PHYSICS OF THE SOLID EARTH, English Translation, VOL. 30, NO.

7/8, FEBRUARY 1995 Russian Edition: JULY{AUGUST 1994

Temperature dependence of lattice thermal conductivity of Earth's mineral substance

G. I. Petrunin and V. G. Popov

Moscow University

c features of the temperature dependence of lattice thermal conductivity of rocks and minerals in the range from room temperature to their melting points have been studied and generalized on the basis of experimental data obtained in the geothermal laboratory of the Physical Department, Moscow University. Discussion in the context of thermal conductivity theory for a crystalline dielectric allows us to relate such features to the complexity of compositional and structural imperfections of real mineral substances. Estimates can then be made of the in uence of these factors on phonon scattering and mean free path. The analysis conducted here allows basic principles for constructing pro les of conductive heat transfer in the crust and mantle to be developed.
In considering the experimental results of studies of heat transfer in rocks and minerals, the principal feature is the thermal conduction theory for crystalline dielectrics, which was formulated by Debye and developed by Peierls and other investigators on the basis of quantum mechanical principles. It is quite clear that the majority of geological materials representing polycrystalline aggregates should be well suited to the application of theoretical conclusions on the character of temperature dependence of thermal conductivity that are based on the idea that the heat transfer intensity due to lattice oscillations is governed by the degree of anharmonicity of these oscillations. However, it is important to bear in mind that the theory developed for a perfect crystal fails to agree quantitatively with experimental results even for single crystals with a small concentration of structural defects and will yield still more discrepancies with data for complex mineral compounds that are \imperfect" in every respect. Thus, to extend the theoretical conclusions to real materials and, in particular, to crust and mantle materials, the theory should be supplemented by characteristics revealed through comparison with experiment. The speci c properties of materials are exhibited, as a rule, in analyses of the change in thermal properties through a wide temperature interval, which includes a high temperature range that has been only poorly studied until recently. The chief cause of this situation is, brie y, the great di culty of running high-temperature experiments at increasing temperatures and with increasing
Copyright 1995 by the American Geophysical Union. 1069{3513/95/300708{0004$18.00/1

Abstract. The speci

emission loss from the surfaces of the samples under study. Leibfried and Schlamann derived a well-known expression (which relates temperature and other properties of material) to describe the phonon thermal conductivity of an ideal dielectric. For three-phonon acoustic scattering at T , this formula can be written in the form MacPherson and Schloessin, 1983]
p

1=3 3 1=3 ' 12 41=3 k M 2 T = C M 2 T 5 h

(1)

where is the Gruneisen parameter, is the volume referred to one atom, is the characteristic temperature, and M is the atomic mass or, for a complex substance, the mean atomic mass. As mentioned above, this formula does not give a quantitative agreement with experiments, and therefore a norming constant C has been introduced to t (1) to experimental data for each structural type of compound. Formula (1) appears to provide qualitative theoretical support for Eucken's empirical law (1911), which shows that the thermal resistivity (1= l ) of a crystalline dielectric at T is directly proportional to its absolute temperature 1= l = const T (2) Here, we consider experimental data on the thermal properties of minerals and rocks and use our recent results together with data from the literature Birch and Clark, 1940 Clauser, 1988 Fujisawa et al., 1968 Kanamori et al., 1968 Kawada, 1966 MacPherson and Schloessin, 1983 Magnitskiy et al., 1971 Petrunin and

617

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petrunin and popov: temperature dependence

Temperature dependence of the thermal resistivity of the major rock-forming minerals: 1, plagioclase (labradorite) 2, microcline 3, garnet 4, pyroxenite 5, synthesized gallious garnet 6, garnet Kanamori et al., 1968] 7, synthesized olivine Schatz and Simmons, 1972] 8, olivine 001] Kanamori et al., 1968] 9, -SiO2 Kanamori et al., 1968] and 10, olivine Fo92 010], P = 2.5 GPa Scharmeli, 1982].
Figure 1.

Temperature dependence of the thermal resistivity of some rocks: 1, granite 2, granite Birch and Clark, 1940] 3, diorite 4, diabase 5, dunite 6, dunite 7, gabbro Birch and Clark, 1940] 8, serpentinite 9, hypersthenite Birch and Clark, 1940] 10, eclogite Kawada, 1966] and 11, mica Kanamori et al., 1968].
Figure 2.

are the temperature dependencies of the heat resistivities of the major rock-forming minerals and magmatic rocks, respectively. First, it is beyond question that over practically all the represented temperature intervals, the heat resistivity of the complex crystalline compounds forming the crust and mantle increases by a law that is also close to linear however, this law di ers from (2) and has the following functional form: 1= = A + BT (3) This relation involves, along with the second term describing thermal resistivity due to the intrinsic phononphonon scattering in a crystal, an additional temperature-independent term A that varies over wide limits for di erent minerals and rocks. It is easily seen that except for quartz, at room temperature this term is comparable to or even exceeds the thermal resistivity contribution related to the anharmonicity of elastic lattice oscillations. Naturally, the rst term in (3) cannot be

Popov, 1983 Petrunin et al., 1989 Scharmeli, 1982 ignored in estimating the thermal conductivity within Schatz and Simmons, 1972]. Shown in Figures 1 and 2 the Earth's mantle.

In the lower right-hand corner of Figure 2, we compare (2) and (3), using them to extrapolate the 300 K data for dunite to the higher temperatures characteristic of the deep upper mantle hence it follows that neglect of the A term results in signi cant overestimation (by two times) of the thermal resistivity. This was one of the reasons that in the 1960s, geophysicists concluded that the Earth's mantle transfers heat conductively with relatively low e ciency. Thus consideration of the e ect of this term on the predicted thermal conductivity of Earth materials requires careful study of their physical nature and estimation of their contribution to the total thermal resistivity at di erent horizons of the mantle. As for the physical nature of A, it is natural to propose its relation to imperfections in the materials and primarily to scattering of phonons at microdefects such as grain boundaries, cracks, voids, etc. Previously Petrunin and Popov, 1983], we made an e ort to justify this assumption by demonstrating the in uence of the homogeneity of a material on the value of thermal resistivity, includ-

petrunin and popov: temperature dependence

619

ing the additional temperature-independent term. It was shown that for particular minerals and rocks, this in uence is substantially suppressed on passing from ne-grained to coarse-grained structures and, especially, to monocrystals and monomineral aggregates. In the same work we discussed experimental Fujisawa et al., 1968] results on simultaneous pressure and temperature e ects on polycrystalline forsterite and concluded that the thermal resistivity decrease obtained by these authors is mainly related to enhancing grain boundary contacts and likely cannot be induced by pressure e ect on the phonon-phonon interactions, since at pressures P = 3 and 5 GPa, the slope of the thermal resistivity versus temperature curve remains constant within the limits of experimental errors. A similar conclusion can be reached from an analysis of isobaric dependencies 1= (T ) constructed from the results of MacPherson and Schloessin 1983], who demonstrated the P ;T e ects on the thermal conductivity of synthesized monocrystals of periclase (MgO) and galite (NaCl) at temperatures of 300{1500 K and pressures of 1.5 to 5.6 GPa. However, in the case under consideration, the weak decrease of the \defective" part of the thermal resistivity A is accompanied by a faintly visible tendency for the slope of the tangent to the isobars to decrease with increasing pressure. Considering the relation of the slope determined by the coe cient B in (3) with structural characteristics such as the lattice constant, Debye temperature, and Gruneisen parameter, we can suggest that the pressure range used is not su ciently large to appreciably change these parameters. Thus at present, the question of pressure variation in the normalizing constant in B and consequently in the coe cient B itself remains open because of insu cient experimental data. This lack casts some doubt on the possibility that relations (1) and (3) are applicable to predicting the thermal conductivity of mantle materials. We here continue our discussion of the physical nature of the coe cient A. Once the e ect of macrodefects on the value of this coe cient has been established, a valid question about the degree of this in uence arises. This in uence can be estimated from comparing the temperature dependencies of poly- and monocrystals of substances. However, in this case, we are interested in the purely qualitative matter of the mechanism of the e ect rather than in numerical estimates for various minerals. In other words, can the value of A be completely explained by the macrodefect e ect, or is part of it induced by some other phonon-scattering mechanism? Such a question arises because, starting from the temperature behavior of monocrystalline olivines and garnets represented in Figure 1, we can assert that phonon scattering at macrodefects does not seem to exhaust the value of the A term and is substantially caused by other scattering mechanisms.

Temperature dependence of heat capacity of rocks: 1, granite 2, diorite 3, diabase 4, gabbro 5, dunite 6, harzburgite and 7, serpentinite.
Figure 3.

First and foremost we dwell on the cause that has nothing to do with thermal resistivity. According to the theory of an ideal dielectric, the law 1= l T applies in a temperature range above the characteristic temperature T , where the heat capacity reaches its classic limit and the temperature behavior of the lattice thermal conductivity is exceptionally well determined by transport processes with anharmonic coupling. The value of for the considered minerals and rocks lies within the limits 500{700 K consequently, in the studied temperature interval (300{1000 K), and especially within its rst half, heat capacity continues to grow, resulting in a decrease in the slope 1= l = f (T ) and an increase in A. This e ect must be greater for higher characteristic temperatures , i.e., for greater increases in the heat capacity. It follows from Figure 3, which shows heat capacity as a function of temperature for ultrabasic rocks that are similar in composition to the upper mantle, that the heat capacity over the indicated temperature interval increases almost 1.5 times, and the proposed e ect must be signi cant. This e ect can be estimated using measurements of thermal diffusivity a = 1 v l, which is directly proportional to the 3 mean free path l of phonons and must well characterize the phonon scattering processes and the associated constraint on thermal conductivity. By analyzing data from the literature as well as our direct measurements of the thermal di usivity for di erent minerals and rocks (Figures 4 and 5), it is easily shown that the contribution of the values of A1 to 1=a at 300 K is smaller by nearly two times than the similar contribution of A to 1= l (Figures 1 and 2) for the same materials. For example, at 300 K, these contributions for the olivine and synthesized garnet monocrystals amount to 28 and 15% (Figure 4), respectively, in contrast to the corresponding 60 and 38% contributions in the case of thermal resistivity (Figure 1). A similar result for rocks can be

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petrunin and popov: temperature dependence

Figure 4.

Temperature dependence of the quantity 1=a for some rock-forming minerals: 1, plagioclase 2, microcline 3, olivine Kanamori et al., 1968] 4, olivine 5, jadeite Kanamori et al., 1968] 6, pyroxenite 7, garnet Kanamori et al., 1968] 8, quartz Kanamori et al., 1968] 9, forsterite Schatz and Simmons, 1972] and 10, gallious synthesized garnet.

Temperature dependence of 1=a for rocks: 1, granite 2, diorite 3, diabase 4, gabbro 5, dunite 6, harzburgite 7, serpentine 8, basalt 9, pyroxenite 10, enstatite 11, peridotite and 12, eclogite.
Figure 5.

obtained by comparing the corresponding dependencies depicted in Figures 2 and 5. This implies that the processes of phonon scattering by structural imperfections are responsible for only 50% of the value of the A term in (3). Moreover, the fact that 1=a is nonvanishing at T = 0 for the garnet and olivine single crystals, which are close to ideal and practically macrodefect-free samples, suggests that apart from macrodefects, the \defective" part of thermal resistivity is contributed not only by the structural imperfections of foreign atom or vacancy types but also by phonon scattering from local changes in the density and elastic modulus characteristics of chemical compounds. In particular, this hypothesis is not in con ict with the data in Figures 1 and 4. From these data for 1= and 1=a as well as for A and A1 , we recognize a certain tendency: namely, these values increase with increasingly complicating chemical composition of the crystal lattice, from close to zero for SiO2 through an intermediate value for pyroxenes and olivines (MgSiO3 , Mg2SiO4 ) to the maximal values which almost completely determine the thermal resistivity of complex solid solutions of plagioclases and feldspars. This hypothesis is important from the point of view of both theory and practice, but it needs special investigation and closer experimental veri cation. This investigation can also shed light on the unusual

temperature behavior of heat conductance and thermal di usivity of some minerals and rocks, which at rst seems contrary to the fundamentals of lattice heat transfer in a lattice dielectric. This speci c feature can be more distinctly traced at high temperatures and consists of the characteristic attening of the corresponding curves at temperatures of 800{1000 K and, in some cases, the tendency of and a to increase with increasing temperature. This is especially clear in Figures 1, 2, 4, and 5 when we consider deviations of the hightemperature points from linear dependence 1= = f (T ) and 1=a = f (T ) over the measured temperature interval 300{800 K. We can argue with con dence that such behavior of the e ective thermal conductivity and thermal di usivity of minerals and rocks in the high-temperature range is not speci c fact but experimental regularity. On the other hand, it is di cult to imagine that there is only one general cause for this behavior. This is connected to the facts that data from di erent authors for the same material often disagree and that the trends of the deviations of heat resistivity from linear dependence vary in character. In particular, for olivine and garnet, the behavior of dependencies 1= = f (T ) and 1=a = f (T ) (Figures 1 and 4) according to Kanamori et al. 1968] essentially di ers from the behavior seen in our labora-

petrunin and popov: temperature dependence

621

tory. For practically all minerals measured by Kanamori et al., the low temperature of 600 K is the threshold above which we see a substantial departure from linear dependence and a subsequent sharp increase in thermal conductivity and thermal di usivity. We are inclined to consider this fact as being due merely to method rather than a methodical e ect being unrelated to material properties, and later on we shall try to unravel this situation in more detail. In our opinion, there are at least three principal causes for the phenomenon studied, each of which can dominate depending on method of study, applied the properties of the substance, and structure, composition, and thermodynamic conditions of the experiment. The possibility that two or even all three causes will operate simultaneously is also not inconceivable. The rst cause is the way temperature increases due to heat radiating from the sample surface a ect the results of measurements. This is a pure methodological cause related especially to the di culties of accounting for the indicated heat losses. It can be shown that for materials with low conductivity, including the rockforming minerals, in a given experiment with a specied object geometry, the dimensionless Biots parameter Bi characterizing the intensity of the radiative heat exchange can reach a tenth at temperatures of 600{800 K. This leads to signi cant overestimation of thermal conductivity and thermal di usivity up to reversing the trend in the temperature behavior. Contrary to the technique of Kanamori et al. 1968], our technique takes into consideration this heat transfer and excludes its inuence on measurement results Petrunin and Jurchak, 1971]. This suggests that it might be realistic to explain the deviation (observed even at moderate temperatures) of the mineral thermal di usivity curves published by Kanamori et al. 1968] methodological. The second cause is an appearance, along with the lattice thermal conductance, of a new heat transfer mechanism. Such a mechanism in a crystalline lattice and, in particular, in mineral and rock can be the heat radiation mechanism with intensity proportional to T 3 and activated in transparent or half-transparent bodies from the beginning of their luminescence (600{700 K). Radiative heat transfer in mineral substances is a special problem of thermal physics that has been clearly formulated and continues to be developed in many laboratories, including geophysical ones Clauser, 1988 Fujisawa et al., 1968 Kanamori et al., 1968 MacPherson and Schloessin, 1983 Scharmeli, 1982 and others]. Here we note only that the principal criterion for identi cation of this mechanism, in our opinion, is a stable tendency for the measured values of thermal di usivity to increase with increasing temperature. It is the growth of thermal di usivity (not thermal conductivity) that results in the e ect. The problem is that because of anharmonic

vibrations of atoms about lattice points, the isobaric heat capacity Cp continues to grow also at temperatures higher than the characteristic temperature, inducing a monotonic increase in the e ective thermal conductiv1 ity ef = 3 Cp v l even if the radiation mechanism is absent and the free path of phonons l remains constant for unknown reasons. This may explain why the mean free path of phonons reaches its minimal value l = v min . In reality, the mean lifetime of phonons is determined by scattering processes, among which the three-phonon Umklapp processes become dominant. According to the theory, the frequency of such processes increases proportionally with temperature and shortens the mean phonon lifetime. The minimal value min is determined by the maximal frequency of atomic vibrations, which in a real discrete lattice structure must in turn be bounded by the Debye spectrum cut-o frequency: k (4) max = h Thus for the minimal value of min , we have, by de nition, 1 = h (5) min = max k and, consequently,

lmin = vh=k (6) The thermal Debye temperature can be replaced, with a su cient accuracy, by its acoustic approximation:
1=3 = h 3Na v (7) k 4 M where Na is Avogadro's number, is density, and v is the mean sound velocity de ned by the relation between the longitudinal vp and transverse vs components: 3 3 vp vs v 3 = 3 v 3 + 2v 3
s p

(8)

Table 1 gives the results of computations of lmin for major minerals and rocks in the Earth and comparable results obtained from experimental thermal di usivity data obtained by using the formula (9) a = 1 vl 3 It is easily seen that such a comparison leads to an unexpected result: even at room temperature, the mean free path of phonons in the majority of geologic materials (except quartz) proves to be only slightly in excess

622
Table 1.

petrunin and popov: temperature dependence

Mean free path of phonons in minerals and rocks as computed from thermal di usivity data Mineral, rock Formula, Mean v composition atomic km/s kg/m3 103 l300 A l700 A l1000 A lmin A mass M Fo84Fa16 21.54 (5.4) 3.45 9.72 5.72 3.85 3.51 Mg2 SiO4 20.10 (5.56) (3.24) ; 4.12 2.32 3.50

Olivine, 001], Scharmeli 1982] Forsterite, MacPherson and Schloessin 1983] Olivine Quartz, Scharmeli 1982] Jadeite, Scharmeli 1982] Garnet, Scharmeli 1982] Pyroxene, Scharmeli 1982] Microcline, Petrunin et al. 1989] Labradorite, Petrunin et al. 1989] Dunite Harzburgite Eclogite Diorite Gabbro

Fo91Fa9 -SiO2 NaAlSi2O6 ; En96 Fs4 KAlSi3 O6 Ab46 An54 Ol90 Ol63 En15 Gr60En35 ; ;

20.87 20.03 20.21 (22.52) 20.21 21.41 20.83 21.12 20.49 (21.20) (20.50) (20.60)

(5.50) (4.74) (5.80) (6.09) 5.23 (5.00) (4.67) (4.90) (5.20) (5.80) (4.30) (4.60)

3.21 2.65 (3.35) (3.58) 3.18 2.56 2.70 2.82 3.17 3.57 2.60 3.05

10.60 45.19 7.97 5.47 6.75 5.45 4.95 7.96 8.67 5.74 7.40 7.24
Maj

4.52 8.67 4.31 3.94 3.48 4.00 3.57 3.73 3.87 3.44 3.63 4.34

3.41 5.27 3.23 3.28 2.74 3.52 3.38 2.76 2.95 3.20 3.20 3.26

3.56 3.75 3.47 3.53 3.55 3.58 3.77 3.73 3.56 3.46 3.79 3.60

Parentheses indicate the average values for a given type of rocks and minerals according to 1972].

1974] and

Povarennykh et al.

of the minimal value that is reached in the temperature range 700{1000 K. This fact fundamentally changes our present view of high-temperature behavior of lattice thermal conductivity and thermal di usivity of such compounds as complex in their structure and composition as minerals and rocks. First, it sets a limiting temperature of the order of 1000{1200 K for application to rocks and minerals not only for the Leibfried and Schlemann formula obtained for T but for the more general empirical relation (3) as well. The same fact allowed us to begin developing the principles of numerical estimation of conductive heat transfer in the deep mantle on the basis of the known relation where lmin is determined from (6), and the in uence of thermodynamic conditions is taken into account by parameters and v , obtained from relevant seismic models. It follows from (10) that with allowance for all of the preceding, the conductive heat transfer in the mantle must continuously increase (corresponding to the deep behavior of v and ) rather than decrease with depth. Thermal conductivity pro les computed with the help of (10) for the simpli ed PEM seismic models of the upper and lower mantle Dziewonski et al., 1975] are given by Fujisawa et al. 1968] and Petrunin and Orlik 1988]. 1 = Cp a = 3 Cp vlmin (10)

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(Received June 16, 1993.)