12
38AgC1 1 4 C s C 1 mol% improved t h e
g l a s s - f o r m i n g tendency. The c a t i o n ~ g c l PbC12 r a t i o i n t h e c o m p o s i t i o n g i v i n g t h e (
No1
% )h i g h e s t g l a s s - f o r m i n g tendency i n
t h e PbBr2-AgBr-CsBr system was F i g . 1 . C o r r e l a t i o n between g l a s s - widely d i f f e r e n t from t h a t i n c h l o - forming tendency and l i q u i d u s r i d e system. The maximum t h i c k n e s s t e m p e r a t u r e o f PbC12-AgC1-CdC12 9 f t h e g l a s s y p l a t e l e t o b t a i n e d system ( ESSJ : P a r t l y g l a s s and from t h e m e l t o f composition 70PbBr2 p a r t l y c r y s t a l )
21AgBr 9CsBr mol% was 0.9mm.
3.4. Glass-forming tendency o f PbBr2-AgBr-CsBr-CdBr2 system
The g l a s s - f o r m i n g tendency was remarkably improved by e x t e n d i n g t h e t e r n a r y system PbX2-AgX-CsX ( X = C l , B r ) t o t h e q u a t e r n a r y system PbX -AgX-CsX-CdX2 i n both c h l o r i d e and bromide. The g l a s s - f o r m i n g ten&ncy o f PbBr2-AgBr-CsBr-CdBq system t e s t e d under t h e ambient a t -
shown i n F i y . 3 . The dependence o f g l a s s - f o r m i n g tendency on m e l t i n g t i m e i n d i c a t e s t h a t a t r a c e of oxygen was e f f e c t i v e i n g l a s s - f o r m a t i o n
.
T h i s i s known by T a b l e 2 which i n c l u d e s t h e r e s u l t s f o r b o t h bub- b l i n g w i t h d r y C 1 2 gas and t h e s u b s t i t u t i o n of PbO f o r PbBr i n t h e system (62-X)PbBr2 XPbO 1 6 A ~ B r 12CsBr 10CdBr2 mol%.The v i s c o s i t y - t e m p e r a t u r e r e l a t i o n s h i p o f t h e s e oxygen c o n t a i n i n g bromide m e l t s i s shown i n F i g . 4 a l o n g w i t h t h a t o f o t h e r h a l i d e m e l t s
r e p o r t e d i n t h e l i t e r a t u r e [ 8 ] .
Thl ckness Open c i r c l e s show t h e t e m p e r a t u r e s
.
:-
0 . m CsX a t which p r e c i p i t a t i o n of f i n e c r y s t a l occured when t h e m e l t s were : -. 0 . 5 ~ 1 c o o l e d v e r y s l o w l y . Closed c i r c l e sshow t h e t e m p e r a t u r e s a t which
:
-
0.7mn c r y s t a l growth became remarkable.(Ag:Pb=23:771
mi-
* :
-
1,o hm*.-
1-5mn
*:- 2-0
mn
'2
F i g . 2 . Change i n g l a s s - f o r m i n y F i g . 3 . Glass-forming tendency of tendency o f t h e system PbX2-A5X- PbBr2-AgBr-CsBr-CdBr2 s y s t e m C s X w i t h s u b s t i t u t i o n o f B r f o r
c1
melted a t 420°C f o r 30mTable 2 Glass-forming tendency o f t h e m e l t s o f (62-X)PbBr2 16AgBr -XPbO 12CsBr lOCdBr,
-
(X=0,2,5,10 mol%)G l a s s Composition M e l t i n g Maximum G l a s s r o d o f c o n d i t i o n t h i c k n e s s 8mm X l l m m L
A X = O 420°C 30m,Bubbling C 1 2 0.9mm no
B X = O 42OoC 30rn,AmbientAtinos. 2.5mm no
C X = O 420°C 15h, I, 3.0mm no
D X = 2 420°C 30m, It >3.5mm y e s *
E X = 5 I yes**
F X =10 I, ,I y e s *
* ) P a r t l y c r y s t a l l i z e d , * * ) C l e a r g l a s s
C9-242 JOURNAL DE PHYSIQUE
Broken l i n e s r e p r e s e n t e s t i m a t e d
v i s c o s i t i e s .
L
-
fThe v i s c o s i t y - t e m p e r a t u r e c u r v e o f m e l t B i n T a b l e 2 was found i n t h e v i c i n i t y o f t h e ex- t r a p o l a t i o n o f t h a t o f s i n g l e com- ponent PbBr2 toward low tempera- t u r e . The a c t i v a t i o n e n e r g i e s f o r v i s c o u s flow, E o f m e l t B and PbBrZ i n t h e
vicinity
o f t h e i r m e l t l n g t e m p e r a t u r e s were e s t i - mated t o be 12 and 6 Kcal/mol by a p p l y i n g t h e e m p i r i c a l e q u a t i o n(1) t o t h e c u r v e s .
n
= A rl exp ( E n / R T ) 2% 3Ml 350 400The v a l u e s o f E o f oxygen con- Temperature ('C)
t a i n i n g m e l t C , ~ D and E were de-
pendent on t h e d e g r e e o f a s s o c i a -
'
t i o n and e s t i m a t e d t o b e 1 7 , 24 and 20 Kcal/mol, r e s p e c t i v e l y . The i n t r o d u c t i o n o f PbO u p t o a b o u t 5%
i s e f f e c t i v e i n i n c r e a s i n g b o t h v i s c o s i t y and a c t i v a t i o n energy f o r flow i n t h e v i c i n i t y o f l i q - u i d u s t e m p e r a t u r e . When t h e i n t r o -
d u c t i o n o f PbO exceeds 5 % , however, 3M1 t no0 t 500 600 700 I ( ( 8W ( 900 I IOM) I
t h e l i q u i d u s t e m p e r a t u r e of t h e
m e l t becomes t o o h i g h and b o t h Temperature ('C )
v i s c o s i t y and a c t i v a t i o n energy F i g . 4 . V i s c o s i t y t e m p e r a t u r e d e c r e a s e a g a i n . T h i s would b e t h e c u r v e s o f v a r i o u s h a l i d e m e l t s r e a s o n f o r . lower g l a s s - f o r m i n g ( F i v e c u r v e s whose d e t a i l s a r e tendency o f t h e m e l t F t h a n E . I t shown i n t h e i n s e r t a r e t h e was i m p o s s i b l e t o t a k e v i s c o s i t y r e s u l t s o f p r e s e n t s t u d y , o t h e r s d a t a o f m e l t A. I f i t i s assumed a r e from Ref. [8]
.
t h a t t h e r e i s no a s s o c i a t i o n o f
atoms i n oxygen f r e e bromide m e l t A and t h e r e f o r e En of t h e m e l t i s s i m i l a r t o t h a t o f s i n g l e component PbBrZ, t h e v i s c o s i t y o f t h e m e l t A i s e s t i m a t e d t o b e 12-15 c p i n t h e v i c i n l t y o f i t s l i q u i d u s tempera- t u r e ( a b o u t 270°C). T h i s v a l u e i s l a r g e r by 50
-
80% t h a n t h e v i s c o s - i t y o f PbBr2 e x t r a p o l a t e d t o i t s m e l t i n g t e m p e r a t u r e . The h i g h e r g l a s s -forming tendency o f multi-component m e l t o f PbBr2-AgBr-CsBr-CdBr2 sysgem t h a n s i n g l e component PbBr2 would be a t t r i b u t e d t o t h i s d i f f e r - ence i n v i s c o s i t y i n t h e v i c i n i t y o f m e l t i n g t e m p e r a t u r e s . Thus, t h e r e d u c t i o n of l i q u i d u s t e m p e r a t u r e by t h e i n t r o d u c t i o n o f t h e second and t h e t h i r d components would be t h e most p r o m i s i n g way t o improve t h e g l a s s - f o r m i n g tendency o f n o n - a s s o c i a t e d h a l i d e m e l t s .Authors a r e g r a t e f u l t o t h e s u p p o r t of t h e Asahi G l a s s Foundation f o r t h e C o n t r i b u t i o n t o I n d u s t r i a l Technology.
R e f e r e n c e s
[ l ] ZACHARIASEN,W.H., J.Am.Chem.Soc., 54 (1932) 3841 [ 2 ] SUN,K.H., J.Am.Ceram.Soc.,
30
( 1 9 4 n 277[ 3 ] STANWARTH,J.E., J.Am.Ceram.Soc., 54 (1971) 61
[ 4 ] RAWSON,H., I n o r g a n i c G l a s s - F o r m i n ~ S y s t e m s , Academic P r e s s , London (1967)
[ 5 ] POULAIN,M., N a t u r e
293
(1981) 279[ 6 ] LEVIN,E.M., ROBBINS,C.R., MCMURDIE,H.F., Phase Diagrams f o r C e r a m i s t s , American Ceramic S o c i e t y (1964)
[ 7 ] idem, (1969)
[ 8 ] J A N G I G . J .
