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Estimation of Thermal Conductivity in Solids

Can Onur Akyuz
Mechanical Engineering Department
Bogazici University, Bebek, 34342, Istanbul, Turkey



ABSTRACT. Estimation of thermal conduction values of solids is of great importance for many
engineering applications. Especially during preliminary stages of design and for thermal analysis of
systems where experimental ways to determine thermal conductivity values are limited, the need for
an accurate approximation of conductivity arises. The goal of this paper is to present briefly the
background of the theory on thermal conductivity and the Wiedemann-Franz law, and to utilize the
aforementioned law in order to estimate the thermal conductivity of an alloy. This estimation is then
compared with empirical data in literature, and the accuracy of the method is evaluated.


1. Nomenclature

k Total Thermal Conductivity
Electronic Thermal Conductivity
Lattice Wave Thermal Conductivity
L Lorentz Number
Standard Lorentz Number
Electrical Conductivity
Electrical Resistivity
Electrical Resistivity at 293 K
Temperature Coefficient of Resistance
X Molar Fraction of the Solute Component

2. Introduction

Estimation of the thermal conductivity of solid materials is an important process in engineering
applications. Various methods can be used to determine the thermal conductivity of a given
material. These include experimental methods which are employed directly to the sample being
tested. These involve a certain factor being applied to the system (for example a steady heat flux)
and the change in the system can be observed to determine this systems thermal properties.
Thermal conductivity can also be determined using a combination of numerical methods and heat
conduction theory. An example to this is the inverse conduction method, which is used to determine
the thermal conductivity of a material whose temperature distribution, boundary conditions and
initial conditions are known. With such available information it is possible to derive either
analytically or numerically an expression for the thermal conductivity with regards to certain
variables.

The main factors that affect thermal conductivity factor k are temperature, the type of material, the
phase and structure of the material (including lattice defects and imperfections), electrical
conductivity and also external influences, namely magnetic fields [1]. However in practical
applications some of these variable may be eliminated with appropriate assumptions.

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In metals and alloys thermal energy is mainly transported by electrons and lattice waves. Because of
this total thermal conductivity is taken as the sum of electronic thermal conductivity and lattice
thermal conductivity, where heat is transferred by electrons in the former and by phonons in the
latter [2]. This can be expressed as:

( 1 )

In many pure non-transition metals thermal conduction via phonons is negligible at all
temperatures, but in alloys conduction with lattice waves may be as important as, or even more so
than electronic conductivity at low temperatures. This may also be the case at temperatures much
higher than the Debye temperature of the material.

When considering pure metals thermal conductivity associated with heat transferred by electrons
tend to be much higher than thermal conduction by phonons. This allows a reasonable
approximation of heat conduction to be attributed only to . Therefore, by determining , a
reasonable estimation of total thermal conductivity can be acquired.

The Wiedemann-Franz Law

The Wiedemann-Franz Law is one of the most utilized methods to predict thermal conductivity. It
has been derived in 1850s, years before the Drude model representation of electrical conduction,
and quantum description of molecular and atomic interactions. The law was based on the
proportionality of experimentally acquired values of electrical conductivity and thermal electronic
conductivity Furthermore it was also discovered that the temperature of the material also had an
effect on this ratio and a constant called the Lorentz number. Thus the law is expressed as:


( 2 )

Or alternatively by replacing ,


( 3 )

It has been observed that at the same temperature, this ratio has approximately the same value for
metals. Thus the value Lorenz number is usually fixed to:



( 4 )

Which is the standard Lorenz number, and this value is derived from the Drude-Sommerfeld model
(Free electron model) [1]. This law breaks down at intermediate temperatures where effects of non-
elastic electron scattering become significant, and this results in the loss of a portion of the heat
transferred by the electrons. Because of this the thermal conductivity predicted by the Wiedemann-
Franz law can double the real value, as can be observed for pure aluminum at 100 K [3].

Table 1: Values of the Lorenz Constant for Pure Metals (in ) [4]

Metals Cu Ag Au Zn Cd Sn Mo Pb Pt
Lorenz
Const.
2.23 2.31 2.35 2.31 2.42 2.52 2.61 2.47 2.51

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The importance of Wiedemann-Franz Law arises from the fact that the measurement of electrical
conductivity is much easier and more accurate compared to the measurement of thermal
conductivity. With the use of this law, accurate estimations for the thermal conductivity of pure
metals with changing temperatures can be obtained. However this law may present shortcomings
due to the increasing effect of thermal conduction done by phonons. Because of this the law must be
modified for alloys and other solid materials where thermal conduction via phonons play a
significant role.

This law also explains the tendency of materials with high electrical conductivity to also have good
thermal conduction properties, such as copper and gold. Also to note is that most solid materials
that are insulators transfer heat mainly through lattice waves, resulting in low thermal conductivity
levels.

Smith-Palmer Equations

While it is possible to acquire a valid estimation for the thermal conductivity of pure metals using
the Wiedemann-Franz law, the effects of lattice wave thermal conduction cause similar estimations
for alloys and other solid materials to deviate significantly from experimental values. In light of
this, modifications have been made to Wiedemann-Franz Law to compensate for this type of error.

One such modification are the Smith-Palmer equation, which has been derived by Smith and Palmer
through the analysis of Cu-based alloys:


( 5 )

The constants A and B depend on the material/system in question. The first term characterizes the
electronic part of total thermal conductivity, and it is in the form of the Wiedemann-Franz Law. The
phonon component of thermal conductivity is represented by the second term [5].

In order to obtain an even more detailed estimation it is possible to further modify this equation to
account for the change of thermal conductivity with relation to temperature and chemical
composition, by expressing the electrical resistivity term as a function of chemical composition and
temperature.

3. Problem Statement

The goal of this paper is to estimate the thermal conductivity of Ni-Cr alloy with 20% chrome using
different expressions, and to compare the obtained results with experimental values. The
estimations will be carried out using the following expressions:

(1) The Wiedemann-Franz Law with resistivity expressed as a function of temperature and
temperature coefficient of resistance ,
(2) Smith-Palmer equation with corresponding values of A and B for Ni-Cr alloys, and average
electrical resistivity,
(3) Smith-Palmer equation with electrical resistivity obtained using the relevant temperature
coefficient of resistance,
(4) Smith-Palmer equation with electrical resistivity formulated as a function of temperature and
chemical composition.

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The results will then be evaluated to determine if any of the methods mentioned above can be used
in practical applications to obtain a reliable thermal conductivity estimation. If not, reasons of their
shortcomings will be discussed.

4. Formulation

The first estimation method is chosen as the Wiedemann-Franz Law. The values of L, and are
chosen as L = 2.44 , = 0.00017, and , where .
The resistivity can be written as:

( 6 )

Thus the equation becomes:



( 7 )

The second method uses the Smith-Palmer equation and an average electrical resistivity taken as
electrical resistivity at room temperature which is m. The constants A and B are
taken as A = 0.283 and B = 10.2 W . The second equation then becomes:

( 8 )

The third method employs the Smith-Palmer equation with electrical resistivity changing with
respect to temperature. For this case Eq. (6) has been used and the values of A and B are chosen to
be the same as the second method. The equation then takes the form:


( 9 )

The final method involves writing the resistivity of the alloy in terms of temperature and its
chemical composition. To denote chemical composition the molar fraction of chrome will be used.
As such, the variables of this expression will T and X, where T is the temperature and X is the
molar fraction of Cr.

The electrical resistivity of a solid solution can be expressed as the combination of resistivity due to
thermal lattice vibrations and impurities[5]:

( 10 )

The electrical resistivity due to thermal lattice vibrations can be obtained from a liner relationship:

( 11 )

The electrical resistivity due to impurities can be expressed as:

( 12 )

This equation is the Nordheims rule. is a temperature-related coefficient dependent on the alloy.
Combining both terms the general equation for electrical resistivity becomes:
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( 13 )

The term can be approximated as a linear relation for the case of Ni-Cr. Substituting this
expression in the Smith-Palmer equation the following relation is obtained:

( 14 )

This expression is then simplified using a McLaurin expansion with respect to 1/T and 1/X(1-X):

( 15 )

This expression can be further simplified considering the X(1-X) terms in the first term are
negligible compared to 1/T for temperatures above 600 K [5]. Another simplification is done by
introducing constant e:

( 16 )

The appropriate constants for Ni-Cr alloys are ,
and . The final form of the equation is as follows:

( 17 )

5. Results

Using the four different methods estimations for the thermal conductivity of the Ni-Cr alloy has
been obtained, and compared with experimental values, as shown in Fig. 1:



Figure 1. Comparison of the estimations and experimental results.
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The results for all models were derived from a temperature range of 0 K to 1200 K and for X = 0.2.

The first method, which employed the Wiedemann-Franz law directly, gives a steady percentage of
error, which is slightly lower at higher temperatures. This comes from the fact that thermal
conduction through phonons is completely ignored in this formulation. The results of this
estimation also indicate that the phonon component of thermal conduction does not change as the
electronic component.

The third method and also the first method is good at estimating thermal conductivity at lower
temperatures when compared to other methods. In relation with the third, the second method
produces very similar values, but is inferior to the third in lower temperatures. The values of both
the second and the third method deviate strongly from experimental results at high temperatures,
rendering these methods inapplicable for such temperature ranges.

The fourth method, which took into account the chemical composition of the alloy as well as the
temperature was the most successful. It reproduces the thermal conductivity values quite accurately
at higher temperatures, and even though formulated for temperatures values greater than 600 K, the
extrapolated curve provides a reasonably well estimation for lower range temperatures too.

6. Discussion

The goal of this work was to derive an accurate estimation for the thermal conductivity value of Ni-
Cr solid solution system with %20 Cr content. The four different models proposed for this purpose
have been compared with experimental results. The most successful model was the method which
also included the chemical composition of the material. With reasonably low error margins this
model can be used in practical application for the estimation of thermal conductivity.

The Smith-Palmer equations though not accurate in general can reproduce very accurate results for
lower temperatures and, depending on appropriate design parameters, can also be utilized as a valid
model for estimations.

The model based solely on the Wiedemann-Franz law is not recommended for practical
applications, as it gives results that may prove inadequate, due to its neglecting of the thermal
conduction thorough phonons.

The modified Smith-Palmer equation with chemical composition included as a variable can also be
potentially extended for other types of alloys to obtain accurate estimations for thermal
conductivity. The inclusion of the chemical composition to these estimations also improve the range
of applicability of this model, and the versatility of this model offers a valuable tool for design and
practical applications.


References

1. Tritt, Terry M., ed. Thermal conductivity: theory, properties, and applications. Springer,
2004.
2. Ho., C. Y., Aclerman, K. Y., Wu, S.G., Oh, S.G., Havill, T.N.,Thermal Conductivity of Ten
Selected Binary Alloy Systems, Journal of Physical and Chemical Reference Data, Vol.7,
pp. 959-1169, 1978.
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3. Tuttle, J., Canavan, E., DiPirro, M., Thermal and electrical conductivity measurements of
CDA 510 Phosphor Bronze, AIP Conference Proceedings, Vol.1219, 2010.
4. Blatt, F. J., Modern Physics, McGraw-Hill, 1992.

5. Endo, R., Shima, M., Susa, M., Thermal-Conductivity Measurements and Predictions for
Ni-Cr Solid Solution Alloys, International Journal of Thermophysics, Vol. 32, pp. 1991-
2003, 2010.