J. Pkys. Ckem.

Solids

Pergaman Press 1960. Vol. 15, pp. 17-26.

Printed in Great Britain.

THERMAL AND

PROPERTIES TANTALUM

OF GRAPHITE, TO THEIR

MOLYBDENUM

DESTRUCTION

TEMPERATURES~
N. S. RASOR and J. D. MCCLELLAND Atomics International, A Division of North American Aviation, Inc., Canoga Park, California (Received 9 iVovenzber 1959) Abstract-Thermal expansion, specific heat and thermal conductivity have been determined from 1ooOC to near the destruction temperature of molybdenum {m.p. 262O*C), tantalum (m.p. 3~OOC) and four types of graphite (sublimes at 365OC). The thermaf expansion data for the materials investigated show no ~rossly~usual features except those due to impurity evolution. The specific heat of the metals, p~ti~ularlythat of molybdenum, appreciably exceeds the Dulon~Petitvalue. However, their thermal conductivities fotfow closely the Lorenz (Wiedemann-Franz) relation for free electrons. At intermediate temperatures ~1000-2~OOC} the thermal conductivity and specific heat of graphite show no unusuai features. At higher temperatures, however, large and rapid increases in specific heat and thermal resistivity appear, which are consistent with the occurrence of thermally produced lattice defects, presumably vacant lattice sites. A defect concentration of about 0.5 atomic per cent at the sublimation temperature, and a formation energy in the vicinity of 7.7 ev, are indicated. 1. I~ODUCTION

LITTLE info~ation exists concer~ng the thermal properties of materials above XSWC. In addition, considerable disagreement may be found in the results reported by various workers in the temperature region immediately below 15OOC, making confident extrapolation of the properties to higher temperatures difhcuit or impossible. This void in the technical literature is due partially to the rapidly increasing experimental di~~ulty at higher temperatures, and partially to the relatively Limited utilization of the higher temperatures in industrial technology in the past. Recent engineering requirements for materials which can function at very high temperatures demand that data for engineering evaluation be obtained in this region. Such data will also permit extension of the physics of solids into the temperature domain which distinguishes refractory solids as a unique class of materials. In the present work, thermal expansion, specific heat and thermal conductivity have been determined from 1000C to near the destruction _--._.__ * Supported by the United States Air Force under
B

t?mperature of molybdenum ~meIting point 26Z~O~~ tantalum (melting point 3OOO*C~ and graphite (sublimation point 3650C). Afthougb the data were obtained primarily for use in engineering evaluation, many of the effects observed can be interpreted in the light of existing theories of the solid state. 2. METHODS
AND SPECIMRN MAIMZUS

Contract AF33(616)-2909.

Thermal expansion and specific-heat determinations were carried out in a specially designed carbon-tube furnace. Thermal expansion was determined by measuring the distance between fiducial marks on the specimen, using filar telescopes with micrometer eyepieces. Specific heat was determined from the rate of temperature increase resulting from uniform electrical heat dissipation in the specimen. Thermal conductivity was determined between 1000 and 2700C by passing heat from an external heater through a cylindrical shelf specimen to a heat sink along its axis. Conductivity was calculated from the radial temperature drop across the specimen and the heat flow into the heat sink. A carbon helix furnace was constructed especially
17

18

N.

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and

J.

D.

MCCLELLAND

Table 1. Impurity

content of metal specimens

Impurity content (p.p.m.)

Sample

, -4y;;is

,__------__,___ ~ Si
1 Cr 47 23 3 3 / Cu ---

~
Al Ca ___-

--Ta Before After

1 Ni , 1 900

~ i Zr
7300

Co ---I--

i Fe / 2100

Mn 300

~ Ti
j 0

I /

--__
MO

~-

200 ~ 130
730 630

----

1 7300 ~ 170 j 19; 0 i

130 130

1 33 1

i 700

~ 800

Before After

/ I

0 0

for this method. At temperatures above 2700C thermal conductivity was determined from the center-to-surface radial temperature drop resulting from uniform electrical heat dissipation in a specimen rod placed in the carbon-tube furnace. Purified argon or helium was used throughout as the furnace atmosphere. Optical and photoelectric pyrometers were used for temperature measurement. Details of the construction and operation of the experimental apparatus are given elsewhere.(l* 2) Arc-melted unalloyed molybdenum for property determinations was obtained from Climax Molybdenum Company in the form of swaged rods 2 in. and $j in. diameter, having the theoretical maximum density (10.22 g/ems.). The tantalum used was obtained from Fansteel Metallurgical Corporation, which manufactured the bulk metal by pressing and sintering powder. The sintered bar was then savaged to $ in. dia. rods or rolled to 2 in. thick plates whose density (16.66 g/ems) approached the theoretical maximum density. Table 1 gives the Table 2. Characteristics

results of a chemical and spectroscopic analysis of the impurity content of the metal specimens as received, and after heating to near their melting temperatures in the course of the thermal property determinations. These results are typical for all specimens used in the various property determinations. It may be seen that the composition of the molybdenum was not changed significantly as a result of heating to near its melting temperature. However, the heating substantially reduced or completely removed the impurities initially present in the tantalum. Property determinations were made on four types of graphite with the characteristics listed in Table 2. Since the behavior of the Speer Carbon Company types is representative of the group, some of the data on the National Carbon Company types will not be presented here, but may be found elsewhere. (2) The manufacturers cooperated by delivering material only from specified locations in the bulk graphite forms, and a record was kept of the orientation of each specimen. To avoid of graphite types

I
Manufacturer

Type
3474D 7087

Method of forming

Spew Carbon Company ---____National Carbon Company GBH GBE molded extruded

/ Anisotropy I ratio*
_I

~ Specific
Gravity 1.67 1.63

~ I

Structure Very fine-grained and uniform. Coarse-grained with small voids and fissures. Very fine-grained and uniform. and coarse-grained Extremely fragile. Voids and fissures up to + in. dia.

j extruded
extruded

1.08 1.19

0.780 1.18

1.77 1.57

* Ratio of electrical

resistivity normal and parallel to the extrusion axis or molding pressure.

THERMAL

PROPERTIES

OF

GRAPHITE,

MOLYBDENUM

AND

TANTALUM

19

density and orientation variations which occur near the surface of the bulk forms, specimens were taken from the center regions only.
3. THERMAL EXPANSION

The thermal expansion results obtained for molybdenum and tantalum are given in Fig. 1.
3.0 TANTALUM IST HEATING .- LST COOLING V- 2N0 HEATING
A-

could be consistently reproduced to within f 0*0003 in, (0.003 per cent of the specimen length). Above lOOOC, the solid curves in Fig. 1 representing thermal expansion upon initial heating are plots of the equation: E= -

L-Lo
LO

= A+BIT,+CT,

(1)

//

where

L is the specimen length at temperature T, T, = T-20C (i.e. the difference between test

20 s _ g 9 s w 1.0 I ST COOLING -

and room temperature); Lo is the room-temperature length; and A, 3 and C are constants determined from the experimental data. The coefficient of thermal expansion Mmay be obtained by differentiation of equation (l), yielding: x = ; = B+2CT,2.

The values of A, B and C are tabulated in Table 3. The thermal expansion results for two types of graphite in directions both normal and parallel to the crystallographically preferred orientation are

0 500 1000 1500 2000 2500

3CccI

TEMPERATURE,OC

FIG. 1. Thermal expansion of molybdenum and tantaium.

Both metals show a small permanent elongation as a result of the initial heating, but no further permanent elongation was observed upon heating a second time. Measurements on an additional specimen of each metal confirmed the data shown in Fig. 1 within the experimental error. The precision of the elongation determinations was limited by refraction effects introduced by temperature variations in the sight tubes. However, readings

IO00 xt&zmIE:c

3cm

4000

FIG. 2. Thermal expansion of type-3474D graphite.

given in Figs. 2 and 3. All types showed a slightly different behavior upon initial heating than during subsequent cooling and heating. The data above and tantalum above 1000C

Table 3. Expansion equation coeflicients for initial heating of mo~bd~um

__ A
Molybdenum Tantalum 6.00 x 8.97 x
10-4 10-4

B (c-l) 2.95 x10-s 4.80 x IO-6

-.

c (T-2)
2.00 x10-s 144 x 10-9

20

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and

J.

D.

MCCLELLAND

1000C for the direction normal to the forming pressure* upon initial heating were found to be accurately represented by the relationship :

The metal specimens generally appeared bright and untarnished after being heated. No visible change was generally observed in the appearance

E = D+ET,+FT,3/

(2)

TEMPERATURE,C

graphite.

FIG. 3. Thermal

expansion of type-7087

A /
I

It was not possible to represent the curves for the parallel direction by a simple analytical expression. The coefficient of thermal expansion obtained from equation (2) is:

4 ,/ -

IH

TO MOLDING

PRESSUREf

s( = E+-

3 2

FT,3s

(3)

0
500 1000 1500 2000 2500 3000 3500

Values of the constants D, E and F are tabulated in Table 4. For a more convenient comparison of the expansion coefficient dc,equation (3) is plotted in Fig. 4 for the initial heating curves, using the constants in Table 4. * This pressure is normal to extrusion axis or parallel to molding pressure. Table 4. Ex$ansion equation

TEMPERATURE,C

FIG. 4. Coefficient of thermal expansion of four types of graphite.

of the graphite specimens even after several excursions to the vicinity of 3650C. The results in Fig. 1 generally agree with the empirical rule that metals expand approximately normal to forming pressure

coeficients for graphite above 1000C

~ DUO-3) 0 0 0 0 1.29 0.11 1.10 164 ~

Graphite type 7087* 3474D* GBEt GBHt 7087* 3474D* GBEt GBHt

History

E (1O-7/0C) 21.7 9.47 -8.27 6.95 -2.47 4.20 -3.38 4.53

1 F(lO-s/C35
4.98 4.59 8.56 8.18 8.40 5.44 7.26 7.79

Initial heating

Subsequent cooling

* National Carbon Company types. t Speer Carbon Company types.

THERMAL

PROPERTIES

OF

GRAPHITE,

MOLY3D~~UM

AND

TANTALUM

21

2 per cent before melting. The smooth character of the curves and the conformity to the usual quadratic-expansion relation indicates that no major change of structure has taken place in these metals in the temperature range covered. The c-axis of the graphite crystailites tends to be oriented preferentially parallel to the forming pressure in the manufactured forms. The observed larger expansion in these directions is to be expected, since this is the direction of smallest elastic modulus in graphite. It may be seen in Fig. 3 that, parallel to the forming pressure, type 7087 exhibits a curious hump in the expansion curve during initial heating, centered at about 2700C. Repeat tests on different specimens confirmed the existence of such a hump in both types 7087 and GBH and indicated that the magnitude of the effect depended on the time-temperature history of the specimen during the test. Since the effect occurs in a temperature region close to or above the temperature at which the graphite was manufactured, it is likely that it is due to further graphitization (or purification) taking place as the temperature is increased above this value. The absence of the effect in the cooling portion of the data indicates that graphitization {or ~u~~ca~ou) is indeed the cause of the effect in the heating portion. The failure of the effect to appear in types 3474D and CUE is probably due to their being subjected to a higher temperature during manufacture, resulting in graphitization being carried to completion, The absence of the hump in the expansion data for the other directions in types 7087 and GBH (specimen axis normal to the preferred orienta.tion of the c-axis) is consistent with the hump being due to an irreversible change in the c-axis spacing. Indeed, X-ray analysis@) showed a 0.23, O%, 0.04 and 0.00 per cent reduction in the c-axis spacing for types 7087, GBH, GBE and 347413, respectively, due to the heating cycle. This is approximately the same magnitude as the humps in the respective expansion curves. A thermally induced change in the number of interstitial atoms between the graphitic planes could readily account for such a change. It should be stated here that, upon heating, all specimens of type 7087 graphite evolved a considerable amount of odorous vapor, which partially condensed as a lacy white deposit. Much smaller

amounts were observed for types GBH and GBE, and none for type 34741). This correlation with the above effects therefore strongly suggests that the interstitial atoms giving rise to the above effects are impurities.

The specific-heat values obtained for molybdenum and tantalum are shown in Fig. 5. The
.14,r, .I 1

FIG. 5. Specific heat of molybdenum

and

tzmtafum,

results for the four types of graphite described in Table 2 are shown in Fig. 6. The heating cycle was repeated for the original specimen of 7087 and for an additional specimen of all types except GBE.

FIG. 6. Specific heat of four types of graphite.

The results agreed well with those shown in Fig. 6. The specific-heat curves obtained are estimated to be accurate to within f5 per cent. Due to plastic flow, all specimens sagged somewhat under their own weight near their destruction temperatures. This was only a relatively

22

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and

J.

D.

MCCLELLAND

small effect for graphite at 3700C and molybdenum at 2600C. However, sagging of the tantalum specimens above 2500C was so severe as to prevent reliable data from being obtained at higher temperatures by the pulse method. A continuous-heating method,@) using 0.040 in. dia. wires, was used to extend and confirm the data obtained on the rods, and the results are included in Fig. 5. The curves below 1600K in Fig. 5, and below 1100K in Fig. 6, represent previously published experimental data(b) and may be seen to be in satisfactory agreement with the present results. However, the present results are in serious disagreement with published values obtained(s) by extrapolation into the previously unexplored hightemperature region. According to the Dulong-Petit law, the specific heat at high temperatures should approach a fairly constant value of ~6 cal/moleC (~0.062 Cal/g C for molybdenum, O-033 for tantalum and 0.50 for graphite). The amount by which molybdenum and tantalum exceed this value is much larger than can be explained by the difference in specific heats at constant pressure and volume. Large deviations, such as are observed here, are commonly attributed to an electronic contribution to the specific heat, which should be linearly dependent on temperature for a uniform distribution of electronic energy states. A large, rapidly increasing specific-heat behavior, similar to that observed here for molybdenum, has been reported(7) for chromium, which has an electronic structure quite similar to that of molybdenum. The non-linearity occurring at the higher temperatures in Fig. 5 may be due in part to the thermal formation of lattice imperfections, to be discussed later. It may be clearly seen from Fig. 6 that the specific heats of the four graphite specimens investigated are identical within the experimental error. The fact that the values obtained for type GBE appear consistently lower than those for the other types is probably due to the large inhomogeneity of this type. The local density at the point of property determination was probably different from the average density as determined from the bulk sample. The conformity among the various types and the approach to a saturation value above 2200C (the higher Debye temperature for graphite) are in

excellent agreement with the Dulong-Petit law, indicating little electronic contribution. The most striking feature of the data is the abrupt but reversible rise in specific heat above 3300C. Analysis of the temperature dependence of the specific heat in excess of the observed saturation value indicates that it is due to a thermally activated process; i.e. it is proportional to exp(-E/U), where K is the Boltzmann constant. The activation energy E appears to be in the vicinity of 7.7 eV/atom, which leads to two possible interpretations of the effect. Since 7.7 eV is approximately equal to the heat of vaporization for graphite, it is possible that the effect may be spurious and related to the rapid rise in vapor pressure that occurs at these temperatures. However, a detailed analysis of the transient diffusion of carbon vapor from the specimen surface during the heating interval indicates that heat is not removed by vaporization at a rate sufficiently large to account for the observed effect. Alternatively, the effect may be due to the reversible thermal formation of lattice defects that must exist in an equilibrium concentration characterized by an activation energy equal to their energy of formation. Since the activation energy observed is approximately the heat of vaporization of monatomic carbon@) (7.4 eV), elementary considerations suggest that the defects produced are vacant lattice sites (vacancies). An effect similar to the one observed here has been reported(s) in the specific heat of sodium, lead and aluminum near their melting temperatures and ascribed to vacancy formation. Since the vacancy formation energy in these metals is in the vicinity of only 1 eV, the effect is much smaller in magnitude and spread over a proportionately larger temperature interval than in the case of graphite. The excess area under the specific-heat curve resulting from the present effect is equal to an energy which is assumed to be the total energy stored in the vacancies at a given temperature. Therefore, using the known formation energy per vacancy and the magnitude of this excess area, the vacancy concentration may be computed. For lead and aluminum, the concentration reported was O-2 atomic per cent at the melting temperatures, which is quite reasonable according to the vacancy theory of melting. If the excess area under the present specific-heat curve for graphite is divided

THERMAL

PROPERTIES

OF

GRAPHITE,

MOLYBDENUM

AND

TANTALUM

23

by 7.7 eV, the concentration obtained is 0.5 atomic per cent at the sublimation temperature, 3650C. Thus, if it can be assumed that sublimation is equivalent to melting as an indication of the instability of the solid phase, this result is strong confirmation that vacancy formation is responsible for the observed abrupt increase in the specific heat. The equation which includes an exponential vacancy formation contribu~on to the heat content, assuming a 7.7 eV formation energy and O-5 atomic per cent vacancies at 365OC, is: c P = o 52+(4.7x

lo=)

T2
x

(4)

x exp [ -8.9

104/T]cal/g-C,

tantalum and molybdenum were in satisfactory agreement with published value&) and thus will not be repeated here. The resistivity observed for type-3474D graphite, shown in Fig. 7, is typical of that observed for the other types. It should be emphasized, however, that the few per cent deviation from a linear extrapolation above 2800C may result from spurious thermionicemission effects. The resistivity data are presented here primarily because of their significance in relation to the interpretation of the speciik-heat and thermal conductivity data. Thus, the smooth character of the resistivity curve indicates that the large abrupt changes observed in the thermal properties above 3000C are not the result of a spurious change in electrical power input to the specimen.

where T is in IX. The curve in Fig. 6 above 2200C is a plot of this equation and maybe seen to represent the observed data adequately.

iXl

FIG. 8. Thermal TEMPERATUREPC

conductivity of molybdenum talum.

and tan-

Frc.

7. Electrical resistivity of type-3474D parallel to extrusion axis.

graphite 5. THERM4.L CONDUCTIVITY

Vacancy formation should also contribute to the specific heat of molybdenum and tantalum. However, theoretical computations using reasonable formation energies for these metals (between 2 and 3 eV) and vacancy concentrations (0.3 per cent at melting points) indicate that vacancy formation could account for only a small part of the observed excess specific heat, as may be seen in Fig. 5. Thus, except possibly for the slight non-linearity at the higher temperatures, the high values observed are probably due principally to the electronic specificheat contribution. Electrical resistivity of the specimens was determined as a by-product of the specific-heat determinations. The resistivities obtained for

The thermal conductivities of molybdenum and tantalum to 25OOC, obtained by the externalheating method, are shown in Fig. 8. The thermal conductivities of two types of graphite are given in Figs. 9 and 10. For comparison, data obtained from the observation of the temperatures at the bottom of small cavities in a carbon arc electrode were normalized to the present data at 3300C and are shown in Fig. 9. The thermal-conductivity curves obtained by means of the external-heating method have been estimated to be accurate to within &5 per cent, while those obtained by the direct-heating method have an estimated accuracy of f8 per cent. However, it should be emphasized that the time available for completion of the project did not allow

24

N.

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RASOR

and

J.

D.

MCCLELLAND

adequate development of the direct-heating method. The data presented are those for which the required experimental conditions were indeed

-0

\!I
0

MI

0 EXTERN WYROM. q EXTERNI (THERMOCOUPL 0 DIRECT HEATlN METHOD A &El? ARC ELECTRODE DATA i x 1.46

k HEATLYG M-D G

10

1000

1500

2000

2300

TEMPERATURE,C

3000

350:

4000

FIG.

9.

Thermal

conductivity of type-3474D normal to extrusion axis.

graphite

achieved. Nevertheless, time did not permit repeat measurements to be made to obtain the same degree of confidence that characterizes the other

(; 0.20 ti : 2 z ; 2 s s ii! _. 500 1000 1500 2000 2500 3000 3500 4000 0.05 0.10

0.15

::
F

TEMPERATURE,*C

FIG. 10. Thermal conductivity of type-7087 normal to extrusion axis.

graphite

data reported here. Therefore, the thermal conductivity values for graphite above 2700C need confirmation by further work. The theoretical curves in Fig. 8 were computed from the Lorenz (Wiedemann-Franz) relationship :
K=,4' P (5)

using the free-electron value for the constant A = &%a/3ea = 2.45 x 10-s WQ/(C)a, and the published dependence of the electrical resistivity p on the absolute temperature T. As may be seen in Fig. 8, the experimentally determined thermal conductivities of molybdenum and tantalum quite accurately obey this relationship over this temperature region. This allows a fairly confident extrapolation of the data for tantalum to higher temperatures. Since methods requiring radial heat flow were used, the thermal conductivity of graphite was determined only in the direction normal to the extrusion axis or molding pressure. However, the anisotropy ratio for the electrical resistivity is approximately the same as that for the thermal conductivity. Thus, the thermal conductivity in the direction normal to that reported may be estimated by multiplying the reported conductivities by the anisotropy ratio listed under the corresponding type in Table 2. The Lorenz relation cited above is based on the conduction of heat by electrons and is generally valid only for good metals. Graphite, on the other hand, like most non-metals, conducts heat principally by elastic lattice waves.(ra) The elementary theory of lattice conduction predicts that at high temperatures, thermal conduction where is limited principally by the mutual scattering of lattice waves, the thermal resistivity (reciprocal conductivity) should show a linear temperature dependence. The curve below 2700C in Fig. 9 is based on this prediction and corresponds qualitatively with the observed behavior of types 3474D and GBE in this region. However, types 7087 and GBH show an irreversible increase in conductivity upon initial heating (Fig. 10). It should be recalled that these are the types which showed impurity or graphitization effects in the thermal expansion data. Since lattice thermal conductivity is sensitive to lattice imperfection, the removal of imperfections and impurities is probably responsible for the observed irreversible increase. Thus the thermal conductivity of types GBH and 7087 at temperatures above 1600C depends on the thermal history of these materials. Since such irreversible behavior was not observed in types GBE and 3474D, their conductivities are probably unique and represent the intrinsic behavior of polycrystalline graphite at these temperatures.

THERMAL

PROPERTIES

OF

GRAPHITE,

MOLYBDENUM

AND

TANTALUM

25

Above 2700C the conductivity may be seen to decrease rapidly, falling by about an order of magnitude in a relatively small temperature interval. Analysis of the temperature dependence of this very large increase in thermal resistivity indicates that it is a thermally activated process again characterized by an activation energy in the vicinity of 7.7 eV/atom. As discussed previously in relation to the very similar effect in the specificheat data, this leads to two possible interpretations of the cause of the effect: vaporization or vacancy formation. However, in this case vaporization effects would cause the radial temperature drop to appear too small, which is in the wrong direction to explain the observed effect. On the other hand, lattice imperfections introduced by radiation damage have been observedos) to increase the thermal resistivity of graphite by as much as several orders of magnitude, due to increased scattering of lattice waves. It is logical, therefore, to expect the thermal formation of vacancies postulated to explain the specific-heat anomaly to be accompanied by a proportionate increase in thermal resistivity such as is indeed observed. Thus, combining the linear low-temperature thermal resistivity behavior and the exponential contribution due to vacancy formation with a 7.7 eV formation the following theoretical equation is energy, obtained to fit the experimental data for type 3474D :

observedos) initial rate of change of thermal resistivity of graphite with radiation damage (-0.4 cm-set-C/Cal per MW-day), and the corresponding theoretical value(l4) of the fraction of atoms displaced by a given irradiation (4.5 x 10-4 mole fraction per MW-day). The value thus obtained from radiation-damage data is estimated to be approximately: rNo.sX104 cm-see-C cal

1 - = 2+4+(3*46x K -X exp [-%9X

10-s) T+(8.5 10*/T]

x 1011) x (6)

cm-set-C cal

where T is in K. The curve in Fig. 9 is a plot of this equation and may be seen to represent adequately the experimental data. The thermal resistivity per vacancy, Y, may readily be computed from the observed heat capacity and conductivity data to be: bE2 YN - = 2.4x fR 104 cm-set-C cal

per mole fraction of vacancies, where b and f are the coefficients of the exponential terms in equations (6) and (4), respectively, and R is the gas constant. The thermal resistivity per vacancy may also be estimated from the

per mole fraction of vacancies. However, since this value is the change in room-temperature resistivity, the change in resistivity at elevated temperatures should be somewhat larger, as is indeed observed above, due to the more efficient scattering of lattice waves at shorter average wavelengths. The magnitude of this correction probably does not exceed the combined uncertainty in the approximations, so that further analysis does not seem warranted. Nevertheless, the agreement, within an order of magnitude, of the thermal resistivity change values computed from entirely independent considerations again provides strong confirmation that the thermal formation of lattice defects is responsible for the observed abrupt changes in heat capacity and conductivity above 2700C. The behavior of the thermal conductivity of graphite above 2700C obtained by EuLER~~), using a carbon arc method, is in excellent agreement with that observed by the present method. This is strong confirmation that the rapid drop in conductivity is not spurious, since the methods used are entirely different. The expansion data obtained at these temperatures (Section 3) indicate that the large irreversible drop in density, postulated by EULER to explain the effect, does not occur. Also, direct bulk-density determinations by weighing after heating showed that no detectable change had occurred. The absence of a corresponding decrease in both the thermal and the electrical conductivities of the metals near their melting points indicates that thermal scattering of conduction electrons predominates over scattering by thermally produced vacancies. The same conclusion is reached concerning the absence of a corresponding decrease in the electrical conductivity of graphite (Fig. 7).

26

N.

S.

RASOR

and

J.

D.

McCLELLA.ND

6. CONCLUSIONS

The thermal expansion data for most of the materials investigated show no grossly unusual features. An exception is the irreversible behavior of two types of graphite near 2700C in a direction suggesting the removal of interlayer impurity atoms from the graphite lattice. The specific heat of the metals, particularly molybdenum, has been found to exceed the Dulong-Petit value by a large amount as the melting temperature is approached. The thermal conductivities of tantalum and molybdenum have been found to obey the Lorenz (WiedemannFranz) relation closely to near their melting temperatures. Up to 2700C the specific heat of graphite saturates near the Dulong-Petit value and, except for irreversible graphitization effects, the thermal conductivity behaves in accordance with simple lattice-con.duction theory. However, at higher temperatures the specific heat and thermal resistivity experience large and abrupt increases which may be both qualitatively and quantitatively described as due to thermal formation of vacant lattice sites. The changes in both properties are consistent with an energy of formation of 7.7% 0.5 eV for the vacancies and a vacancy concentration of about 0.5 atomic per cent at the sublimation temperature (3650C). This behavior may be of critical engineering significance, since, if volumeheated electrically or by nuclear fuel, graphite may be unstable as a heat-transfer medium above 3000C. An increase in temperature leads to a large drop in thermal conductivity and diffusivity, possibly leading to further increase in temperature and so on until the vapor pressure causes disintegration. The observed effects of vacancy formation on the thermal properties of graphite should also appear in other lattice heat conductors having high vacancy-formation energies. The results obtained show the general character of the observed properties of graphite, molybdenum and tantalum to the accuracy required for engineering analysis. The existence of large, previously unknown effects in these materials has been

established, and further work is indicated to achieve the detailed understanding required for their complete description. Nevertheless, the apparent agreement between the observed data and contemporary theories of the solid state is gratifying and gives an indication of the reliability of the data.
Acknowledgements-The following personnel contributed directly to the technical effort: R. C. DAHLEEN, E. H. ZEHMS. W. E. WALTERS. D. R. WARNERand C. BOTKER. The writers gratefully acknowledge the interest and helpful suggestions of the members of the Solid State Physics Group headed by D. BOWEN. This report covers work conducted from March 1955 to June 1956 administered under the direction of the Materials Laboratory, Directorate of Research, Wright Air Development Center, with Captain S. V. ZALE~KI and Lt. MYRON W. BELAGAof the Materials Laboratory, Research Division, acting as project engineers. REFERENCES 1. RASOR. N. S. and MCCLELLAND J. D., Rev. Sci. Instrum. 31, 595 (1960). 2. RAZOR N. S. and MCCLELLAND J. D., Wright Air Development Center Tech. Rep. 56-400, Part I (Nov. 1956). 3. WALKER P. L. and IMPERIAL G., Nature, Lond. 180, 1184 (1957). 4. AVRAMESCU Z. techn. Phys. 20,213 (1939). A., 5. SIMON F. and ZEIDLER W., Z. phys. Chem. 123, 383 (1926); JAEGER F. M. and VEEXSTRAW. A., Rev. Trav. Chim. Pays-Bas 53,677 (1934); CLUSIUS K. and LOSA C. G., Z. Naturf. lOA, 939 (1955); MAGNUSA., Ann. Phys., Lpz. 70, 303 (1923). 6. STULL D. R. and SINKE G. C., Thermodynamic Properties of the Elements, American Chemical Society, Washington D.C. (1956). 7. ARMSTRONG D. and GRAYSON-SMITHH., Canad. L. J. Res. 28A, 51 (1950). 8. THORN R. J. and WINSLOW G. H., J. Chem. Phys. 26, 186 (1957). 9. POCHAPSKY E., Acta Met. 1, 747 (1953). T. 10. WORTHINGA. G., Phys. Rev. 28,190 (1926); MALTER I,. and LANGMUIR B., Phys. Rev. 55,745 (1939). D. 11. EULER J., Naturwissenschaften 39, 568 (1952). 12. TYLER W. W. and WILSON A. C., Jr., Phys. Rev. 89, 870 (1953). 13. SMITH A. W. and RA.SOR S., Phys. Rev. 104, 885 N. (1956). 14. HENNIG G. R. and HOVE J. E., Proc. Internat. Conf. Peaceful Uses of Atomic Energy 7, 666 (1956).