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PHYSICS OF THE SOLID EAR TH

English Translation

VOL

NO

FEBRUARY

Russian Edition

JULY AUGUST

T emperature dependence of lattice thermal

conductivity of Earth s mineral substance

G I P etrunin and V G Popov

Moscow University

Abstract The speci 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 experimen tal results of studies of

heat transfer in rocks and minerals the principal fea

ture is the thermal conduction theory for crystalline

dielectrics which was formulated by Debye and devel

oped by Peierls and other investigators on the basis of

quantum mechanical principles

It is quite clear that

the majority of geological materials representing poly

crystalline aggregates should be well suited to the ap

plication 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 im

portant to bear in mind that the theory developed for

a perfect crystal fails to agree quantitatively with ex

perimental results even for single crystals with a small

concentration of structural defects and will yield still

more discrepancies with data for complex mineral com

pounds 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 re

vealed through comparison with experiment The spe

ci 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 tem

perature 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 exper

iments at increasing temperatures and with increasing

Cop yright by the American Geophysical Union

emission loss from the surfaces of the samples under

study

Leibfried and Schlamann

derived a well known ex

pression which relates temperature and other proper

ties of material to describe the phonon thermal conduc

tivity of an ideal dielectric For three phonon acoustic

scattering at T this formula can be written in the

form MacPherson and Schlo essin

p

k

h M

T

C M

T

where is the Gruneisen parameter is the volume re

ferred 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 for

mula does not give a quantitative agreement with ex

periments and therefore a norming constant C has been

introduced to t to experimental data for each struc

tural type of compound

Formula appears to provide qualitative theoretical

support for Eucken s empirical law which shows

that the thermal resistivity l of a crystalline di

electric at T is directly proportional to its absolute

temperature

l const T

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 Clauser Fujisawa et al

Kanamori et al Kawada MacPherson and

Schloessin Magnitskiy et al Petrunin and

petr unin and popov

petr unin and popov Figure Temperature dependence of the thermal re sistivity of the major rock

Figure Temperature dependence of the thermal re

sistivity of the major rock forming minerals plagio

clase labradorite microcline garnet pyroxen

ite synthesized gallious garnet garnet Kanamori

et al synthesized olivine Schatz and Sim

mons olivine Kanamori et al

SiO Kanamori et al and olivine F o

P GPa Scharmeli

Popov Petrunin et al Scharmeli

Schatz and Simmons Shown in Figures and

are the temperature dependencies of the heat resistivi

ties of the major rock forming minerals and magmatic

rocks respectively

First it is beyond question that

over practically all the represented temperature inter

vals the heat resistivity of the complex crystalline com

pounds forming the crust and mantle increases by a law

that is also close to linear however this law di ers from

and has the following functional form

A BT

This relation involves along with the second term de

scribing thermal resistivity due to the intrinsic phonon

phonon scattering in a crystal an additional tempera

ture independent term A that varies over wide limits for

di erent minerals and rocks It is easily seen that ex

cept for quartz at room temperature this term is com

parable to or even exceeds the thermal resistivity con

tribution related to the anharmonicity of elastic lattice

oscillations Naturally the rst term in cannot be

temperature dependence

the rst term in cannot be temperature dependence Figure Temperature dependence of the thermal re sistivity

Figure Temperature dependence of the thermal re

sistivity of some rocks

granite granite Birch

and Clark

diorite

diabase

dunite

dunite gabbro Birch and Clark serpenti

nite hypersthenite Birch and Clark eclog

ite Kawada and mica Kanamori et al

ignored in estimating the thermal conductivity within

the Earth s mantle

In the lower right hand corner of Figure we com

pare and using them to extrapolate the 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 s geophysicists concluded that

the Earth s mantle transfers heat conductively with rel

atively 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 ther

mal 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 we made an e ort to justify this assump

tion by demonstrating the in uence of the homogeneity

of a material on the value of thermal resistivity includ

petr unin and popov

temperature dependence

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 F ujisawa et al

results on simultaneous pressure and temperature

e ects on polycrystalline forsterite and concluded that

the thermal resistivity decrease obtained by these au

thors 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 and GPa the slope of the thermal resistiv

ity versus temperature curve remains constant within

the limits of experimental errors A similar conclusion

can be reached from an analysis of isobaric dependencies

T constructed from the results of MacPherson and

Schloessin who demonstrated the P T e ects on

the thermal conductivity of synthesized monocrystals of

periclase MgO and galite NaCl at temperatures of

K and pressures of to GPa However

in the case under consideration the weak decrease of the

defective part of the thermal resistivity A is accom

panied by a faintly visible tendency for the slope of the

tangent to the isobars to decrease with increasing pres

sure Considering the relation of the slope determined

by the coe cient B in with structural character

istics such as the lattice constant Debye temperature

and Gruneisen

parameter we can suggest that the pres

sure range used is not su ciently large to appreciably

change these parameters

Thus at present the ques

tion 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

and are applicable to predicting the thermal con

ductivity 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 temper

ature dependencies of poly and monocrystals of sub

stances 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 ex

plained 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 repre

sented in Figure 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 scatter

ing mechanisms

and is substantially caused by other scatter ing mechanisms Figure Temperature dependence of heat capacity of

Figure

Temperature dependence of heat capacity

of rocks

granite diorite diabase gabbro

dunite harzburgite and serpentinite

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 l T ap

plies 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 de

termined by transport processes with anharmonic cou

pling The value of for the considered minerals and

rocks lies within the limits K consequently in

the studied temperature interval K and es

pecially within its rst half heat capacity continues to

grow resulting in a decrease in the slope l f T

and an increase in A This e ect must be greater for

higher characteristic temperatures i e for greater in

creases in the heat capacity It follows from Figure

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 indi

cated temperature interval increases almost times

and the proposed e ect must be signi cant This e ect

can be estimated using measurements of thermal dif

fusivity a

v l which is directly proportional to the

mean free path

l of phonons and must well character

ize 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 and it is easily shown that the contribu

tion of the values of A to a at K is smaller by

nearly two times than the similar contribution of A to

l Figures and for the same materials For ex

ample at K these contributions for the olivine and

synthesized garnet monocrystals amount to and

Figure respectively in contrast to the correspond

ing and contributions in the case of thermal

resistivity Figure A similar result for rocks can be

petr unin and popov

petr unin and popov Figure Temperature dependence of the quan tit y a for some rock

Figure Temperature dependence of the quantity a

for some rock forming minerals plagioclase mi

crocline olivine Kanamori et al olivine

jadeite Kanamori et al pyroxenite gar

net Kanamori et al quartz Kanamori et al

forsterite Schatz and Simmons and

gallious synthesized garnet

obtained by comparing the corresponding dependencies

depicted in Figures and This implies that the pro

cesses of phonon scattering by structural imperfections

are responsible for only of the value of the A term

in Moreover the fact that a is nonvanishing at

T for the garnet and olivine single crystals which

are close to ideal and practically macrodefect free sam

ples suggests that apart from macrodefects the defec

tive part of thermal resistivity is contributed not only

by the structural imperfections of foreign atom or va

cancy types but also by phonon scattering from local

changes in the density and elastic modulus characteris

tics of chemical compounds In particular this hypoth

esis is not in con ict with the data in Figures

and

From these

data for and a as well as for A

and A we recognize a certain tendency namely these

values increase with increasingly complicating chemical

composition of the crystal lattice from close to zero

for SiO through an intermediate value for pyroxenes

and olivines MgSiO Mg SiO to the maximal val

ues which almost completely determine the thermal re

sistivity 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 spe

cial investigation and closer experimental veri cation

This investigation can also shed light on the unusual

temperature dependence

can also shed light on the unusual temperature dependence Figure Temperature dependence of a for roc

Figure

Temperature dependence of a for rocks

granite diorite diabase gabbro dunite

harzburgite serpentine basalt pyroxenite

enstatite peridotite and eclogite

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 trans

fer in a lattice dielectric

This speci c feature can be

more distinctly traced at high temperatures and con

sists of the characteristic attening of the correspond

ing curves at temperatures of K and in some

cases the tendency of and a to increase with increas

ing temperature This is especially clear in Figures

and when we consider deviations of the high

temperature points from linear dependence f T

and a f T over the measured temperature interval

K

We can argue with con dence that such behavior of

the e ective thermal conductivity and thermal di usiv

ity 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 de

viations of heat resistivity from linear dependence vary

in character In particular for olivine and garnet the

behavior of dependencies f T and a f T

Figures and according to Kanamori et al

essentially di ers from the behavior seen in our labora

petr unin and popov

temperature dependence

tory For practically all minerals measured by Kanamori

et al the low temperature of 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 ma

terial 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 re

sults of measurements This is a pure methodological

cause related especially to the di culties of account

ing for the indicated heat losses It can be shown that

for materials with low conductivity including the rock

forming minerals in a given experiment with a speci

ed object geometry the dimensionless Biots parameter

Bi characterizing the intensity of the radiative heat ex

change can reach a tenth at temperatures of K

This leads to signi cant overestimation of thermal con

ductivity and thermal di usivity up to reversing the

trend in the temperature behavior

Contrary to the

technique of Kanamori et al our technique takes

into consideration this heat transfer and excludes its in

uence on measurement results Petrunin and Jurchak

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 methodological

The second cause is an appearance along with the lat

tice thermal conductance of a new heat transfer mech

anism Such a mechanism in a crystalline lattice and

in particular in mineral and rock can be the heat radi

ation mechanism with intensity proportional to T and

activated in transparent or half transparent bodies from

the beginning of their luminescence K Ra

diative heat transfer in mineral substances is a special

problem of thermal physics that has been clearly formu

lated and continues to be developed in many laborato

ries including geophysical ones Clauser Fujisawa

et al Kanamori et al MacPherson and

Schloessin Scharmeli 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 ther

mal 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 C p continues to grow also at temperatures

higher than the characteristic temperature inducing a

monotonic increase in the e ective thermal conductiv

ity ef

C p 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 scatter

ing processes among which the three phonon Umklapp

processes become dominant According to the theory

the frequency of such processes increases proportion

ally 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

max

k

h

Thus for the minimal value of min we have by de ni

tion

and consequently

min

h

max

k

l min vh k

The thermal Debye temperature can be replaced

with a su cient accuracy by its acoustic approxima

tion

h

N a

M

k

v

where N a is Avogadro s number is density and v is

the mean sound velocity de ned by the relation between

the longitudinal v p and transverse v s components

v

v

p

v

s

v v

s

p

Table gives the results of computations of l min for

major minerals and rocks in the Earth and comparable

results obtained from experimental thermal di usivity

data obtained by using the formula

a

v

l

It is easily seen that such a comparison leads to an un

expected result even at room temperature the mean

free path of phonons in the majority of geologic materi

als except quartz proves to be only slightly in excess

petr unin and popov

temperature dependence

T able

Mean free path of phonons in minerals and rocks as computed from thermal di usivity data

 

Formula

Mean

v

 

km s

kg m

Mineral rock

composition

atomic

l

A

l

A

l

A

l min

A

 

mass M

Olivine Scharmeli

F o Fa

 

 

Forsterite MacPherson and

Mg SiO

Schloessin

Olivine

F o Fa

 

 

Quartz Scharmeli

SiO

Jadeite Scharmeli

NaAlSi O

Garnet Scharmeli

Pyroxene Scharmeli

En Fs

Microcline Petrunin et al

KAlSi O

Labradorite Petrunin et al Ab An

Dunite

Ol

Harzburgite

Ol En

Eclogite

Gr En

Diorite

Gabbro

P arentheses indicate the average values for a given type of rocks and minerals according to Maj and Povarennykh

et

al

of the minimal value that is reached in the temperature

range K

This fact fundamentally changes our present view of

high temperature behavior of lattice thermal conductiv

ity and thermal di usivity of such compounds as com

plex in their structure and composition as minerals and

rocks First it sets a limiting temperature of the order

of 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

as well

The same fact allowed us to begin developing the prin

ciples of numerical estimation of conductive heat trans

fer in the deep mantle on the basis of the known relation

C p a

C p vl min

where l min is determined from and the in uence of

thermodynamic conditions is taken into account by pa

rameters and v obtained from relevant seismic mod

els It follows from 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 for the simpli ed PEM seismic models of the

upper and lower mantle Dziewonski et al are

given by Fujisawa et al and Petrunin and Orlik

References

Birc h F and H Clark The thermal conductivity of rocks

and its dependence upon temperature and composition

A m

J Sci P and P

Clauser C Opacity The concept of radiative thermal con

ductivity in Handbook of Terrestrial Heat Flow Density

Determination pp

Kluwer Academic Publish

ers

Dziewonski A M A L Hales and E R Lapwood Para

metrically simple Earth model consistent with geophysical

data Phys Earth Planet Inter

Fujisawa

H

N

Fujii

H Mizutani

H Kanamori

and

S Akimoto Thermal di usivity of Mg SiO Fe SiO

and NaCl at high pressures and temperatures J Geophys

Res

Jurchak R P et al Study of Thermophysical Properties

of Dielectrics at High Temperatures in Teplo zicheskiye

svoystva tverdykh veshchestv Thermophysical Properties

of Solids pp Nauka Moscow

Kanamori H N Fujii and H Mizutani Thermal di usivity

measurement of rock forming minerals from to K

J Geophys Res

Kawada K Studies of thermal state of the Earth The th

paper Variation of thermal conductivity of rocks Part

Bul l

Earth Res

Inst

Univ

Tokyo

MacPherson W R and H H Schloessin Apparent lattice

and radiative thermal conductivity at temperatures from

to K and pressures up to GPa Results for

petr unin and popov

temperature dependence

MgO and NaCl in High T emperatures High Pressures

pp

Magnitskiy V A G I Petrunin and R P Jurchak Behav

ior of the thermal di usivity of some eld spars and pla

gioclases at temperatures K Doklady AN SSSR

Ma j S Przewodnicto ciepla i temperatura w gornym pla

szczu ziemi Acta Geophysica Polonica

Petrunin G I and R P Jurchak Allowance for e ect of

the radiative heat exchange in thermal di usivity mea

surements by the plane temperature waves method Vest

nik MGU Ser Fiz Astron

Petrunin G I and E V Orlik Conductive heat transfer in

the Earth s mantle Doklady AN SSSR

Petrunin G I and V G Popov On phonon thermal con

ductivity at the upper mantle interfaces Izv AN SSSR

Fizika Zemli

Petrunin G I V G Popov and M I Timoshechkin Tem

perature behavior of heat capacity thermal di usivity and

thermal conductivity of gallium garnets TVT

Povarennykh A S G T Prodayvoda and A Ju Serga

On the importance of the averaged elastic constants of

minerals Mineral Sh L vov

Scharmeli G H Anisotropy of olivine thermal conductivity

of GPa and up to K measured on optically non

thick samples in High Pressure Research in Geoscience

edited by W Schreyer pp Stuttgart Germany

Schatz J F and G Simmons Thermal conductivity of

Earth materials at high temperatures J Geophys Res

Received June