LOW TEMPERATURE THERMAL PROPERTIES OF CYCLOHEXANOL : A GLASSY CRYSTAL SYSTEM

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LOW TEMPERATURE THERMAL PROPERTIES OF

CYCLOHEXANOL : A GLASSY CRYSTAL SYSTEM

E. Bonjour, R. Calemczuk, R. Lagnier, B. Salce

To cite this version:

JOURNAL DE PHYSIQUE

CoZZoque C6, suppZSment au nO1 2, Tome 42, de'cembre 1981 page 126-63

LOW TEMPERATURE THERMAL PROPERTIES OF CYCLOHEXANOL

:

A GLASSY CRYSTAL SYSTEM

E. Bonjour, R. Calemczuk, R. L a g n i e r and B. S a l c e

Service des Basses TempSrature s, kxboratoire de Cryophy sique, Centre d 'Etudes Nucl6aires de GrenobZe, 85 X, 38041 GrenobZe Cedex, Frame

4 b s t r a c t .

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S p e c i f i c h e a t and thermal c o n d u c t i v i t y measurements on llglassy" c r y s t a l 1 in e and c r y s t a l 1 in e c y c l o h e x a n o l a r e r e p o r t e d . The g l a s s y c r y s t a l phase shows t h e same anomalous b e h a v i o u r found i n glasses a t h e l i u m tempera- t u r e s .

R e c e n t l y s e v e r a l experiments have shown t h a t c r y s t a l s c o n t a i n i n g s t r u c t u r a l d i - s o r d e r can a t l o w temperatures d i s p l a y t h e same k i n d o f anomalous b e h a v i o u r found i n amorphous s o l i d s . The s t u d y o f t h i s c l a s s o f systems i s a p r o m i s i n g way t o c l e a r up t h e m i c r o s c o p i c o r i g i n o f t h e e x c i t a t i o n s r e s p o n s i b l e f o r t h e s e anomalies. Glass 1 i ke b e h a v i o u r has been w e l l e s t a b l i s h e d f o r some s u p e r i o n i c c o n d u c t o r s as L i 3 N (1) 6nd 6-a1 umine ( 2 ) , i r r a d i a t e d q u a r t z ( 3 ) and o t h e r s d i s o r d e r e d c r y s t a l s ( 4 ) .

I n t h i s paper we p r e s e n t t h e r e s u l t s o f s p e c i f i c h e a t C and thermal c o n d u c t i - v i t y K measured between 1.5 and 20 K on a new t y p e o f d i s o r d e r e d c r y s t a l ; n a m e l y t h e " g l a s s y " c r y s t a l l i n e phase ( c r y s t a l I [ 5 1) o f cyclohexanol

.

We a l s o p r e s e n t t h e r e - s u l t s c o r r e s p o n d i n g t o t h e c r y s t a l I 1 1 phase o b t a i n e d by t h e r e c r y s t a l l i z a t i o n o f the p r e v i o u s l y measured " g l a s s y " c r y s t a l 1 in e samples.

A " g l a s s y " c r y s t a l can be o b t a i n e d by c o o l i n g t h r o u g h a m e t a s t a b i l i t y r e g i o n a n o r i e n t a t i o n a l l y d i s o r d e r e d phase such as t h e s o - c a l l e d p l a s t i c phases ( 6 ) . A t l o w temperatures t h e o r i e n t a t i o n d i s o r d e r becomes s t a t i c i n t h e e x p e r i m e n t a l t i m e s c a l e and on warming we observe a g l a s s t r a n s i t i o n phenomenon.

P l a s t i c c r y s t a l l i n e cyclohexanol i s s t a b l e between 299 K ( m e l t i n g p o i n t ) and 265 K b u t i t i s e a s y l y s u p e r c o o l e d and g l a s s t r a n s i t i o n t a k e s p l a c e around 150 K. Polymorphism o f c y c l o h e x a n o l has been f u l l y d e s c r i b e d by Adachi e t a1 [ 5

1.

P r i o r t o t h e l o w temperature measurements we have performed a d i f f e r e n t i a l scanning c a l o . r i m e t r y s t u d y on o u r p r o d u c t (Merck, Typanalyse) i n o r d e r t o determine t h e r i g h t c o n d i t i o n s t o o b t a i n t h e phases i n v e s t i g a t e d . Our r e s u l t s c o n f i r m those o f Adachi. So t h e c r y s t a l I 1 1 phase was prepared by h e a t i n g t h e c r y s t a l I up t o 240 K and t h e n co- o l i n g t o l o w t e m p e r a t u r e s .

The thermal c o n d u c t i v i t y K(T) was measured u s i n g s t a n d a r t s t e a d y s t a t e t e c h - n i q u e s from 1 . 5 t o 20

K.

The m a j o r problem a r o s e from t h e l o w m e l t i n g p o i n t (299 K) o f cyclohexanol which p r e v e n t e d us u s i n g a c l a s s i c a l arrangement. The most e f f i c i e n t way was t o p u t t h e sample i n s i d e a PVC c y l i n d e r shaped c e l l ( v e r y t h i n w a l l s ) and,

C6-64 JOURNAL DE PHYSIQUE

t o p e r f o r m measurements on t h e sample and t h e c e l l t o g e t h e r . Next s t e p was t o mea- s u r e K(T) o f t h e c e l l . T a k i n g i n t o a c c o u n t t h e r e s p e c t i v e c r o s s s e c t i o n a l areas o f t h e c e r l and t h e sample, i t was p o s s i b l e t o deduce t h e e x a c t thermal c o n d u c t i v i t y o f c y c l o h e x a n o l .

The s p e c i f i c h e a t measurements were performed, between 1.5 and 20 K u s i n g an a d i a b a t i c d i f f e r e n t i a l method, o p e r a t e d a t c o n s t a n t h e a t i n g r a t e , as d e s c r i b e d i n p r e v i o u s papers ( 6 ) .

The s p e c i f i c h e a t r e s u l t s a r e d i s p l a y i n F i g . 1 as a C/T3 v e r s u s T p l o t and t h o s e o f thermal c o n d u c t i v i t y K a r e r e p r e s e n t e d i n Fig.2.

Fig.l.

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S p e c i f i c h e a t o f cyclohexanol

Fig.2.

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Thermal c o n d u c t i v i t y o f q c l o h e x a n o l @ " g l a s s y " c r y s t a : I 0 " g l a s s y " c r y s t a l I

0 c r y s t a l I 1 1 0 c r y s t a l I 1 1

F o r camparison t h e s o l i d and dashed 1 in e s show t h e r e s u l t s o f s i l i c a and s e l e n i u m g l a s s (1 it e r a t u r e )

.

c y c l o h e x a n o l i s a good c r y s t a l , i n t h e sense t h a t t h e m o l e c u l a r mass c e n t e r s f o r m a p e r i o d i c l a t t i c e , t h e e x i s t e n c e o f l a r g e s c a l e d e n s i t y f l u c t u a t i o n s (71, v o i d s ( 8 ) o r some k i n d o f f r e e volume ( 9 ) w h i c h a r e sometimes proposed s n o u l d be excluded.

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( 4 ) U.A. ACKERMAN, D. MOY, R . C . POTTER, A.C. ANDERSON and W.N. LAWLESS, Phys. Rev. B

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( 5 ) K. ADACHI, M. SUGE and S . SEKY, B u l l . Chem. Soc. Japan

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