Journal of Low Temperature Physics, Vol. 89, Nos.

3/4, 1992

THERMAL EXPANSION OF HELIUM FILLED AEROGEL

AT THE LAMBDA POINT

P. Thibault, J.J. Prejean, L. Puech.

CRTBT-CNRS, BPI66 , 38042 Grenoble cedex

Under reasonable assumptions, we s h o w t h a t He-

filled Aerogels should exhibit a strong negative
t h e r m a l e x p a n s i o n at the ~ point : ~ = - 10-3/K. We
o b s e r v e d an e x p a n s i o n s m a l l e r t h a n 10-6/K a c r o s s
the t r a n s i t i o n . This v e r y s t r o n g d i s c r e p a n c y can
be related either to (i) specific elastic
p r o p e r t i e s of the gels, (ii) the d e p e n d a n c e of T~
on the p o r e size is d r a s t i c a l l y d i f f e r e n t of what
c o u l d be expected.

1 INTRODUCTION

L i q u i d H e l i u m in silica a e r o g e l s is k n o w n to
behave very differently than in o t h e r p o r o u s
media. 1,2,3; this difference is currently
a t t r i b u t e d to the s p e c i f i c f r a c t a l g e o m e t r y of
t h e s e gels4, 5 A l t h o u g h the onset t e m p e r a t u r e of
the s u p e r f l u i d i t y is only s l i g h t l y d e p r e s s e d , the
exponent of the superfluid transition is
significantly changed, and a violation of t h e
Josephson scaling relation is apparently
observed 2 .
Unlike conventional porous media, the
aerogels have exceptionally small bulk modulii
(E=I0 bars, c o m p a r e d to 7x.105 bars for b u l k SiO2),
so t h a t we can e x p e c t a s i g n i f i c a n t feed-back
e f f e c t of the H e l i u m o n t o the gel w h e n c r o s s i n g
the lambda transition. A measurement of t h e
t h e r m a l e x p a n s i o n of the gel c o u l d t h e n p r o v i d e
i n f o r m a t i o n on t h e r m o d y n a m i c properties of the
H e l i u m inside the gel.
677

0022-2291/92/1100-0677506.50/0© 1992 Plenum Publishing Corporation

678 P. Thlbault, J. J. Prejean, and L. Puech

2 THERMODYNAMICS OF THE EXPANSION

In a t y p i c a l e x p e r i m e n t , h e l i u m is free to
e n t e r in the p o r o u s matrix, the v o l u m e of w h i c h is
free to adjust. The h e l i u m will a d j u s t its d e n s i t y
to r e a c h the same c h e m i c a l p o t e n t i a l as o u t s i d e
(~4) • The v o l u m e of the p o r o u s s a m p l e w i l l t h e n
a d j u s t to m i n i m i z e the t h e r m o d y n a m i c a l p o t e n t i a l
V0E
adapted to that situation : ~ =
2
8v
(~0)2 + (F4(N,T,V) - N ~4) + Pext V, where Pext is
the p r e s s u r e e x e r c e d on the sample, N the n u m b e r
of He a t o m s in the sample, V its v o l u m e , V 0 the
v o l u m e w h e n t h e r e is no h e l i u m and Pext=0, and
6 V = V - V 0. The first t e r m is the e l a s t i c e n e r g y of
the gel, a n d the s e c o n d the g r a n d - p o t e n t i a l for
the He. U s i n g the a b o v e e x p r e s s i o n for [/ we f i n d
8v ~F 4
E(~) + ( ~ - ) T , N +Pext = 0. We w r i t e F4=Vf4(T,p,~),
8v
where Q=N/V is the density of the helium, ~-
V
c h a r a c t e r i z e s the d e f o r m a t i o n of the gel and f4 is
the free e n e r g y of H e l i u m p e r unit v o l u m e a n d
~F4 ~f4 ~f4,
c a l c u l a t e ~vT, N = ( f 4 - P ( ~ ) T , E ) + (--~£,T,p-

The second term expresses the way f4 is changed

w h e n the d e n s i t y of the gel v a r i e s at f i x e d p,
w h i l e the first is -P, the p r e s s u r e of the h e l i u m
in the p o r e s . In the e x p e r i m e n t P=Pext, a n d we
finally o b t a i n :

8v i 8f4) 8v _ +~ ~s4)
(-v-) = - E ~ £ T,p and 0tT - V~T ~£ T,p (i)

s4 b e i n g the entropy of He per unit volume. As an

~s4,
order of m a g n i t u d e for --~--)T,p, we a s s u m e that :

(i) the m a i n effect of changes in S is to c h a n g e

the linear size of all the pores by 1/3 £, (ii)
 Thermal Expansion of Helium Filled Aerogel 679

the dependance of s4 on comes from the shift in

T%(£) . s4(T,£)=s4(T-TI(S)) ; and (iii) that Tl(g)is
the t e m p e r a t u r e at w h i c h ~(T) r e a c h e s some l e n g t h
characteristic of the p o r o u s m e d i u m . N e i t h e r of
these hypotheses are o b v i o u s , but an a p p r o a c h
s i m i l a r to (ii) y i e l d s a g o o d o r d e r of m a g n i t u d e
e s t i m a t e for the t h e r m a l e x p a n s i o n of b u l k H e l i u m
at Tl a n d (iii) yields the right order of m a g n i t u d e
of the s h i f t s in Tl in p o r o u s media. U n d e r t h e s e
Cp ~T~
c i r c u m s t a n c e s one can e s t i m a t e ~T = - E "Tl~g w h e r e

~T~ ATx
E = 10 6 Pa, cp=10 6 j/m3/K , - - + 1 0 -3
T~E 3VT~
as evaluated from the shift ATI= 5mK and the
exponent V of b u l k helium Thus, we expect ~T -~ -
10 -3 K -I close to the ~ point.

3 EXPERIMENTAL VALUE FOR ~T

We m e a s u r e d the c h a n g e s in t h e l e n g t h 1 = 8 . 7
m m of a n e u t r a l l y r e a c t e d a e r o g e l s a m p l e 6, at a
0
d e n s i t y 0 . 1 6 g / c m 3. The r e s o l u t i o n is a b o u t IA.
The m e a s u r e m e n t s were p e r f o r m e d w i t h l i q u i d h e l i u m
c l o s e to the v a p o r p r e s s u r e , for 1 . 5 K < T < 2 . 5 K . We
observed that the expansion below T~, is
essentially controlled by the fountain pressure
that develops in t h e gel w h e n t h e t e m p e r a t u r e
v a r i e s in time. We can a n y w a y e s t i m a t e t h a t for
dT/dt = 0 we w o u l d h a v e I~TIS2.10-6/K. A more
accurate determination of ~ T is p o s s i b l e b u t it
w i l l be d i f f i c u l t to i n t e r p r e t , s i n c e for s u c h
small values, slight c h a n g e s of the p r o p e r t i e s of
the first l a y e r s a d s o r b e d on t h e gel c o n t r i b u t e
l a r g e l y to ~T 7
The m e a s u r e m e n t of ~ T d o e s not a l l o w t h e
d e t e r m i n a t i o n of a c r i t i c a l e x p o n e n t , b e c a u s e the
effect of the k transition on the gel is
a p p a r e n t l y minor. This fact is in c o n t r a d i c t i o n
680 P. Thibault, J. J. Pr~ean, and L. Puech

with the a n a l y s i s we have proposed. One (or more)

of the h y p o t h e s i s (i-iii) is t h u s not c o r r e c t .
Concerning (i), it is to be e x p e c t e d t h a t the
s m a l l e s t pores will contract less than the largest
ones. If the d i s c r e p a n c y o b s e r v e d comes f r o m that
fact, it i m p l i e s a r a t i o of 1 to = 5 0 0 in t h e
d e f o r m a t i o n at d i f f e r e n t l e n g t h scales. (ii) is
c e r t a i n l y not s t r i c t l y correct, but we c o n s i d e r it
like a d i m e n s i o n a l - a n a l y s i s a r g u m e n t t h a t s h o u l d
p r o v i d e the c o r r e c t o r d e r of m a g n i t u d e . Finally,
c o n c e r n i n g (iii), if the n a t u r e of the t r a n s i t i o n
in the gel is d i f f e r e n t than in the bulk, b e c a u s e
of the f l u c t u a t i o n s of the order p a r a m e t e r involve
(for instance) v o r t i c e s a r o u n d p i e c e s of SiO27,
theses f l u c t u a t i o n s might well be far less c o u p l e d
to l i n e a r sizes of the p o r e s t h a n a r g u m e n t (iii)
claims.
In a n y case, the m e a s u r e m e n t of ~ T r i s e s a n e w
q u e s t i o n on the nature of the i t r a n s i t i o n in the
aerogels.

REFERENCES

i. M . H . W Chan,K.I. Blum, S.Q. Murphy, G.K.S. W o n g

and J.D Reppy, PRL 61, 1950 , (1988)
!. W o n g , Crowell, Cho and Reppy, PRL 65, 2410,
(1990)
3. M u l d e r s N., M e h r o t r a R., G o l d n e r L. a n d G.
Ahlers, PRL 67, 695, (1991)
4. V a c h e r R., W o i g n i e r T., P e l o u s J. , Courtens
E., PRB, 37, ii, 6500, (1988)
5. We are v e r y g r a t e f u l l to P e l o u s J., W o i g n i e r
T . , V a c h e r R. for p r o v i d i n g us samples of n e u t r a l l y
r e a c t e d gels.
6. P. Thibault et al, in progress.
7. G. W i l l i a m s PRL 59, 17, 1926, (1987)