JOURNAL DE PHYSIQUE

CoZZoque CS, suppZ6ment au nO10, Tome 42, octobre 1981 page C5-541

VERY LOW FREQUENCIES INTERNAL FRICTION MEASUREMENTS OF ICE I h

J. Tatibouet, J. Perez and R. Vassoille

Groupe d 'Etudes de W t a Z Z u r g i e Physique e t Physique des MaMriaux, I . N. S. A.,

B&. 502, E.R.A. 463, 69621 ViZZeurbanne Cedex, France

Abstract Very low f r e q u e n c i e s i n t e r n a l f r i c t i o n measurement

(1 - 10' 4 - ~ z ) i n i c e p e r m i t t e d t o i n c r e a s e t h e knowledge of t h e
i n t e r n a l f r i c t i o n of i c e , e s p e c i a l l y t h e r e l a x a t i o n phenomenon.
The a c t i v a t i o n e n e r g y of t h e r e l a x a t i o n i s 0.25 eV, a c a r a c t e r i s -
t i c v a l u e of t h e m i g r a t i o n of r o t a t i o n a , l d e f e c t s . I t f o l l o w s a
C u r i e Law.
Experiments a f t e r d i f f e r e n t cooling r a t e put i n evidence t h e r o l e
of intrinsic defects.

1 . Introduction - Until t o day i n t e r n a l f r i c t i o n of I c e Ih h a s been

s t u d i e d i n t h e k i l o h e r t z [ l , 2 , 3 3 and H e r t z 141 frequencies ranges.
bleasurenient have a l s o been made by u l t r a s o n i c waves t e c h n i c s f5].
E x p e r i m e n t s made on s i m p l e c r y s t a l s a t 1 H e r t z between 100 and
273 K show 3 noteworthy f e a t u r e s .
i ) a r e l a x a t i o n peak o b s e r v e d by o t h e r s a u t h o r s a t h i g h e r f r e q u e n -
c i e s [I, 2, 33.
i i ) an i n c r e a s e of t h e i n t e r n a l f r i c t i o n a t h i g h t e m p e r a t u r e (230-
273 K ) .
i i i ) A t high temperature, i n t e r n a l f r i c t i o n becomes a m p l i t u d e de-
pendant. The h i g h e r t h e t e m p e r a t u r e , t h e more p r o n o u n c e d . t h i s a m p l i t u d e
dependence.
.High t e m p e r a t u r e phenomena a r e a t t r i b u t e d t o t h e movement o f d i s l o c a -
t i o n s u n d e r t h e c y c l i c s t r e s s and s e v e r a l i n t e r ~ r e t a t i o n shave been y e t
developped 1 6 , 71.
The o r i g i n of t h e i n t e r n a l f r i c t i o n peak i s n o t f u l l y e x p l a i n e d .
Bass[8] h a s i n t e r p r e t e d t h e m e c h a n i c a l r e l a x a t i o n by a r e a r r a n g e m e n t o f
w a t e r m o l e c u l e s w i t h t h e h e l p of t h e r o ~ a t i o n n a l ( o r Bjerrum) d e f e c t s ,
i n r e s p e c t of t h e B e r n a l and Fowler r u l e s . From an a n a l o g o u s way,
Gosar 19) h a s c o n s i d e r e d t h a t e a c h w a t e r molecule i s a p o i n t d e f e c t i n
t h e i c e l a t t i c e , and h a s ; : e n e r a l i z e d t h e model of Bass by i n t r o d u c i n g
t h e c o n c e p t of e l a s t i c d i p o l e s p r e v i o u s l y d e v e l o p p e d . He c a l c u l a t e d t h e
f r e e e n e r g y of t h e c r y s t a l by i n t r o d u c i n g t h e p r o t o n d e s o r d e r e n t r o p y
w i t h t h e h e l p of g r a p h t h e o r y a s Nagle 110) d i d i t f o r t h e d i e l e c t r i c
relaxation.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1981582

C5-542 JOURNAL DE PHYSIQUE

So we have t r i e d t o e x t e n d t h e e x p e r i m e n t a l s t u d y of t h e i n t e r n a l
f r i c t i o n peak i n I c e by u s i n g measurements t e c h n i c s a t v e r y low f r e -
quencies ( 1 - t ~ KZ).
- ~ The p r i n c i p a l aim of t h i s work was t o compare
t h e i n f l u e n c e of i n t r i n s i c o r e x t r i n s i c r o t a t i o n n a l d e f e c t s on t h e r e -
l a x a t i o n t i m e a s s o c i a t e d t o t h e i n t e r n a l f r i c t i o n peak.
2. E x p e r i m e n t a l r e s u l t s .
.
2.1 E x p e r i m e n t a l p r o c e d u r e -
I n t e r n a l f r i c t i o n measurements a t
v e r y low f r e q u e n c i e s were made w i t h an i n v e r t e d t o r s i o n a l pendulum w i t h
a v e r y weak i n e r t i a l moment. T h i s pendulum working i n f o r c e d o s c i l l a -
t i o n s i s presented a t t h e p r e s e n t conference [ l l ] . The t o r q u e i s t r a n s -
m i t t e d t o t h e specimen by a magnet between two Helmholtz c o i l s . The
s t r a i n i s d e t e c t e d by mean of p h o t o v o l t a i c c e l l s .
S t r a i n and s t r e s s s i g n a l s a r e b o t h s e n t t o a c a l c u l a t o r which com-
p u t e s i n t e r n a l f r i c t i o n and a v a l u e p r o p o r t l o n n a l t o t h e modulus.
3
The specimen ( p a r a l l e l e p i p e d a l 8 2 X 60 mm ) a r e m e c h a n i c a l l y
X

c u t t e d from s i n g l e c r y s t a l s grown by Bridgman inethod i n t h e G l a c i o l o g y

L a b o r a t o r y i n Grenoble. The r e s i s t i v i t y of t h e employed w a t e r i s more
thanlo~~~/cm.
2 . 2 . R e s u l t s . - F i g u r e l showsthe g e n e r a l shape of an i n t e r n a l
f r i c t i o n spectrum a t t h e i n t e r m e d i a t e f r e q u e n c y of 1 0 - ~Ha. We f i n d na-
t u r a l l y t h e same f e a t u r e s t h a t when e x p e r i m e n t s a r e made a t l Hz. The
r e l a x a t i o n peak i s s h i f t e d t o w a r d s t h e lower t e m p e r a t u r e s by f r e q u e n c y
e f f e c t a s t h e i n t e r n a l f r i c t i o n a s s o c i a t e d t o t h e d i s l o c a t i o n s movement
which inc:reases a t t e m p e r a t u r e a s low a s 200 K (230 - 240 X a t 1 Hz).

4"'

F i g . 1 : I n t e r n a l f2iction/tempe- Fig. 2 : High Temperature I n t e r -

r a t u r e 10- Hz. nal F r i c t i n
&",... = 5 10- S .
T h i s h i g h t e m p e r a t u r e i n t e r n a l f r i c t i o n i s a l s o a m p l i t u d e depen-
d e n t a s shown t h e same f i g u r e .
We have a l s o r e p r e s e n t e d on f i g u r e 2 t h i s i n c r e a s e of i n L e r n a l f r i c t i o n
f o r three d i f f e r e n t frequencies. The e x p e r i m e n t s were made a t c o n s t a n t
d i s l o c a t i o n d e n s i t y . Indeed we have v e r i f i e d t h a t a f t e r e v e r y measure-
ment a t 1oe2 and I O - ~ Hz we found a g a i n e x a c t l y t h e i n i t i a l v a l u e ob-
t a i n e d a t 1 Hz. I n a f i r s t a p p r o a c h , t h e h i g h t e m p e r a t u r e i n t e r n a l
f r i c t i o n i s t h e more i m p o r t a n t t h e f r e q u e n c y i s low i n agreement w i t h
t h e i n t e r p r e t a t i o n given i n reference [ 6 ) .
The aim of t h i s work b e i n g t h e s t u d y of t h e r e l a x a t i o n peak, we
have n o t developped t h i s p o i n t and we s h a l l f o c u s e d on t h e low tempera-
t u r e i n t e r n a l f r i c t i o n ; we have r e p r e s e n t e d on f i g u r e 3 t h i s peak
v e r s u s t e m p e r a t u r e a t d i f f e r e n t f r e q u e n c i e s . We n o t i c e t h e s h i f t oP t h e
t e m p e r a t u r e peak t o w a r d s t h e low t e m p e r a t u r e and t h e i n c r e a s e of t h e
r e l a x a t i o n i n t e n s i t y with decreasing frequency. I n order t o put i n evi-
dence t h e r o l e of i n t r i n s i c d e f e c t s o u t of e q u i l i b r i u m i n t h e r e l a x a -
t i o n phenomena, we have made measurements of i n t e r n a l f r i c t i o n d u r i n g
a t e m p e r a t u r e r i s e a f t e r two d i f f e r e n t c o o l i n g r a t e s from an e q u i l i -
;jrlurn s ~ a t e(we have choosen t h a t o b t a i n e d a f t e r 1 h 30 a t 230 K ) .
i ) low c o o l i n g r a t e = 0.3 K/min.
i i ) f a s t c o o l i n g r a t e = 2.7 m min.
'eYt

F i g . 3 : R e l a x a t i o n Peak v s tempe- P i p . 4 : R e l a x a t i o n Peak a f t e r

rature a t different fre- d i f f e r e n t c o o l i n g ra$e.
----
q u e n c i e S.
- : 2,7 K/min
: 0,3 ~ / m i n
Thus t h e f i g u r e 4 e x h i b i t s t h e r e l a x a t i o n peaks measured i n t h e s e
two c o n d i t i o n s a t d i f f e r e n t f r e q u e n c i e s . We can o b s e r v e i n a l l c a s e s a
s h i f t of t h e t e m p e r a t u r e peak t o w a r d s t h e low t e m p e r a t u r e s when c o o l i n g
i s f a s t . We can a l s o n o t i c e t h e i n f l u e n c e o f t h e measurement t i m e ( i . e .
measurement f r e q u e n c y ) . I n I O - ~ , I O - ~ and 1 0 ' ~ Hz e x p e r i m e n t s o n l y t h e
low t e m p e r a t u r e p a r t of t h e peak i s s h i f t e d .
C5-544 JOURNAL DE PHYSIQUE

3 . Discussion - From o u r e x p e r i m e n t a l r e s u l t s we h a v e d o n e a n a t t e m p t
t o g i v e a more c o m p l e t e c a r a c t e r i z a b i o n o f t h e r e l a x a t i o n p e a k , h a v i n g
d o n e e x p e r i m e n t s on a l a r g e r f r e q u e n c y r a n g e . A s r e c a l l e d p r e c e d i n g l y
t h e m e c h a n i c a l r e l a x a t i o n i n I c e d u e t o t h e r e o r i e n t a t i o n o f w a t e r mo-
l e c u l e due t o t h e a p p l i c a t i o n of a c y c l i c s t r e s s , w i t h t h e h e l p of ro-
t a t i o n a l ( o r I3jerrum) d e f e c t s . As t h e o r i g i n o f t h e s e d e f e c t s c a n b e
e i t h e r i n t r i n s i c o r e x t r i n s i c t h e r e l a x a t i o n t i m e c a n be g i v e n by [ 4 ] :

where Em and EF a r e r e s p e c t i v e l y t h e m i g r a t i o n and forrnatj.on e n e r g i e s

o f B j e r r u m d e f e c t s (13 = 0 . 2 1 eV ; EF = 0 . 3 4 eV) p21 and C i s t h e con-
m o
c e n t r a t i o n of t h e e x t r i n s i c d e f e c t s a b l e t o g e n e r a t e Bjerrum d e f e c t s .
-1 6
i s b e t w e e n 3.10 S (21 and 6.9 1 0 - ' ~ s /3]. On f i g u r e 5 we h a v e
0
1
plotted v e r s u s T . We f i n d a n a c t i v a t i o n e n e r g y o f t h e phenomenon
U = 0.25 -+ 0.01 eV which d o e s c o r r e s p o n d t o t h e m i g r a t i o n e n e r g y o f r o -
10%
t a t i o n d e f e c t s . I n an o t h e r h a n d , a t
t e m p e r a t u r e s where t h e p e a k i s o b s e r v e d
t h e term - EF/kT i n t h e t h e o r i t i c a l ex-
10 -
3
p r e s s i o n i s n e g l i g e a b l e i n f r o n t of CO
and t h i s a l l o w s u s t o c a l c u l a t e t h e ex-

io2-
t r i n s i c defects concentration C from
t h e apparent r e l a x a t i o n time
= sv
U 0.25 r0.01
z = 6.8 I O - ~ S . We f i n d
<
40 - 0 <C
aPjj- 10-7. T h i s c o n c e n t r a t i o n i s
i n good Egreement w i t h t h e i m p u r i t y
c o n c e n t r a t i o n of t h e a r t i f i c i a l i c e
1 - c r y s t a l s o r d i n a r l y used i n our experi-
ments.
-
*,
10

I I I I
5 7 8 9 CzO

pig. i: Z v s T1
F i g . 6 : Comparison o f o u r r e -
s u l t s w i t h t h e o r y and o t h e r s
experiments.
K : KuroFwa S : S c h i l l e r
4 : Kawada ( d i e l e c t r i c r e l a x a -
*:tion)
HF doped i c e
: our r e s u l t s
Figure 6 allows u s t o s i t u e
o u r d a t a by comparison t o
-5
to- 3
t h a t o f o t h e r s w o r k e r s and -
(0
l
t h e t h e o r i c a l curves. I ' I ~ I ' I ~
W I
4 5 6 7 8
 Relaxation i n t e n s i t i e s a t d i f f e r e n t frequencies are also interes-
t i n g f e a t u r e s . On f i g u r e 8 we h a v e p l o t l e d ( t g versus temperature
-4
f o r f r e q u t ? n c i e s from 10 t o 1 0 Hz. E x p e r i m e n t a l r e s u l t s show t h a t r e -
l a x a t ~ o nphenomena c a n be r e a s o n a b l y d e s c r i b e d by a C u r j e Law a s
tg = &-. T h i s f a c t d o e s n o t seem t o c o n f i r m t h a t t h e r e i s a p h a s e
$ , r a n s i t i o n n e a r 110 - 1.20 K a s
ct was n o t i c e d p r e v i o u s l y .
'he v a l u e of A c a l c u l a t e d from
4' t,ur d a t a i s 1.5 I O - ~ eV which
1s i n good a g r e e m e n t w i t h t h e

501,, y',-
~ t i e o r i c a lv a l u e f r o m t h e e l e c -
b r a s t a t i c model o f B a s s (83.

, , Fig.8/tgB)
-4

50 100 150 20 0 K

w i t h / J = d j p o l e moment o f h y d r o g e n bond, C44 = e l a s t i c c o n s t a n t , V = vo-

0
lumr o f u n i t c e l l and = d i e l e c t r i c constant.
L a s t l y o u r measuren!ents a f t e r d i f f e r e n t c o o l i n g r a t e s a l l o w u s t o
p u t j n e v i d e n c e t h e r o l e o f i n t , r i n s i c d e f e c t s o n r e l a x a t i o n phenomena.
We have p r e v i o u s l y d e s c r i b e d t h i s phenomenon i n t h e c a s e o f 1 Hz expe-
r i m e n t s o n p u r e o r doped speci.mens [l 3 1 . Our e x p c . r i m e n t s c o n f i r m t h a t
e v e n a t low f r e q u e n c i e s where m e a s u r e m e n t s t i m e a r e l o n g i n t r i n s i c de-
f e c t s c a n be f r o z e n by a f a s t c o o l i n g r a t e , i n d u c i n g a s h i f t of t h e
r e l a x a t i o n t o w a r d s low t e m j > e r a t u r e . A t e q u i l i b r i u m t h e d e f e c t s concen-
t r a t i o n a l l o w i n g t h e r e l a x a . t i o 1 1 i s g i v e n by C I C + exp - E~/~T.
Out o f e q u i l i b r i u n i we c a n e s t i m a t e t h e v a r j . a t i o n A C o f t h i s concen-
t r a t i o n (1)
exp. -
Em
kT -
-.
Em
k(T +AT) where A T i s t h e s h i f t o f
C C +AC

t h e t e m p e r a t u r e peak.
Under t h e s e a s s u m p t i o n s we f i n d t h a t f o r example a f t e r I O - ~ Hz
e x p e r i m e n t s A ~i s e q u a l t o - 4 K ; t h i s v a l u e i m p l i e s an i n c r e a s e i n
t h e d e f e c t s c o n c e n t r a t i o n o f 4 10-
8
.
As, a t 230 K , s t a r t t e m y e r a t u r e o f t h e c o o l i n g , we h a v e a n i n t r i n -
s i c d e f e c t s c o n c e n t r a t i o n of 7.2 10-', i t means t h a t a t t h e p e a k tem-
p e r a t u r e we h a v e " f r o z e n " about t h e h a l f of t h e i n t r i n s i c d e f e c t s i n
e q u i l i b r i u m a t 230 K .
4 . Conclusion - V e r y loh7 f r e q u e n c i e s i n t e r n a l f r i c t i o n of I c e a l l o w e d
u s t o g i v e a more c o m p l e t e d e s c r i p t i o n o f r e l a x a t i o n peak i n i c e .
C5-546 JOURXAL DE PHYSIQUE

E x p e r i m e n t s on a l a r g e f r e q u e n c y r a n g e c o n f i r m e d t h e r o l e o f t h e B j e r -
rum d e f e c t s on r e l a x a t i o x i .
An a c c u r a t e v a l u e o f Lhe m i j i r a t i o n e n e r g y o f t h e s e d e f e c t s i s
found ( E = C , 2 5
m
-
i
0 , 0 1 eV) and a C u r i e l a w i s o b s e r v e d . I n o r d e r t o
p r e c i s e t h e r o l e o f " f r o z e n " r o t a t i o n a l d e f e c t s we i n t e n d t o d o expe-
r i m e n t s with d o p e d i c e c r y s t a l s .

6. References

3 K n x e r fI.O., Nagun S., Z i e g l e r G. (1955) Naturwiss. 15, 427.

2 Sehiller P,, ( 1 9 5 8 ) Z. f u r P h y s i k Bd 1 5 3 , p . 1-15.
3 KuroPva D . (1964) C o n t r i b u t i o n no 667 .
I n s t . Low Temp. S c i .
HohkaYdo University A 1 8 , p . 1-62
4 V a s s o i l l e It., T a t i b o u G t J . , P e r e z J., Gobin P.F. ( 1 9 7 4 ) Cl1 Xcad.
S c i . P a r i s S 6 r i e B , 278 no 1 0 , 409-412.
5 T a t i b o u S t J . , V a s s o i l l e R., P e r e z J. ( 1 9 7 5 ) J . o f G l a c i o l o g y
vol. 1 6 , 7 3 , 161-169.
6 V a s s o i l l e R., May C., P e r e z J. (1978) J. o f G l a c i o l o g y , v 0 1 21
-
85,375-3 84
7 i'erez <J., Maf C . , T a t i b o u g t J , , V a s s o i l l e R., (1980) J. of Glacio-
l o g y , v o l . 25, E, 133-149.
8 B a s s R., ( 1 9 5 8 ) z. P h y s . , 1 5 3 , 1 6 ; P r o c . Roy. Soc. London, A , 247,
426-464.
9 G o s a r P., ( 1 9 7 4 ) P h i l . Mag., 29, no 2, 221-240.
1 0 Nagle J . F . ( 1 9 6 6 ) J. Math. I'hys., 2, 1 181-1492
1 1 E t i e n n e S., C a v a i l l 6 J.Y., P e r e z J . , S a l v i a M., ( 1 9 8 1 ) , 1 c I F U ~ S7 . ,
Lausanne .
1 2 Hobbs P.V. ( 1 9 7 4 ) I c e P h y s i c s , O x f o r d , C l a r e d o n I'ress.
I 3 V a s s o i l l e R., Tatibou2t J., Perez J., (1979) Proceedingaof
E u r o p e a n C o n g r e s s I F U A S M a n c h e s t e r , p. 407-412.