APPLICATION OF NORBURY RULE TO THERMAL CONDUCTIVITY

IN INTERMETALLIC COMPOUNDS

YOSHIHIRO TERADA, TETSUO MOHRI AND TOMOO SUZUKI

Hokkaido University, Graduate School of Engineering, Division of Materials Science and
Engineering, Sapporo 060, Japan

ABSTRACT
Thermal conductivity data at room temperature, which are measured by laser-flash method,
arc presented in B2 aluminides and titanides, and in nickel based L1 2 compounds. The thermal
conductivity X is changed in the following order of the compounds. ),(NiAl) >),(CoAl)>
),(FeAl), X(NiTi)< ,(CoTi)< X(FeTi), ,(Ni3 AI)>.(Ni 3 Si) and X{Ni 3 Ga)>k(Ni3Ge). According
to Norbury rule originally proposed for the concentration dependence of electrical resistivity,
the increasing rate is greater in the solid solution, where the position of solute elements is more
remote in horizontal distance from a host metal in the periodic table. It is found that this rule
holds for the thermal conductivity measured for the intermetallic compounds with the
combination of a series of guest constituents and a fixed host constituent both in the B2 and
L12 intcrmctallic compounds.

1. INTRODUCTION
The thermal conductivity is one of the most important properties to be explored in the high
performance materials at elevated temperatures. Materials with a high thermal conductivity are
desirable to avoid the hot spot phenomenon during the application at elevated temperatures.
The thermal conductivity data will be needed for the estimation of cooling ability. However,
the thermal conductivity data as well as the electrical conductivity data in intermetallic
compounds are quite limited.
This is partly because the precise shaping of specimen of the compounds with low ductility is
very tedious. On the other hand, the laser-flash method for the thermal conductivity
measurement is very suitable and convenient, since the preparation of a coin-shaped specimen
for the laser-flash measurement is very easy to achieve even for brittle materials.
The comprehensive survey program for the thermal conductivity in intermetallic compounds
has been started in 1993 by the group of the present authors at Hokkaido University. The
thermal conductivity data for B2 aluminides and titanides have been already published[l], and
those for nickel based L12 compounds are under preparation for publication[2]. It appears
from these investigations that the thermal and electrical conductivities would be further
decreased in a series of compounds as the positions of the two components become distant
from each other in the periodic table. And it is discussed that this feature is analogous to the
Norbury rule, which is induced from a lot of data of electrical resistivity change in dilute solid
solutions[3].
The aims of this report are to review the previous data for the B2 and L12 compounds and to
elucidate the correlation between the original Norbury rule found for electrical resistivity in the
solid solutions and the " Norbury rule " proposed for the thermal conductivity in the
intermediate phases.

2. EXPERIMENTAL

The details of experimental measurement were mentioned in the previous paper[l]. Here, it
is briefly stated. All specimens were prepared by arc-melting using high purity elemental
metals. The alloy buttons were sealed off in quartz tubing under a vacuum of 1 x 10-4 Pa,
followed by homogenization and then water-quenched. The disc specimens 10 mm in diameter
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Mat. Res. Soc. Symp. Proc. Vol. 364 01995 Materials Research Society
and 2 mm in thickness were cut off from the button ingots by electro-discharge machining.
Both faces of the discs were mechanically polished to provide smooth surfaces and to obtain
parallelism. The single phase with B2 or L1 2 crystal structure is confirmed by X-ray
diffraction and metallography. Grain size of the specimens ranges from 300 to 500 Rtm in all
specimens. Thermal conductivity at room temperature was measured by a laser-flash method
using an ULVAC TC-7000.

3. RESULTS AND DISCUSSIONS

3.1 Review of the thermal conductivity data for B2- and Li12-type compounds

In Fig.i, taken from the previous work[l], the thermal conductivities of the stoichiometric
aluminides (XAI), titanides (XTi) and gallides (XGa) are plotted against the constituent X.
The value of MnAI having a different crystal structure is supplementary added. All these
elements belong to the first transition metal series in a periodic table. For aluminides, the
thermal conductivity increases with increasing atomic number of the transition metal
element X. This tendency holds also for gallides (XGa). On the contrary, for titanides (XTi),
the thermal conductivity decreases with increasing atomic number of the transition metal
element X.
The thermal conductivities of the four stoichiometric L12 compounds (Ni 3 X) are plotted
against the constituent X, as shown in Fig.2[2]. It is obvious that the thermal conductivity of
Ni 3Si is smaller than that of Ni3AI. Also, the thermal conductivity of Ni3Ge is smaller than
that of Ni3Ga. It is concluded that the thermal conductivity of Ni 3 X decreases when the
constituent X is changed from 3B subgroup to 4B subgroup element.
In order to examine the carrier responsible for heat conduction in these compounds, the
relation between the electrical conductivity and the thermal conductivity in the stoichiometric
B2 compounds is presented in Fig.3, which is taken from the previous work[l]. In this figure
also plotted is the stoichiometric L1 2 compound Ni 3 AI. Thermal conductivities at room
temperature are obtained by the present authors and the electrical conductivities adopted here
are the values reported in the literature[4-12]. Unfortunately, the electrical conductivity data
for nickel based Li 2 compounds other than Ni 3A are not available.

- 100 / . 50
0
"a"a xAl
A N~i
3
G
XTi -

0 0
NiNiM
"" XGa 5V 3
3-~

0 C

0 1II 0 4B
Mn Fe Co Ni 3B 4B
Element X Element X

Fig. 1. Thermal conductivity at room Fig. 2. Thermal conductivity at room

temperature of stoichiometric aluminides
(XAI), gallides (XGa) and titanides (XTi)
against the element X. The values are
obtained by the extrapolation to the
stoichiometry by plotting the thermal
conductivity against the deviation from
stoichiometry[l].
temperature of stoichiometric nickel based
L12 -type compounds (Ni 3 X) against the
element X. The values are obtained by the
extrapolation to the stoichiometry by
plotting the thermal conductivity against the
deviation from stoichiometry[2].

202
 SA5th period
"E15 - 0 6th period

a C.
e-i-
V (But)
OFe
0
Ni3AI (Y.C)
b• 10 - V1
CoAl S"2°/
NiTi CoTi A (1k,)

SFeAI
NiGa o(Sel) 4 (Gof) oo A.0
0 ~ VV ,'Goffi (All)
5 S 5
-covo
U
-~CoGa
V (Gofy
,j(But)
(Yam) il
./ , 1(W OM PtAS

O ON
C)(Cof All) (Ya) Wiedemann-Franz law
Ni2 \IH~,
U I(All)
I)
0 (Y, 0 I f-&I I j
0 100 7A 8- 1B 20 3B 40 5B

Thermal conductivity, A/ Wm-'K-1 Element X

Fig. 3. Wicdcmann-Franz relation of Fig. 4. The increment of electrical

stoichiomctnic B2 intcrmetallic compounds
and Ll 2 compound of Ni 3AI. Thermal
conductivity data are obtained in our
studies [1,2], and electrical conductivity
ones are converted from the electrical
resistivity reported in the literature[4-12].
resistivity in copper at room temperature
caused by the addition of a solute element
at one atomic per cent. The data reported
by Linde are employed[16]. The increase
in the electrical resistivity is greater in the
solid solution, when the position of solute
elements is more remote in horizontal
distance from copper in the periodlic table.

It is well-known that the Wiedcmann-Franz law holds for metallic materials, i.e., pure metals
and alloys at higher temperatures [13-15], which is given by the following equation;

X =( 3
2 2
k /3 e2 )T G=L TG, (1)
where X is the thermal conductivity, a is the electrical conductivity, k is Boltzmann constant, e
is electric charge of an electron, and T is absolute temperature. The term within the
parenthesis, L, is known as the Lorentz number. A proportionality constant of a against X is
found to be equal to 7.5 x 10-6 W Q K-I at 300 K in pure metals [15].
The straight line in Fig.3 indicates the Wiedemann-Franz relation at 300 K. It is found in this
figure that there is a fairly large scatter of the data of the electrical conductivity in NiAl, CoAl
and FeTi, having more than two data sources. It is reasonable to say that all the plots of these
B2 intermetallic compounds and that of Ni 3 AI fall on the line. This indicates that these B2 and
L1 2 intermetallic compounds satisfy the Wiedemann-Franz law at room temperature, and,
thereby, one may attribute the heat carrier to the electron rather than phonon, which is
indicative of typical metallic behavior.

3.2 Norbury rule originally proposed

The empirical rule is well established that the increase in electrical resistivity is greater in the
terminal solid solution, when the position of solute elements is more remote in horizontal
distance from a host metal in the periodic table[3]. This empirical rule was firstly found by
Norbury in 1921, and this has been named as the Norbury rule.

203
 Figure 4 shows, as a typical example, the increment of electrical resistivity of copper at room
temperature caused by the addition of a solute element at one atomic per cent, Ap. In this
figure, the data reported by Linde are adopted[16]. The solute elements are arranged in the
order of atomic number. It is apparent that the increase in electrical resistivity is greater in a
solid solution, when the position of solute elements is more remote in horizontal distance from
copper in the periodic table. The quantitative statement of the Norbury rule is known as the
Linde rule, which is expressed in the form of;
2
dp/dx =kl +k2(NI -N2) , (2)

where p is the resistivity, X is the concentration of solute, NI and N2 are valences of host metal
and B subgroup solute elements, and kl and k2 are constants. It is clear that the equation (2)
corresponds exactly with the experimental data for B subgroup solute elements in Fig.4, where
the resistivity change Ap increases in a parabolic manner. It is confirmed that this rule holds in
the case that the host metal is silver or gold[16].
In order to understand the present results obtained for intermetallic compounds, we extend
the Norbury rule to the change in conduction properties of a series of compounds, such as the
B2 aluminides, the B2 titanides, and the nickel base L12 compounds. We claim that there is a
superficial analogy between the changing rate of conductivities with the solute elements and
the magnitudes of the conductivities of the intermetallic compounds within the fixed crystal
structure.

257 W.. o.K I

200
E -0

"$ C.

-o 100

0
50 100 0 1 2 3 4
Al concentration, x/ at%

Fig. 5. Thermal conductivities of various Fig. 6. Difference of the thermal

phases in the Ni-Al alloy system. The U-
shaped line, which represents the
conductivity of disordered fcc solid
solution, is drawn on the basis of the
Nordhcinm equation.
conductivity between the disordered state
and ordered state in Cu 3 Au[18-21], Ni 3 Mn
[22,23], Ni 3 Fe[24] and Ni3 AI. The thermal
conductivities of the ordered state in Ni 3Ai,
Ni 3Ga and Ni3Ge are also shown.

204
3.3 Thermal conductivity of the terminal solid solutions and intermetallic compounds
Figure 5 shows the thermal conductivities of phases started from the nickel terminal solid
solution, several intermediate phases, including Ni 3 AI and NiAI, to pure aluminum phase in the
Ni-Al alloy system. In this figure, the U-shaped line running from Ni to Al is drawn on the
basis of the Nordheim equation[17], of which original form is given as;

P = PBX + PA(1-X) + k3X(1-X), (3)

where PA and PB are the electrical resistivity of the components, X is the solute concentration,
and k3 is constant. Assuming that the Wiedemann-Franz law is applicable to all the solid
solution region in the alloy system and taking the inverse of resistivity, the thermal
conductivity X.can be rewritten as eqn.(4);

X = 1 / { X/Xk+ (1-X)/XA + k 3 *X(1-X) }. (4)

Thus, the constant k3* in the above equation can be defined from the conductivity data in
nickel solid solution. The U-shaped line thus obtained indicates the conductivity change in the
hypothetical continuous fcc solid solution of the Ni-Al system. All the values of thermal
conductivities of intermetallic compounds are larger than the values of solid solutions expected
from the Nordheim rule. This result indicates that the ordering increases the conductivity,
irrespective of the crystal structure. In general, the decrease in electrical resistivity caused by
ordering has been well established in the Kurnakov compounds, such as Cu3Au[18-211,
Ni 3 Mn[22,23] and Ni 3Fe[24] for the L1 2 crystal structure and FeCo[25,26] for the B2 crystal
structure.
For the L1 2 -type compounds, including Ni 3 AI, the thermal conductivities are plotted in Fig.6
as a function of AN. The separation between the constituents of the compound in the periodic
table is defined as AN. All the previous data of electrical resistivity are converted to the values
of thermal conductivity by using eqn.(1). This figure is regarded as an extension of Fig.4 and it
can be seen that the " Norbury rule " is applicable in both the ordered state and the
concentrated disordered state.
It should be noted that the relation shown in Fig.6 is not always common for the L12
compound. For example, in Au 3Cu[18,27, 28] and Pd 3 Fe[29] it is observed that the resistivity
of the ordered state is larger than that of the disordered. -Further experimental works on the
accumulation of data and the theoretical works based on electron theory are needed to get a
general understanding on the origin of the Norbury rule for the solid solution and the " Norbury
rule " for the compounds.
4. CONCLUSION
Thermal conductivity of B2-type aluminides and titanides with iron group transition metals
and of nickel based L1 2 -type compounds has been investigated at room temperature using a
laser-flash method. The results are summarized below.
1) The stoichiometric B2 and L1 2 compounds obey the Wiedemann-Franz relation at room
temperature. Electrons rather than phonons are dominant carriers of heat in these compounds,
which is indicative of typical metallic behavior.
2) The thermal conductivity of B2 and L1 2 compounds is greater when the position of a guest
element is more remote in horizontal distance from a fixed host component in the periodic
table. It appears that the Norbury rule can be applied to the conductivity change of a series of
compounds.
3) Thermal conductivities of the phases in the Ni-Al alloy system are larger than those of the
hypothetical fcc phase expected from the Nordheim rule. This indicates that the thermal
conductivity usually increases with ordering, i.e., with the formation of intermetallic
compound, irrespective of the crystal structure.

205
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support provided by Grand-in-aid for
Scientific Research from the Ministry of Education, Science and Culture under Contract
No.06215101.
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