Bijl, D.

Physica XXI
P u l l a n , H. 285-298
1955

A NEW METHOD FOR MEASURING THE THERMAL

E X P A N S I O N OF SOLIDS AT L O W T E M P E R A T U R E S ;
T H E T H E R M A L E X P A N S I O N OF C O P P E R AND
A L U M I N I U M AND T H E G R U N E I S E N R U L E
by D. B I J L *) and H. PULLAN 9)
Clarendon Laboratory, Oxford

Synopsis
A d e s c r i p t i o n is g i v e n of a n a p p a r a t u s for m e a s u r i n g t h e t h e r m a l e x p a n s i o n of
solids a t low t e m p e r a t u r e s . T h i s is b a s e d o n t h e m e a s u r e m e n t of t h e c h a n g e of
c a p a c i t y of a c o n d e n s e r p r o d u c e d b y a c h a n g e in l e n g t h of t h e s p e c i m e n . E x p e r i m e n t a l
r e s u l t s o n t h e t h e r m a l e x p a n s i o n of c o p p e r a n d a l u m i n i u m a r e d i s c u s s e d in r e l a t i o n
w i t h G r t i n e i s e n ' s rule. T h i s r u l e is s h o w n t o b r e a k d o w n a t t e m p e r a t u r e s b e l o w a b o u t
0.3 0, t h e e x p a n s i o n b e c o m i n g s m a l l e r t h a n t h e v a l u e s p r e d i c t e d b y G r t i n e i s e n ' s rule.
T h i s d e v i a t i o n c a n b e e x p l a i n e d in t e r m s of B o r n - V o n K a r m a n ' s l a t t i c e d y n a m i c s .

1. Introduction. A detailed knowledge of the thermal expansion of solids

at low temperatures is of great value for a better understanding of the
equation of state; its importance is second only to that of the specific heat.
While, however, a very large number of measurements of the specific heat of
solids at low temperatures has been carried out, surprisingly little experi-
mental work has been done on the thermal expansion in the same temper-
ature range. Except in a few experiments only integral expansions over wide
temperature intervals were measured and even these experiments were rarely
extended below 90°K. Further experimental data are obviously of interest.
In this paper we propose to describe a step to fill this gap. In § 2 we give a
description of a new experimental method which is particularly suitable for
low temperature work. The apparatus is an improved version of that already
used for preliminary measurements 2) (henceforth quoted as loc. cit.). § 3
deals with results obtained for copper and aluminium between 20°K and
300°K. In § 4 we collect some theoretical considerations and in § 5 we discuss
our results in relation with the modern theory of thermal expansion.
In loc. cit. we have already pointed out that, even in the case of monatomic
cubic crystals, in general a breakdown of Griineisen's rule must be expected
at low temperatures, where this rule was held to be valid. This point was
illustrated by a discussion of the Brillouin model of a solid 8). Our preliminary
*) Now at St. Salvator's College, University of St. Andrews, Scotland.
§) Now at the National Research Council, Ottawa, Canada.

- - 285 - -
286 D. BIJL AND H. PULLAN

experiments induced these considerations, although they can now be dis-

carded in favour of our present results. Our present experiments show that
the thermal expansion at low temperatures is smaller than would follow from
the Grtineisen rule. This is confirmed b y very recent experimental work on
copper b y other investigators 21), which came to our notice while this paper
was being written. B a r r o n's theory 1) which is based on lattice dynamics
predicts the same behaviour.

2. The apparatus, a) P r i n c i p l e of the method. The dilato-

meter is essentially a condenser whose capacity is determined b y the difference
in length between the specimen and a suitably shaped piece of copper. This
condenser is placed in the tank circuit of a radio frequency oscillator, and a
change of temperature of the dilatometer results in a change of frequency
which can be measured b y standard methods. The relative change in length
between the specimen and the copper piece can be calculated from the change
in oscillator frequency after calibration. The measurements have been made
virtually absolute b y comparing the copper with diamond, which has a very
much smaller thermal expansion than copper.
The dilatometer is built in a vacuum tight jacket; this is surrounded b y a
similar jacket which is immersed in the cooling liquid. B y evacuating the
space between the jackets and b y balancing the heat loss of the inner jacket
with an electric heater, the dilatometer can be held at a temperature con-
siderably above the boiling point of the liquid used. In this way any desired
temperature between 20°K and room temperature can be maintained. This
temperature is measured with a platinum resistance thermometer.
b) T h e d i 1 a t o m e t e r. A cross-sectional diagram of the dilatometer in
its final form is shown in fig. 1 which is approximately to scale. The specimen
S stands on an optically flat plate off used quartz Q which is supported
b y a quartz ring q. S is surrounded b y a copper reference ring R which stands
also on the plate Q. The top of S touches a copper plate P which can move
(without tilting, see below) over distances up to about 0.5 mm. The capacity
between P and R (which is placed in the tank circuit of the oscillator) then
depends only on the difference in length of P and R. The reference ring is
connected to the other parts of the oscillator b y a coaxial line Co and the
copper-glass seal Se. Both the inner and the outer conductor of Co are made
of copper and the amount of dielectric is small in order to reduce the change
of capacity of Co with temperature to a minimum.
The cylindrical specimens (length about 2 cm) have a rounded top and
stand on a circular rim or on three small points; a central hole h is useful for
placing S in the centre of R (see below). The base of the reference ring, which
is made of very pure copper, is milled so that it stands on three small points
and is held in position b y a fibre disk F and three steel springs sl, which are
looked to the baseplate Bp. The tolerance obtainable with a good lathe is
 THERMAL EXPANSION OF SOLIDS AT LOW TEMPERATURES 287

sufficient for the preparation of the specimen ; this is an important ad~'antage

over the optical interference methods.
The moving plate P is integral with a vertical rod r which is clamped at
the centre of two carefully annealed phosphor bronze membranes M 1 and
M 2. The membranes are clamped at their peripheries to the barrel B. The
lower membrane is clamped between a shoulder in the barrel and a knife-
edged annular distance ring Ar, the upper membrane between Ar and a
second knife-edged ring ar. A washer W and a locking nut N hold the whole
system rigid in the barrel. A similar system is used for clamping, the mem-
branes to the rod r. The use of two membranes some distance apart greatly

Th Sp

F D

Fig. 1. T h e d i l a t o m e t e r .

reduces the tendency towards tilt without altering the resistance against
vertical motion of P b y more than a factor of two. Therefore this system of
mounting the moving plate allows small vertical displacements of the plate
P while tilt of P under temperature changes is negligibly small. A phosphor
bronze conical spring Sp which is held in position b y a plate Rp ensures
contact between S and P under all circumstances.
The barrel B is clamped in the vertical case Ca with three horizontal
screws; Ca is bolted to the lid L of the inner vacuum jacket. A platinum
resistance thermometer Th is wound on a thin walled copper cylinder which
is placed in the annular space between the barrel and the case. The leads of
Th pass through the pumping tube Pt. Heat contact between the thermome-
ter and the dilatometer is secured b y the presence of some helium gas in the
inner vacuum jacket.
288 D. BIJL AND H. PULLAN

The base-plate is held in position b y an annular distace ring D (touching

the other parts of the dilatometer with small points) and three steel springs
s2, which clip into slots in the base-plate. B y undoing the springs s2 the whole
lower part, including the specimen, can be removed without altering the
moving plate system. A threaded boss H is used during assembly to hold a
locator plug (not shown in the diagram) ; this carries a vertical rod fitting in
the hole h in the specimen, thus keeping the specimen in the centre of the
reference ring. After assembly the locator plug is removed.
Unless stated otherwise, all parts of the dilatometer have been machined
from a single piece of pure high-conductivity copper, in order to reduce any
effects of warp and thermal hysteresis. As a test we measured the frequency
of the oscillator at various temperatures of the dilatometer with a specimen
of the same copper as the reference ring. In the ideal case the only change in
frequency should be due to the change in surface area of the reference ring
and a small change of gap in the condenser. The actual change of freqency
was somewhat larger, however, and it could be shown that the coaxial line Co
was responsible for this. The effect was reproducible and small, so that the
results could be corrected for it.
c) T h e o s c i 1 1 a t o r. The oscillator used is a Colpitt oscillator in
which a small condenser -- in our case the dilatometer condenser -- is placed
in series with the usual condensers as has been described b y C 1 a p p s).
This circuit is characterised b y high frequency stability, and moreover the
frequency is very sensitive to changes in the capacity of the small condenser,
which makes the Clapp oscillator very suitable for our purpose.
In the design of the actual layout of the oscillator careful consideration
has been given to the reduction of changes in stray capacities with alterations
t,f temperature. The lead between the coil and the dilatometer condenser is
made as short as possible b y placing the coil on top of the outer vacuum
jacket. This has the additional advantage that the coil is immersed in the
cooling liquid and therefore is at constant temperature during the experi-
ments. In order to eliminate the capacitive effect of the silvering of the Dewar
vessel the coil is surrounded b y a screening can. The coil is wound on the
glass part of a commercial copper-glass seal. Furthermore the coaxial lead
from the coil to the cap of the cryostat is designed especially to reduce the
effect of variations of the height of the liquid on the capacity; for details we
refer to s). The long term stability of the oscillator at a frequency of about
3 Mc/s is under all circumstances better than two parts in hundred thousand,
which is the accuracy of the wavemeter used for measuring the frequency.
d) C a l i b r a t i o n and temperature measurement. The
calibration of the dilatometer is carried out at room temperature in the
following way. A micrometer is mounted vertically below the dilatometer
in a support which is clamped to the case. A glass rod follows displacements
of the micrometer spindle and is guided b y a vertical hole in a brass plug
 THERMAL E X P A N S I O N OF SOLIDS AT L O W T E M P E R A T U R E S 289

which is screwed in the threaded boss H. The rod passes through the ~lole in
the quartz plate and carries at the top a d u m m y specimen, which touches the
moving plate. Thus known separations between the condenser plate and the
reference ring can be produced and the relation between the separation and
the frequency established. A correction has to be applied for the fact that
during the experiments the coil is immersed in the cooling liquid.
The temperature of the dilatometer is measured with a platinum resistance
thermometer connected in a Wheatstone bridge. The balance detector is a
galvanometer amplifier 19), which allowed temperature changes smaller than
0.001 degree to be detected. This sensitivity is very useful for estabiishing and
maintaining temperature equilibrium in the dilatometer; the requirements
for the actual measurements of temperature are far less stringent.
The thermometer is calibrated at the ice-point and at the boiling points of
oxygen and hydrogen; intermediate temperatures are calculated using the
interpolation tables of L i n d e r 18).
e) S e n s i t i v i t y and accuracy. An estimate of the sensitivity
can be obtained in the following way. If it is assumed that the total capacity
in the dilatometer is the only capacity controlling the f r e q u e n c y / ( w h i c h is
correct to a good approximation), then ] is given b y
4z~/2 L(C + E) = 1,
where C is the dilatometer capacity, E accounts for the distributed capacity
(for instance in the coaxial line Co, compare fig. 1) and L is the inductance
of the coil. Hence
20l/l = -- (~C + 6E)/(C + g).
Now the accuracy of the wavemeter is about 2 parts in 100,000, so the
smallest measurable change in frequency is given b y ( 6 / / / ) = 2 x 10-5;
taking C = 30 pF, E = 15 p F and assuming for the moment that 6E = 0,
we find 6C = 1.8 x 10-a p F or the smallest detectable capacity change. The
relative sensitivity is thus 6C/C = 6 x 10 -5. This is approximately equal to
6 X / X , where X, the separation of the plates, is about 2 x 10 -2 cm; we
therefore have for the smallest detectable changes of the width of the gap
6X = 12 x 10-~ cm. As 6X is produced b y a specimen of length l = 2 cm,
the smallest detectable difference in dilatation between specimen and refer-
ence ring is 6X/l = 6 × 10 -7. This estimate is only approximate, largely
because we have assumed that 6E = 0. We calculate for the actual accuracy
of the measured length changes 3 × 10 -6 cm; this figure for the accuracy
is about the same as that quoted b y N i x and M a c N a i r 2 ° ) using an
optical interference method. We have every reason to believe that our
method could be made much more accurate if the apparatus were redesigned.

3. Experimental results, a) C o p p e r. Apart from its intrinsic value, an

accurate knowledge of the thermal expansion of copper is important because
Physica X X I 19
290 D. B I J L A N D H. P U L L A N

copper is used as the reference material in our measurements. F u r t h e r m o r e ,

previous accurate measurements between 90°K and room t e m p e r a t u r e allow
a detailed check of our apparatus to be m a d e in this t e m p e r a t u r e range.
A compilation of previous d a t a and m a n y references m a y be found in a
Report of the National Bureau of Standards 11). This report also contains a
table of values of the integral of t h e r m a l expansion between 100°K and room
temperature, based on the investigations of B u f f i n g t o n and L a t i-
m e r ~) and N i x and M a c N a i r 20), which agree excellently with each
other. The values below 100°K are based on one value in this range 15) b y
Keesom, V a n A g t and J a n s e n and the Grfineisen relation in the
form used b y Nix and MacNair. While this paper was being written new
m e a s u r e m e n t s between 25°K and 300°K b y R u b i n , Altman and,
J o h n s t o n 21) came to our notice. E x c e p t Keesom et alii, all investigators
mentioned used an optical interference method.
In our preliminary measurements the reference ring (loc. cit.), which was
m a d e of a block of copper supplied b y J o h n s o n M a t t h e y Ltd. (specification
Bss 1433, p u r i t y better t h a n 99.98% ), was compared with a specimen of
fused quartz. The expansion of quartz was supposed to be given b y an inter-
polation formula calculated b y V a 1 e n t i n e r and W a 1 1 o t 23). This
procedure was unsatisfactory for various reasons. In the first place the inter-
polation formula was based on too few measurements to be reliable ; secondly
the expansion of fused quartz is known to differ appreciably for specimens of
different origin and t h e r m a l t r e a t m e n t . Finally, the expansion coefficient
becomes negative of about the same absolute m a g n i t u d e as the positive
•expansion of copper at the lowest temperatures in our range. For these
reasons our preliminary values of the expansion of copper cannot be expected
to be reliable at low temperatures and our final experiments have shown t h a t
this is indeed so.
In our final measurements copper was compared with a d i a m o n d specimen
and furthermore t h e y were carried out with an improved a p p a r a t u s *).
D i a m o n d has a very small thermal expansion, and a simple extrapolation to
low temperatures of D e m b o w s k a's d a t a 1~) with the aid of the Grfin-
eisen relation shows t h a t the t h e r m a l expansion of d i a m o n d can be com-
pletely neglected below 90°K ; at room t e m p e r a t u r e the required correction is
not more t h a n a few percent. Thus the use of d i a m o n d makes the measure-
ments on copper virtually absolute, as stated already in § 2a.
B y the generosity of Industrial Distributors, Ltd., (1946), a d i a m o n d rod
of dimensions 9.84 x 1.50 x 0.81 m m was m a d e available. This rod was
m o u n t e d in a special holder which m a d e incorporation in the dilatometer
possible. Parts of a copper cylinder, m a d e of the same material as the referenc
ring, were cut a w a y so as to give a block shown in cross section in fig. 2a.

*) This i m p r o v e m e n t consisted in a better design of the coaxial line (compare fig. 1).
 THERMAL EXPANSION OF SOLIDS AT LOW TEMPERATURES 291

The diamond D stands on a flat part of the block B; a phosphor sl~ring S

presses D gently against the rims rl and r 2. Small parts of the rims are cut
away in order to prevent movement of the rod D perpendicular to the plane
of the drawing (see fig. 2b). This construction keeps the diamond vertical,
notwithstanding the large difference in expansion between the copper and
the diamond. The base of B rests on three points P; the copper foil F prevents
damage of the moving plate by the hard diamond.

........... (~)

Fig. 2. The holder for the diamond specimen.

The final experimental values of the relative length change

( = l T - - 1.273.2)/1273.2) and the linear expansion coefficient/5 (which are aver-
ages of several experiments) are given in Table I. The values of /5 were
TABLE I

Copper
= (IT - - 1273.2)/1273.2 fl = (l/l)(al/aT)p
T(°K) I ~xlo~ [ 3xlo' T(°K) ] 6x l0 s ] f i x 106
20 --2.908 130 ~2.141 12.6
30 --2.901 150 --1.887 13.6
40 --2.889 1.6 170 --1.599 14.3
50 --2.866 3.0 190 --1.306 14.9
60 --2.827 4.6 210 --1.002 15.3
70 --2.772 6.7 230 --0,693 15.7
80 --2.694 8.8 250 --0.377 16.1
90 --2.594 I0. I 270 --0,052 16.4
110 --2.382 11.5 273.2 0

obtained by differentiation of a smooth graph of the experimental values of

against temperature. The estimated accuracy of the values of fl and ~ is 2
units in the last decimal place. The values of ~ above 90°K agree within the
experimental error with the values in the Table in the N.B.S. report and
therefore with Nix and MacNair's results. Keesom a al.'s 15) value at 20°K,
× 103 = --2.906 4- 0.020, which was obtained by an absolute method, agree
very well with our value at that temperature. This may be somewhat for-
292 I). BIJL AND H. PULLAN

tuitous however, as their value at 170.3°K, 8 x 103 = -- 1.579, and at 87.6°K,

8 × 103 = -- 2.575, are 2% smaller than the values in the N.B.S. report and
than our values. Throughout our temperature range our values of 8 are not
more than 15/o lower than those of R u b i n et al. 21), which is within the
estimated accuracy. The excellent agreement of our results with those of
other investigators constitutes a good check of our method and apparatus.
Our preliminary results give not such good agreement with the work of other
investigators, as might be expected. The accuracy of the values of fl is
naturally much less than those of 8, especially at the lowest temperatures.
b) A 1 u m i n i u m. Aluminium was investigated in order to obtain more
data about the validity of Grtineisen's relation. The most accurate and
detailed absolute measurements above 90°K have been carried out by N i x
and M a c N a i r 20) ; their paper contains many references to previous work.
The specimen used was made from material of spectrographic standard
(Johnson Matthey, Ltd., catalogue number JM 340, purity 99.9945/0).

TABLE II

Aluminium
(~ = (l T - - b273.2)//273.2 ~ (1/1) (Ol/OT)p
T(°K) [ c5 × l0 s [ 8 × 106 T(°K) [ c5 x l0 s [ fix 10 6
20 --3.738 130 --2.854 15.6
30 --3.733 150 --2.519 17.1
40 --3.723 1.5 170 --2.159 18.4
50 --3.700 3.0 190 --1.779 19.5
60 --3.661 4.9 210 --1.379 20.6
70 --3.603 7.0 230 --0.959 21.4
80 --3.519 9.4 250 --0.519 22.2
90 --3.409 11.2 270 --0.069 22.4
110 --3.154 13.9 273.2 0

The results of several experiments are collected in the Table II. The
estimated accuracies of the value of 8 × 103 and fl × 106 are 2 units in the
last decimal place. Nix and MacNair's values above 90°K are about 1.5%
below our values. E b e r t ' s g ) value, 8 × 1 0 3 = - 3 . 7 3 at 20°K is in
excellent agreement with our value at the same temperature; his value at
195°K, 8 × 103. = -- 1.65, and at 83°K, 8 × 103----- --3.42,are both 2%
smaller than our values at these temperatures. The agreement is quite satis-
factory taking into account the different origins of the specimen and the fact
that Ebert used fused quartz as reference material.

4 (a). Theoretical considerations on the Gr~neisen rule. The most detailed

theory of the thermal expansion of solids which has been made so far has
been given by G r f i n e i s e n !3) and his results still form the usual basis
for the discussion of experimental results. His theory is essentially based on
the assumption of a Debye frequency spectrum, and in Griineisen's treat-
 T H E R M A L E X P A N S I O N OF SOLIDS AT L O W T E M P E R A T U R E S 293

ment it is not easy to assess the significance of this assumption. Many later
investigators apparently have not fully appreciated the actual position and,
as H u m e-R o t h e r y 14) has shown, considerable confusion has been
the result. It is therefore advisable to give a brief account of the present
theoretical position before discussing our experimental results.
a) In most of the theories of the equation of state of solids a crystal of N
similar particles is treated as a set of 3N harmonic oscillators whose frequen-
cies are supposed to depend on the volume. A straightforward application
of statistical mechanics allows the calculation of the Helmholtz free energy
F. By using the thermodynamic relation
a/~ = -- ~F/aVOT, (1)
where a ( = l/V)(OV/OT)p) is the coefficient of thermal expansion and
y.(= (-- 1/V) (~V/OP)T) is the isotheruaal compressibility, it can be shown
(see, for example, S 1 a t e r 22) t h a t

a/u = (k/V) Z i 7i Bi, (2a)

where
(hvJkT) 2 exp (hvJkT)
B i =
{ e x p (hv,/kT) - - I} 2

7i ---- -- d In vi/d In V; (2b)

vi is the frequency of the i-th vibration and the summation is made over the
whole spectrum. The quantities 7i are a measure of the volume dependence
of the corresponding frequencies; vi (----r~(V)) and n ( = n(V)) must be taken
at the volume V corresponding to the given pressure P and given temper-
ature T. The pressure is usually atmospheric so that practically P = 0. Rela-
tion (2) can be written in a more familiar form by introduction of the specific
heat at constant volume of the lattice waves, Cl, which is given by

CI = k E i Bi.
We can now write for (2a)
a = 7, c , , (3)
where 71 = E~ 7i B~/EiBi (4)
is the Grfineisen factor. Grtineisen 13) was the first to point out that for m a n y
simple substances 7l is approximately constant at average temperatures.
Now the variation of n/V with temperature is also small, and so to a good
approximation the coefficient of thermal expansion is proportional to the
specific heat. This rather loose statement is usually called Griineisen's rule.
In this paper we require a more precise formulation and we take Grfineisen's
rule to imply that 71 is exactly constant.
In general there is no theoretical reason to expect this to be strictly true
294 D. B I J L AND H. PULLAN

(see (4), in which the quantities Bi are functions of temperature). A d m i t t e d l y ,

a solid having a Debye frequency spectrum can be shown to obey Griin-
eisen's rule exactly 22). B u t it is wellknown t h a t the Debye spectrum is only
a crude a p p r o x i m a t i o n to the spectrum of a real solid (except for the lowest
frequencies) and therefore provides an inadequate basis for a n y b u t the
a simplest discussion of t h e r m a l expansion.
It is not difficult to show t h a t according to (4) 7t tends to constant limits
at high and very low temperatures; these limits are usually different 1) 4).
Consequently, at i n t e r m e d i a t e temperatures deviations from Grfineisen's
rule m u s t be expected. An actual calculation of these deviations requires
a more detailed model t h a n we have considered so far.
Two models have been used for m o n a t o m i c solids. The Brillouin model
has been considered in loc. cit. In this, the solid is t r e a t e d as an isotropic
c o n t i n u u m in which transverse and longitudinal waves can be excited. These
waves are supposed to have the same m i n i m u m wavelength, but, because
their velocities of propagation are different, t h e y have different m a x i m u m
frequencies. If it is assumed t h a t t h e y have different values of 7o it can
easily be shown t h a t under these circumstances 7z varies with temperature.
A more detailed model has been considered b y B a r r o n 1). Assuming
central forces between the atoms in a cubic face centered lattice and taking
into account only the interaction between nearest neighbours, B a r r o n
calculated 7t with the aid of (4), neglecting the effect of the change of volume
on the frequencies v~. B a r r o n found a decrease of 7t with decreasing
t e m p e r a t u r e ; the rate of change of 7~ with T is m a x i m a l for T ~ 0.2 0o0,
where 0oo is the high temperature limit of the characteristic temperature.
Furthermore, independent of the force law, (7~)0o -- (71)0 = 0.3. Barron's
result for 700 ~ 2 is shown as a dashed line in fig. 3, and will be compared
with our experimental results in § 5.
b) A discussion of the t h e r m a l expansion of metals should consider the
presence of the conduction electrons. To a first a p p r o x i m a t i o n this can be
done b y adding an extra term F8 to the free energy 24) ; this term is of the form
F8 = T / (T/Te),
where T8 is the characteristic t e m p e r a t u r e of the conduction electrons (see
for example F o w 1 e r 10)). For free electrons T8 can be expressed in terms
of the effective mass of the electrons m and the n u m b e r of electrons per cm 3,
n(= n(V)), when
T8 = (h /Smk) (5)
Using the relation (1) as before we now find instead of (3)
= (7,c, + cs)/v (6a)
with
78 = -- d In Ts/d In V; (6b)
 T H E R M A L E X P A N S I O N OF SOLIDS AT L O W T E M P E R A T U R E S 295

C, is the specific heat of the c o n d u c t i o n electrons. The first t e r m at ttxe right

h a n d side has been discussed above; the second t e r m describes the influence
of the conduction electrons, and should be d o m i n a n t at v e r y low temper-
atures. This can be seen as follows.
We can define an 'effective' 7 for a metal, 7,,, b y the relation
a/~ = (~,,,,/V) (C~ + C,),
where C l + C, is t o t a l specific heat. I t is easily seen t h a t (compare (6a))

7,. = (7, C, + ~,~C,)/(C, + C,).

F o r most solids 7~ "~ 2; the value of 7, is more difficult to assess. According

to (5) and (6b), for a free electron gas 7, = ~ ; we will t e n t a t i v e l y assume t h a t
it is not v e r y different for an actual metal. Now at o r d i n a r y t e m p e r a t u r e s
C, >~ C, and therefore 7,, = 71, so t h a t (6a) is reduced to (3). At (low)
t e m p e r a t u r e s where C, ~ C, (for most metals at a few degrees absolute)
7,,, < )h- At v e r y low t e m p e r a t u r e s C~ ~ Cr and so we should have )J,, = 7 , ~ ~.
This implies t h a t for metals a drastic decrease of 7~ with decreasing
t e m p e r a t u r e m u s t be e x p e c t e d at v e r y low t e m p e r a t u r e s . Actual metals
p r o b a b l y h a v e values of ~ different from ~ (for instance if m depends on V),
and it would be v e r y interesting to determine t h e m experimentally. This
would require a separation of the effects of the lattice waves and the con-
duction electrons on the t h e r m a l expansion, which could be carried out in
the following manner.
If we define a q u a n t i t y )J,',, b y the relation

= c,

we find t h a t (compare (6a))

7 . = 7t + 7~ CJCz,
At sufficiently low t e m p e r a t u r e s we have Ct ~ T 3 and p r o b a b l y C, ~ T,
while 7~ and 7, should be constant. Assuming this to be correct, a plot of
e x p e r i m e n t a l values of ~,',, against 1/T 2 would be a straight line from which
b o t h constants could be determined. No e x p e r i m e n t a l results are as yet
available for this t r e a t m e n t .

5. Discussion o] experimental results. In this section we will discuss the

e x p e r i m e n t a l check of relation (6a) for the metals investigated. I t follows
from K o k and K e e s o m's m e a s u r e m e n t s on c o p p e r 16) and alumi-
nium 17) t h a t even at our lowest t e m p e r a t u r e s C t >~ C,, and therefore (6a)
reduces to (3). Using B r i d g m a n ' s value for ~ near room t e m p e r a t u r e 5)
and G i a u q u e and M e a d's values of C112) we h a v e calculated 7z with
the aid of (3) from our e x p e r i m e n t a l results for ft. The results are shown as
full d r a w n curves in fig. 3. The a c c u r a c y of these results depends on the
296 D. BIJL AND H. PULLAN

accuracy of our measurements and the accuracy of the other experimental

results used. It is therefore not easy to assess the final accuracy of the values
of Yv We estimate that near room temperature the accuracy of y~ is about
2%; this is corroborated by the good agreement with the values given by
G r ii n e i s e n 18). At lower temperatures the accuracy decreases to about
5% at 90°K and about 15% at 40°K.
Below T ~ 0.3 0oo y~ drops sharply with decreasing temperature, while at
higher temperatures a much smaller, almost linear, decrease is found. A
similar behaviour has been found by R u b i n e t al. 21), although these
authors find a less marked decrease of y~ below T ~ 0.3 000. It must be
remarked that the decrease of y~ with decreasing temperature is at variance
with our preliminary results (loc. cit.), but for reasons already given in § 3a
these are less accurate than our present results and can be discarded.
A more rigorous check of '(3) can be made by taking into account the varia-
tion of u and V with temperature under constant pressure. This correction
amounts to not more than 5% in our case and therefore can be carried out
in the following simple way. The values of y~just discussed, which we indicate
t
by Yt, were calculated using the relation

al o = ( ;IVc) c,, (7)

where xc and V~ are taken at room temperature. Now according to Grtin-
eise we should have to a first approximation

a= (zo/Vo) 7t C/(1 -- bEt) 2 ~ (uo/Vo) Y0 (1 + 2bEt) Cl,

where u0 and V 0 are the values of v. and V at the absolute zero, E r is the
thermal energy and b is a small constant, so t h a t throughout our temperature
range bEt ~ 1. A comparison between (3), (8) and (9) gives the following
relation between Yl (defined by (3)) and y; (defined by (7))

y, = (1 + 2bERt ) (1 -- 2bEt) y;.

Taking the values of b from N i x and M a c N a i r's 2o) work and calcu-
lating E r as a Debye function with the values of 0oo as characteristic temper-
ature (compare fig. 3) we obtain the 'true' values of Yl, which are shown as
dotted and dashed lines in figure 3. It must be noted that this simple pro-
cedure for correcting for the variation of n and V becomes rapidly less
accurate at higher temperatures and has then to be replaced by a more
rigorous method.
It. can be concluded from figure 3 that the relation (3) is satisfied (within
our range of measurements) with a constant value of Yt at temperatures
t
above T ~ 0.3 0oo. The slow increase of Yt therefore is only a consequence of
the fact that we neglected the variation of ~ and V. But the decrease of y;
below T ~ 0.3 0o0 is practically unaffected by the volume correction and
therefo_re require.s another explanation.
 THERMAL EXPANSION OF SOLIDS AT LOW TEMPERATURES 297

In looking for an explanation of the breakdown of the Griineisen-rule at

low temperatures three possibilities must be considered. We have already
seen that the influence of the conduction electrons can be neglected in our
temperature range. The zero point motion leaves Grtineisen's rule unaffected,
except possibly when it causes marked anharmonicity of the lattice vibra-
tions. Therefore we have to consider the third possibility, an explanation in
terms of lattice waves.
A comparison between Barron's theory and the experimental results
indicates that in fact the lattice waves cause the variation of y~ at low
temperatures. The agreement is only qualitative, but this is not'surprising
in view of the approximate character of Barton's theory and the difficulty of
measuring very small thermal expansions accurately. The available experi-
mental evidence suggests that the drop of y~ below T ~ 0.3 0oo is larger than
2"5

F AQ
/.
1.J"
jTh
2"0 f
t "t , ~
.t: t"
e /
(r.)~
I'B

I.G
0 0"5 T/O,, I-O
Fig. 3. ord. Griineisen F a c t o r . abs. r e d u c e d t e m p e r a t u r e .
T h e v a r i a t i o n of t h e Griineisen f a c t o r 7~ w i t h r e d u c e d t e m p e r a t u r e for c o p p e r
(0oo = 315°K) and a l u m i n i u m (0oo = 389°K.
c a l c u l a t e d w i t h c o n s t a n t v o l u m e a n d compressibility.
........ c o r r e c t e d for v a r i a t i o n s of v o l u m e ;
B a r r o w ' s theory, (70)th is t h e t h e o r e t i c a l low t e m p e r a t u r e l i m i t ;
• e x p e r i m e n t a l v a l u e s of 7t g i v e n b y Grtineisen 13).

that predicted b y the theory. For a full understanding of the situation more
accurate experiments and a more detailed theory are needed.
The physical implication of the deviation of Griineisen's rule is simple.
The Grtineisen factor at a given temperature is a weighted average over the
y~ of the excited lattice waves. Now the excitation of the waves is a function
of temperature and furthermore, the quantities ),~ have in general different
values.As a result the measured r~ varies with temperature.This is apparently
most marked at temperatures around 0.2 0oo, in which temperature range
Grtineisen's rule generally was held to be valid. We can conclude also that
the shape of the frequency spectrum of the lattice is affected when the
298 THERMAL E X P A N S I O N OF SOLIDS AT LOW T E M P E R A T U R E S

volume of the crystal is altered. Similar behaviour must be expected in m a n y

simple solids of various types. This is corroborated by unpublished measure-
ments on iron and potassium bromide, for here also a drop of y~ with de-
creasing temperature is found below T ~ 0.3 0oo.

We are indebted to Professor Sir F r a n c i s S i m o n, C.B.E., F.R.S.,

for his stimulating interest, to the University of Oxford, for the award of a
Pressed Steel Company Limited research fellowship (D.B.) and to the De-
p a r t m e n t of Scientific and Industrial Research for a maintenance grant (H. P.).
We would also like to t ha nk Mr. T. H. K. B a r r o n for m a n y useful dis-
cussions, Mr. E. T i 1 b u r y for constructing the dilatometer and Mr. W.
S u m n e r for his help with the experiments.
Received 8-2-55.

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