THERMAL CONDUCTIVITY OF GOLD AND SILVER

AT HIGH PRESSURES

B. SUNDQVKT and G. BACKSTR~M

Department of Physics, University of Umel. S-901 87 Ume& Sweden

(Received 28 Lkcember 1971: accepted 6 June 1978)

Abstract-The thermal diffuskties of gold and silver have been measured under pressure up to 2.5 GPa at room
temperature. From the measured data the pressure dependence of the thermal conductivity, A. has been calculated.
The values found for the pressure coefficient A-’ &I/G’ were 3.9 x lo-* GPa-’ for gold and 4.0 x IO-‘ GPa-’ for
silver at atmospheric pressure. The results

I. MTRODUCTlON annealed were bent to their intended shape prior to

thermal conductivity, of most metals has annealing, whichwas carried out in air at less than
extensively studied a function temperature. 0.1 torr at a temperature of 1000K. This temperature was
Very work, however, been devoted kept for 4 hr, after which the oven was allowed to cool at
measurements of pressure dependence A. a rate of about 100K hr-‘. Details of the experimental
We recently presented experimental results procedure and of the high pressure apparatus are found
the pressure of A copper up in previous papers [ 1,2].
2.5 GPa[l] also the accurate measurements A
for in the pressure range. the 3.RFSuLlS
present we present measurements of Experiments were carried out on six silver specimens
thermal conductivity gold and up to GPa. and five gold specimens. As in the case oi copper and
aiuminium no significant difference in the pressure
coefficient of a was found between annealed and un-
The of measurement been described annealed specimens. Therefore only two gold specimens
[ 1,3]. We do not measure A directly but rather and one silver specimen were annealed. The average
the thermal diffusivity a, defined from A = gpc,, where p absolute values of a at atmospheric pressure and at
is the density and c, the specific heat capacity of the T= 315 K for the unannealed specimens were CI=
specimen. The measurement of a is carried out using a (I.75 kO.05) cm2 s-’ for silver and a=
method similar lo that due lo Angstriim. We have, (1.30?0.02) cm2 s-’ for gold. The errors given are the
however, modified this lo take into account lateral heat mean deviations of measured values from the average
loss by conduction from the specimen to the surrounding over all specimens. For the annealed specimens the
solid pressure medium. The thermal conductivity can corresponding values were found lo be 0 = I.81 cm* s-’
easily be calculated from the measured values of a, since for silver and a = 1.33cm* s-’ for gold. These results are
the density of metals as a function of pressure is well good agreement with the values a=
known and the pressure dependence of c,, can be cal- ;?.73 * 0.07) cm* s-’ and g =(1.28*0.06)cm2s-’ ior
culated from thermodynamic considerations. silver and gold, respectively. recommended by Toulouk-
The greatest advantage of this method is that the ian et al. [4].
heavy power losses from the heater to the pressure In Fig. I we show typical results obtained for a as a
medium are of no consequence. Another advantage is function of pressure for gold and silver. We made a total
that the final expression for a only contains phase shifts of ten pressure runs on the five gold specimens. The
and relative amplitudes. Therefore no absolute tempera- maximum pressure reached in the individual runs varied
ture measurements are necessary, and no corrections from 1.5GPa lo over 2.6GPa. The agreement between
have lo be applied for the change in thermopower of the the results from different runs on the same specimen was
thermocouples under pressure. generally within 0.5%. We found that, within the
The specimen material was obtained from Koch-Light experimental errors, g is a linear function of l? The
Laboratories Ltd., Colnbrook, England, in the form of pressure coefficient of a was found lo be
silver and gold wire, l.Omm in diameter. The stated [g(O)]-‘&z/M = (3.5 + 0.6) x lo-* GPa-‘. The error given
purity was 99.999% for the gold and 99.998% for the is the mean deviation from the weighted average. Those
silver. These figures refer only to metallic impurities in runs which span a larger range in pressures have
the material from which the wires were drawn. received more weight, as have also those runs which
Measurements were done both on annealed specimens show a smaller scatter of the individual data points.
and on specimens “as received”. The specimens to be In the case of silver the scatter in the data was

1133
1134 B. SUNDQVIST
l.Sl
0 1 2 3
PRESSURE (GPa)
Fig. 1. Typical experimental results for a(P). Circles denote
results obtained during the first pressure cycle while squares
refer to a second pressure cycle. Open symbols denote increasing
pressure and filled symbols decreasing pressure.
appreciably larger. We made a total of fourteen runs on
the six specimens. As in the case of gold the agreement
between the results from different runs on the same
specimen was excellent. However, the average results
for the individual specimens showed a mean devia-
tion from the grand average of 20%. The mean
pressure coefficient of a is [g(O)]-‘au/@ =
(3.62 0.8) X 10e2GPa-‘.
To obtain the pressure coefficient of A we must find
the pressure dependences of p and c,. The density of
gold and silver vs pressure can be taken from Vaidya and
Kennedy[Q The heat capacities have never been
measured under pressure for these metals, but we may
use the thermodynamic relation[6].
(~),=-n[*2+(~)p]
where u is the specific volume and a the volume expan-
sion coefficient. Using values of a given by Simmons(7]
we obtain [c,(O)]-‘&./@ = -2.5 x lo-‘ GPa-’ for gold
and d4.4~ lo-‘ GPa-’ for silver. Considering that eqn
(1) gives quite accurate results in the case of
copper [8,9], the values obtained above are expected to
be accurate to within lo%, an acceptable uncertainty in
view of the fact that the total pressure coefficient of c, is
small compared to the pressure coefficient of 4.
The pressure coefficient of A can now be calculated to
be [A(O)]-‘aA/@ = (3.9 + 0.6) x low2GPa-’ for gold and
(4.020.8) x 10-2GPa-L for silver. These results can be
compared to the values 3.9~ 10-2GPa-’ for commer-
and Ci. B~CKSTT&M
cially pure gold and 4.4 x 10e2GPa-’ for commercially
pure silver given by Starr [ lo].
4. DISCUSSION
The total thermal conductivity is the sum of the elec-
tronic thermal conductivity, A., and the lattice thermal
conductivity, A,. At room temperature AdA is only about
0.9% for gold and 1.1% for silverill]. As A. is the
dominating part of A we would like to eliminate as far as
possible all effects of A, on the measured results to be
able to study A, only. The pressure dependence of the
lattice thermal conductivity in this temperature regime
has been studied by Bohlin and Andersson[l2], who
found the expression
d(ln A,)/a(ln V) = -7y + l/3 (2)
in which y is the Grtineisen parameter. By using values
for the bulk modulus B. given by Vaidya and
Kennedy[S] and y from Gschneider [13] we obtain the
pressure coefficients for the electronic thermal conduc-
tivity: [A.(O))]-'aMaP = 3.8x 10m2GPa-’ for gold and
3.9 X lo-* GPa-’ for silver.
In general, the electronic thermal resistivity We = A;’
can be written as W. = WO+ W, + W,, where W,, is the
electronic thermal resistivity due to impurities and W, is
that due to electronelectron scattering. We can relate
WOto the low temperature limit of the electrical conduc-
tivity, oo, by the Widedemann-Franz law, uoWo =
(LOT)-‘. Here Lo is the Lorentz number 2.443~
10-8V2K-2. From a measurement of u0 we can thus
evaluate Wo. The residual resistance ratio was measured
after the pressure runs for two unannealed samples of
each metal, and from these “worst case” measurements
we conclude that W, should be less than 1% for all
‘samples, and thus negligible. The fact that we have not
been able to distinguish between the pressure coefficients
of annealed and unannealed samples makes this assump-
tion even more plausible.
Laubitz[l4] has explained the high temperature
behaviour of A. for the noble metals by the term W,. At ’
room temperature, however, W, is less than 1% of We
for all of these metals [14], and therefore we should not
expect to see any pressure effects from this term. In the
following discussion we thus take We = W,.
Bohlin[lS] has given a simple analysis of the volume
(1)
dependence of the phonon-limited electronic thermal
resistivity W,, starting from the well-known Bloch-
Wilson expression[l6]. In this formula a Debye model
with a characteristic temperature 0 is used for the
phonon spectrum and all Umklapp processes are neglec-
ted. In spite of these simplifications this theory has
predicted the pressure coefficients of A for copper and
aluminium with reasonable accuracy[l, 21. Bohlin[lS]
gives a formula for r-‘[a(ht W,)/a(ln V)+ l/3] as a
function of T/B, which is shown graphically in Fig. 2 for
three values of the number n of conduction electrons per
atom.
We have calculated a(ln W,)/a(ln V) from our results
for aA./@. These values have been plotted in the figure
using values of B from Gschneider[l3]. Fiffled symbols
 Thermal conductivity of gold and silver at high pressures 1135

and used in the calculation of dA/aP is too high. From

eqn (1) we calculate the pressure coefficient as
-0.88. lo-’ GPa-’ using thermal expansion data given by
Kroeger and Swenson[20]. This would give a pressure
coefficient of 5.0*10-*GPa-’ for aluminium, and this
result is indicated by the squares in Fig. 2. This result is
in better agreement with what was said above concerning
. the neglect of umklapp processes.
Laubitz and Cook[21,22] have given a more detailed
analysis of W, for simple metals, in which W, is
divided into two parts, one “elastic” part which can be
computed from the electrical conductivity through the
Lorentz number as (uf.,,7’)-’ and a remaining “inelastic”
part W. which is equal to W. = W., - (aLoT)-‘. The
“elastic” part corresponds to scattering of electrons
through large angles. This scattering mechanism is
Fig. 2. The theoretical function [(a In W,)/(a(ln V)+ 1/31/y vs equally effective in reducing both charge and heat flow,
T/O for 1. 2 and 3 electrons per atom, respectively, as given by and is dominant in W, at high temperatures. The “in-
Bohlin[lS]. Symbols denote experimental results, which are dis-
elastic” part W, corresponds to small-angle or “vertical”
cussed in the text.
scattering of electrons. This mechanism does not reduce
charge flow very much but may be very effective in
refer to A, and values corresponding to the total A are reducing heat flow, especially at low temperatures where
shown using open symbols. Bohlin’s expression for the W, = W.. At high temperatures W, decreases as W, =
pressure dependence of W, is based on a model which ATm2[21].Furthermore, in this temperature range W, can
neglects all Umklapp processes. This neglect leads to a be relatively easily calculated, the accuracy of the results
maximum in W&“/B), which has been observed being determined mainly by the accuracy of the electron-
experimentally only in a few metals [ 17,181, and thus to a phonon interaction potential used.
minimum in a(ln W,)/a(ln V). Bohlin’s formula would The “elastic” part of W, has in fact been previously
therefore tend to underestimate the pressure dependence studied through measurements of r. Accurate resistivity
of W, at intermediate temperatures, but at high T the measurements under pressure have been carried out for
agreement should get better. most metals, even as functions of temperature[23-251,
We can see from Fig. 2 that the agreement between and thus our measurements of W, do not give any new
theory and experiment is indeed excellent in the case of information on this quantity. Theoretical calculations of
gold and silver, for which T/e is fairly large. This the pressure dependence of (r give fairly accurate
agreement, however, is probably fortuitous in view of results[24-271, even if there still are numerical dis-
the fairly large expected errors. For comparison we have crepancies.
also plotted our previous results for ahrminium and To find the pressure dependence of W, only we have
copper. For copper the results differ appreciably from used previously published values [19,28-301 of the
the theoretical value. Copper shows no maximum in Lorentz function L, = A./UT to find the relative magni-
W,(T/fI)[19], and we should therefore expect Bohlin’s tudes of W, and W,. We have then calculated the pres-
analysis[lS] to underestimate the volume dependence of sure dependence of W, from our measurements on gold,
W,. It is reasonable to expect a more detailed cal- silver, copper [1] and aluminium[2] using values of u(P)
culation of [a(ln W,)/a(ln V)+ 1/9/r to give a value from Bridgmanpl, 321, and the results are shown in
somewhat larger than 2. The deviation from this expec- Table 1. In this table we also show the pressure
ted value is of the same order of magnitude as the mean coefficient of A as [A(O)]-‘dA/aP and the pressure
deviation in the experimental results [I], and it is possible coefficient [AJO)]-‘aA,/AP obtained by eliminating A,
that a large part of this deviation comes from experi- through eqn (2). The volume derivative a(ln W,)/a(ln V)
mental uncertainties. For aluminium the agreement be- has been calculated from the pressure dependence of A.
tween theory and experiment is very good. This and is shown together with a(ln W,)/a(ln V). As a
agreement is, in fact, rather unexpected. The Bloch- comparison we also show the same quantifies as cal-
Wilson expression[l6] for W, completely neglects culated from the experimental results of Starr[ lo].
Umklapp processes, and consequently the theoretical For all of the noble metals we find that the volume
W,(?‘/B) has a very large maximum, especially for a dependence of W, is clearly much stronger than the
trivalent metal like aluminium. Experimentally, only a volume dependence of the total W.. For gold W, Q W,
very small maximum is found[l8]. Since it is the maxi- and the results depend strongly on the assumptions in
mum in W&70) that gives rise to the minimum in the calculating the effects of A,, but for copper and silver the
function [a(ln W,)/a(ln V) + 1/31/y vs T/e, we would not errors should be. less. The strong volume dependence of
expect the Iatter minimum to be as deep as predicted by W, also gives an increase in the Lorentz ratio L, =
Bohlin’s theory. We would rather expect the curve to fall A,(aT)-‘. The pressure dependence of L, is shown in
only slightly below 2. We suspect, however, that the the last‘column of Table 1.
value [c,(O)]-‘&,/@ = - 1.8. 10e2GPa-’ given in [9] For aluminium we find, using our previous results[2],
 1136 B. SUNDQVIST and G. BKCK~TR~M

Table 1. Measured pressure dependences of A, A,, and W,, and the calculated volume dependences of W, and W,
for the noble metals and aluminium. For ahnninium the set of values marked with the superscript x corresponds to
values of aA/dP calculated using a theoretical value for ac,/aP. In the table we define D(y) I y-lay/#, P =0

Metal Reference O(l) D(Ae) - D(WJ a(ln "e) a(ln w ) WL,)

_.--K
(GPa-') (GPa-') (GPa-') a(ln V) a(ln V) (GPa-')

AU this work 3.9x10_' 3.8x10-' 30x10_' 5.8 45 0.6x10-'

1101 3.9 3.8 25 5.8 37 0.6

A9 this work 4.0 3.9 6 4.3 7 0.1

1101 4.4 4.3 13 4.7 14 0.5

CU [II 3.1 2.9 13 4.4 20 0.8

UOI 2.9 2.7 8 4.1 13 0.6

Al [2; 4.1 3.7 -3 2.9 -2 -0.9

[21X 5.0 4.6 5 3.6 4 0

that W, increases with pressure and that L, decreases. noted that very similar results for W, are found from the
Using instead a theoretical value of ac,,/aP as indicated results of Starr[lO], and thus we do not believe that our
above we find that W, decreases under pressure, having measured values of A(P) are very much in error.
approximately the same pressure coefficient as the total From Bohlin’s formula[l, 2, IS] for W, we find that
W,. The Lorentz ratio L, thus stays approximately for a free-electron metal the pressure coefficient of W,
constant under pressure. For aluminium the results for should be very small at high temperatures, and a similar
W, are thus rather inconclusive, indicating only that the result can also be derived from Laubitz and Cook[21].
pressure coefficient of W. is small. The probability of vertical transitions, however, must be
The strong pressure dependence of WV for the noble rather sensitive to the area of the Fermi surface. Direct
metals could be explained by an error in the calculation measurements[33] show that the distortions of the Fermi
to subtract A,. However, eqn (2) usually overestimates surfaces for the noble metals increase strongly under
the pressure dependence of h,[12] which would instead pressure. The Fermi momentum kF on the “belly” of the
tend to reduce the pressure dependence of W,.It would surface inreases more slowly with pressure than simple
also be possible that we have used too small absolute volume scaling would indicate, while the area of the
values of AP The values used, however, are generally “necks” increase five to ten times faster than they
accepted as being reasonably accurate. It should also be should. This might mean that the Fermi surface area
Table 2. A collection of all available accurate experimental data for the volume dependence of A for metals about
room temperature. Also shown are the volume dependences of W., W. and 15~.As in Table 1 two sets of values are
shown for aluminium

Metal Reference T a(ln a) a(ln W,)/a(ln V) 3(ln W ) a(ln L )

v --A-
(K) a(ln'V) exp. theory 1151 a(ln V) 3(ln V)

AU This work 315 -5.9 5.8 5.7 45 0.9

1101 273 -5.9 5.8 5.6 37 0.8

A9 This work 315 -4.5 4.3 4.4 7 0.1

1101 273 -4.9 4.7 4.3 14 0.5

CU 111 310 -4.7 4.4 3.3 20 1.2

[lOI 273 -4.4 4.1 3.2 13 0.9

Al 121 315 -3.3 2.9 2.8 -2 -0.7

i21X 315 -4.0 3.6 2.8 4 0

Pb 1351 303 -7.2 6.9 (4) 0.6

Sn L351 303 -7.1 6.7 (3.8) - 0.8

 Thermal conductivity of gold and silver at high pressures
increases more slowly under pressure than the free elec-
tron model indicates and thus that the relative proportion
of vertical scattering decreases, giving a strong relative
decrease in WVfor these metals. For aluminium, on the
other hand, the change in the average &F can be
described to within 1% up to 10 GPa by the free electron
model, as found experimentally through positron anni-
hilation experiments[34]. This would explain the small
a W,/aP found for this metal.
In Table 2 we have collected all available accurate
experimental data on the pressure dependence of A, W,
and W. for metals at room temperature. Data are taken
from this work, Refs. [l, 2, IO], and Bridgman’s[35]
results for lead and tin, using a radial heat flow method.
All data have been reduced to the basic volume depen-
dence to facilitate a comparison with theory. The
experimental volume dependence of W, is compared to
the theoretical predictions by Bohlin 1151. As the Fermi
surfaces of the polyvalent metals are quite complicated
we would not expect this model to give valid results for
these metals. The predictions are fairly good, however.
For lead and tin we do not consider the experimental
accuracy high enough to warrant a calculation of W,.
The rather strong volume dependnece of L. suggests a
strong volume dependence of W,, but this could also be
due to experimental errors.
In conclusion we can say that the pressure dependence
of A, for simple metals can be fairly accurately predicted
by free-electron theory. The fact that the electronic
Lorentz function L. increases under pressure for all
metals examined, except possibly aluminium, could be
used to examine further the inelastic or “vertical” scat-
tering of electrons by phonons. Since the pressure
dependence of L= is rather small, however, it might
conversely be possible to obtain information on A, for
metals or alloys having a high proportion of lattice
thermal conductivity by comparing the pressure depen-
dencies of the thermal and electrical conductivities.
Acknowledgemenf-This work was financially supported by the
Swedish Natural Science Research Council.
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