Spectra.: Structure of F
Spectra.: Structure of F
Spectra.: Structure of F
2029
by F. Seitz and D. Turnbull (Academic, New York, 1958), 23Although Hughes's curves are densitometer traces,
p. 353. the experimental procedures followed were such that the
~VJ. T. Ritter, J. Chem. Phys. ~53 3461 (1970). results should be proportional to the absorption coeffi-
Handbook of Mathematical Eunctions saith Formulas, cient, or nearly so tA. E. Hughes (private communica-
G~aPhs, and Mathematical Tr. bles, 3rd ed. , Natl. Bur. tion)]. In any case, the quantitative significance of the
Std. Appl. Math. Ser. 55, edited by M. Abramowitz and experimental results is not of major importance for our
I. A. Stegun (U. S. GPO, Washington, D. C. , 1965), primary purpose, which is to illustrate our computation-
pp. 928-935. al approach.
Eormulae and Tables for Statistical Sbrk, edited by 4A. M. Karo and J. B,. Hardy, Phys. Rev. 141, 696
C. R. Rao, S. K. Mitra, and A. Matthai (Statistical (1966).
Publishing Society, Calcutta, India, 1966). G. Raunio, L. Almqvist, and R. Stedman, Phys. Hev.
G. F. Imbusch. W. M. Yen, A. L. Schawlow, D. E. 178, 1496 (1969); J. R. D. Copley, R. W. Macpherson,
McCumber, and M. D. Sturge, Phys. Rev. 133, A1029 and T. Timusk, ibid. 182, 965 (1969).
(1964) . 26J. E. Ralph and M. G. Townsend, J. Phys. C 3 8
2~A. E. Hughes, Proc. Phys. Soc. (London) 87, 535 (1970).
(1966). C. C. Klick, D. A. Patterson, and R. S. Knox, Phys.
22C. B. Pierce, Phys. Rev. 148, 797 (1966). Rev. 133, A1717 (1964).
/". IO
Io"
O. -Quartz
~o II C Axis
IO-'
S
Io
l
IO
I.o IO IOO Iooo
Temperature, 'K
I.o
I I
IO
I
loo
the conductivity were as low as it could possibly be, Temperature, K
corresponding to a diffusion of the vibrational en-
FIG. 3. Comparison of the thermal conductivity of vit-
ergy from one atom to the neighboring ones. But reous silica with that of the polymer PMMA (Befs. 14-17)
this is not the case. A crystal containing as few sobd varnish (GE 7031) (Ref. 18), vitreous selenium
as 0. 1% of foreign ions can have a conductivity lower (Ref. 12), and vitreous Geo2 (germania) (Ref. 19). The
than that of the glasses (see Fig. i). If an average curve for silica is a composite curve after Fig. 2.
THERMAL CONDUCTIVITY AND SPECIFIC HEAT OF. . .
nant lattice vibrations or 10 intermolecular spacings.
Qnly Rt the highest temperatures, where glasses Rnd
crystals have approximately equal conduetivities,
is l of the order of the intermolecular spacing,
i. e. , 10 7 em. 2' We will return to this point later
in Fig. 9. Consequently, the problem has to be
stated as follows: Why do all noncrystalline solids
have the same (high) conductivity at low tempera-
tures, and why do Rll the curves have the same
characteristic shape with a plateau in the neighbor-
hood of 10 'K'P This question was the starting point
for the present investigation.
Two models have been suggested to explain the
conductivity of glasses. In the first model,
Klemens proposed tllat the scRtterlng 18 cRused
by spatial fluctuations in the sound velocity and by -7 l l I
tudinal ones. At temperatures below the plateau FIG. 4. Specific heat of vitleous Si02 and CFy'stal
(10 'K), the heat is mainly carried by longitudinal quartz, plotted as C„T vs T. A: I. R. Vitreosil (Ref.
29) B. vitreous silica (after Refs. 30-32); C &-quartz
phonons, which are uncoupled fxom the transverse {after Refs. 29, 33, and 34). The bvo short dashed lines
yhonons. At around 10 'K, the onset of the anhar- indicate the specific heats calculated from elastic mea-
monic interaction couples the phonons in the dif- surements: For vitreous silica, C„, = 8. 07 & 10 ? (W sec
&
ferent branches and hence lowers the mean free g ~'K 4)T3, calculated from v~„, 1 =4. 1&& 105 em sec (Ref.
,
path of the longltudinRl phonons, which cRu8es the (
25). For crystal quartz Co e& =5. 5+ 10? see g ~ K ~)T
plateau. Eventually, the conductivity increases calculated from v~~ e& =4. 4&&105 cm sec ~ (Ref. 35). See
Rgain becRuse the speclflc heat lncreRses. As Rn also Table I. The dashed curve shows CvT 3 for quartz
in the Debye approximation for a Debye temperature of
alternative model, Klemens" proposed that in non-
552'K (based on the number density of cggoms in the
crystalline solids the heat carrying plane-wave quartz).
phonons are resonantly scattered by local. ized
phonons in a way similar to the resonant scatter-
ing found in crystals containing substitutional model has also been applied to Se" Rnd, GeQ2, and "
molecules with low-f requency quasi. rotational de- it has been concluded that the frequencies needed
grees of freedom (see Fig. 1) or in crystals con- to explain the phonon scattering do agree with the
taining defects causing resonant modes. 28 Such a frequencies of these excess modes.
scattering, in particular, could explain the plateau Both the structure scattering and the localized
occurring in the temperature region in which most mode scattering do not give a plausible reason for
of the heat is carried by yhonons whose frequencies a particularly important experimental fact, namely,
are close to those of the spatially localized modes. that all noncrystalline solids have practically iden-
These modes should be observable in the specific tical thermal conductivities. This fact suggests
heat of glasses. It is known that the low-tempera; that the scattering must have a very simple origin,
ture specific heat of the same substance in the extremely independent of structural details or the
5C
ple to bath time constants shown in Fig. 6. Heat
0 PMMA
1 pulse duration was varied between 0. 5 and 2 sec.
~ IO5
41
The time constants for the thermal equilibration
I/J
TABLE I. Specific-heat samples used in this investigation. Also listed is room-temperature mass density, molecu-
lar weight, and the O'K Debye sound velocity ez as calculated from elastic measurements, except for Se {see footnotef).
Temp. Mass
Mass range density Molec. Vg
(g) ('K) (g cm"3) weight (10~ cmsec ~)
-quartz
G'. Valpey 44. 0 0. 8 —2. 0 2. 6 60. 09
0'-quartz Valpey 122. 9 0. 1-0.9
Speetrosil B Thermal American 29. 0 0. 3-2. 0 60. 09
Spectrosil B Thermal American 110.0 0. 13-0.8
Pyrex 7740 " Corning 43. 0 0. 3-2. 0 3. 65'
Pyrex 9700" Corning 46. 0 0. 3-2. 0
Vitr. Se Xerox' 53. 6 0. 1-1.5 4. 25 78. 96 1.54'
Vitr. Ge02 Cornell 57. 3 0. 08-1.8 3.6 104. 6 2. 6~
81Br (cryst. ) Cornell" 39.7 0. 08-1.2 3.43' 165.4 1.59'
~After Ref. 35. 'Sample kindly supplied by Dr. Mark Myers, Xerox
Approximate composition (by weight): Si02 80. 5%, Research Laboratory.
f Since elastic data were unavailable,
8203 12. 9/0, Na20 3. 8%» Al203 2. 2%» K20 0. 4%» and the value listed
Li20 0. 2%. was calculated from the specific heat of the crystalline
After %. P. Mason, in American Institute of Physics phase, see I. C. Lasjaunias, Compt. Rend. B269, 763
Handbook (Mcoraw-Hill, Neer York, 1963), pp. 3-88. 0.969).
Extrapolated to 0 'K. gAfter Ref. 47.
Approximate composition (by weight): Si02 80%» "Same sample as the one studied in Ref. 50.
8203 13%, Na20 5%, and Al203 2%. This sample was After J.
T. Lewis, A. Lehoezky, and, C. V. Briscoe,
kindly supplied by Dr. A. A. Erikson, Corning Research Phys. Bev. 161, 8VV (196V). Mass density quoted is the
Laboratory, one at 4'K.
2034 R. C. ZELLER AND R. O. POHL
quartz tube and quenched in air after melting. ~ The 10 I
l
I I l
I
.I I.O lO
proportional to the temperature. Thus, if C„and v FIG. 8. Thermal conductivity of vitreous silica, Pyrex
are known, l (va, ) can be determined from the ex- 7740, and selenium between 0. 06 and 100'K and of alumin-
periment with the help of Eq. (1). A simple esti- ogermanate glass between 1 and 100'K. For comparison
mate of the error to be expected if this method is included is the conductivity of vitreous Ge02 (Fig. 3 and
used to determine the frequency dependence of the Ref. 19). Our data on vitreous silica and on Pyrex 7740
agree closely with those obtained by Herman (Ref. 2).
phonon mean free path was made as follows: The
The data on Se are twice as large as those reported in
phonon scattering rates 7 „', (&o) resulting from iso- Ref. 12. As far as we know, this is the only case where
topic mixtures in crystals are known both from the conductivity of a noncrystalline solid has been found
theory and experiment. s %Ye analyzed the thermal to be sample dependent. This difference may result from
conductivity data obtained on Ge crystals of dif- a difference in sample preparation: White et g$. (Ref. 12)
ferent isotopic compositions' with the dominant- quenched their sample in water; our sample was cooled in
phonon approximation and obtained a relaxation air.
rate g „', (or~, ) which varied as the fourth power of
frequency and which differed from the theoretically
predicted rateg6 r, '„(~)by less than a factor of 2. possibly introduced by not using the vitreous spe-
Another test for the validity of the dominant-phonon cific heats will be discussed below, but it is negli-
approximation, involving phonon resonance scat- gible for the present discussion, which deals with
tering, was performed by Narayanamurti and Pohl. " temperatures above 1'K. The sound velocities
used were the ones listed in Table I. At high tem-
III. EXPERIMENTAL RESULTS AND DISCUSSION peratures, the mean free paths for crystalline
and vitreous materials alike approach the order of
A. Thermal Conductivity
a few angstrom, i. e. , the interatomic separation,
The thermal conductivities of vitreous and crys- as is to be expected. As the temperature decreases,
talline SiO~ measured in this investigation have been the mean free path increases very rapidly (almost
compared in Fig. 1. In Fig. 8 we compare the con- exponentially) in the crystal. The mean free paths
ductivities of several vitreous materials. As we in the vitreous samples also increase, although not
pointed out in the introduction, all noncrystalline as rapidly, and with no sign of a resonance scatter-
materials have practically identical conductivities. ing process. In the region around 10 'K, the mean
This is confirmed by our measurements. Our data, free path in these samples varies approximately as
which extend to lower temperatures, show that the the fourth power of the temperature, or in the dom-
conductivities vary as T" with n-1. 8, below 1'K. inant-phonon approximation,
The mean free paths, determined for quartz, vi- l ~ etta, m (3)
treous silica, germania, ' and selenium with the
((d aom) r
help of Eq. (1) in the dominant-phonon approxima- reminding us of a Rayleigh scattering process.
tion, are compared in Fig. 9. The specific heat Static point defects, such as foreign atoms, vacan-
used for this analysis was that of the crystal phase, cies, interstitial atoms, or isotopes in crystal
except for GeO„ for which the specific heat is lattices, cause such phonon scattering.
available only for the glassy phase. 7 The error %e attempt to explain the observed mean free
THERMAL CONDUCTIVITV AND SPEeIFIC HEAT OF. ..
OOMI
IO
I I
IO
~ ~
IO
I ~
IO I A bers to perform thermal conductivity experiments.
i
On the other hand, it is known from numerous
~ ~
slop
P OOM IOIO 10 IO Io' sec-'
studies that the phonon scattering in crystals con-
I I /
I I
I
I I I
I
20
expected to influence the electric yolarizability,
Fiory measured the dielectric constant of a piece
'.
e IO-
of vitreous silica cut off from one of our specific-heat Cl 5
samples, at temperatures above 0. 1'K, in the fre- I
I-
quency range 102-10 sec '. The dielectric constant 20- b
20
decreased with decreasing temperature, and was IO— / —IO
/
temperature independent below 0. 5 K to within the /
/
experimental resolution. With the assumption that /~a T~
/
the yolarizable ions have dipole moments of order
1 debye (uncorrected for local fields), Fiory's
measurements lead to an upper limit of 10'6 cm ' .OI
I
IO
Science Center for actually producing it. Dr. J. ials Science Center performed the spectrochemical
Both of the Analytic Facility of the Cornell Mater- analyses on the Pyrex.
*Work supported by the U. S. Atomic Energy Commis- Center Report No. 1453 (unpublished).
sion under Contract No. At(30-1)-2391, Technical Report 5Charles Kittel, Phys. Rev. ~75 972 (1949).
Additional support was 26P. G. Klemens, Proc. Roy. Soc. (London) A208, 108
No. NYO-2391-130 (unpublished).
received from the Advanced Research Projects Agency (1951).
2~P. G. Klemens, in Ref. 20, p. 162.
through the facilities of the Materials Science Center at
Cornell University, Material Science Center Report No.
~
R. 0, Pohl, in Localized Excitations in Solids, edited
1556 (unpublished). This work is part of the M. S. thesis by IL F. Wallis (Plenum, New York, 1968), p. 434.
of R. C. Zeller submitted to the Cornell Graduate School 296. K. White and J.
A. Birch, Phys. Chem. Glasses
(unpublished). We also refer to this thesis for a review 6, 85 (1965).
of the work up to 1970 on the thermal conductivity, spe-
3
P. Flubacher, A. J. Leadbetter, J. A.. Morrison,
cific heat, elastic properties, and light scattering and and B. P. Stoicheff, J. Phys. Chem. Solids ~12 53(1959).
absorption performed on noncrystalline solids, Materials
3
F. Simon, Ann. Physik 68, 241 (1922).
Science Center Report No. 1453 (unpublished). F. Simon and F. Lange, Z. Physik 38, 227 (1926).
)Present address: Department of Physics, Northamp- E. F. Westrum, Jr. , in Proceedings of the
I'ourth
ton County Area Community College, Bethlehem, Pa. International Congress on Glass, Paris, 1956 (Chaix,
18017. Paris, 1956), p. 396.
A. Eucken, Ann. Physik 34, 185 (1911}.
3
B. Wietzel, Z. Anorg. Allgem. Chem. 116, 71 (1921).
. , ( 3~0. L. Anderson, J. Phys. Chem. Solids 12, 41 (1959).
y
38ee Charles Kittel, Introduction to Solid State Physics, E. F. Westrum, Jr. , in Thermodynamics and Trans-
3rd. ed. (Wiley, New York, 1966), Chap. 6. Port Properties of Gases, Liquids and Solids (McGraw-
Wo Do Sewal d and V. Narayanamurtl, Phys e Reve Hill, New York, 1959), p. 275.
463 (1966). YC. T. Anderson, J. Am. Chem. Soc. 59, I036 (1937).
5R. A. . Fisher, G. E. Brodale, E. W. Hornung, and W. Desorbo, J. Chem. Phys. 21, 1144 (1953).
W. F. Giauque, Rev. Sci. Instr. 40, 365 (1969). 39Jean-Claude Lasjaunias, Compt. Rend. 269, B763
6E. H. Ratcliffe, Glass Technol. 4 113 (1963). (1969).
H. E. Seeman, Ph. D. thesis (Cornell University, 4oG. E. Gibson and W. F. Giauque, J. Am. Chem. Soe.
1927) (unpublished). 45, 93 (1923).
8R. A. Fisher, G. E. Brodale, E. W. Hornung, and 4~J. E. Tucker and W. Reese, J. Chem. Phys. 46,
W. F. Giauque, Rev. Sci. Instr. 39, 108 (1968). 1388 (1967).
A. C. Anderson, W. Reese, and J. C. Nheatley, Rev. B. Dreyfus, C. Fernandes, and R. Maynard, Phys.
¹