European Polymer Journal 38 (2002) 18871897

www.elsevier.com/locate/europolj

Electrical and thermal conductivity of polymers lled

with metal powders
Ye.P. Mamunya a, V.V. Davydenko a, P. Pissis
a

b,*

, E.V. Lebedev

Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine, Kharkovskoe chaussee 48, Kiev 02160, Ukraine
b
Department of Physics, National Technical University of Athens, Zografou Campus, 15780 Athens, Greece
Received 12 July 2001; received in revised form 16 January 2002; accepted 7 February 2002

Abstract
The electrical and thermal conductivity of systems based on epoxy resin (ER) and poly(vinyl chloride) (PVC) lled
with metal powders have been studied. Copper and nickel powders having dierent particle shapes were used as llers.
The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer
matrix volume for the systems ERCu, ERNi, PVCCu and to create ordered shell structure in the PVCNi system. A
model is proposed to describe the shell structure electric conductivity. The percolation theory equation r
u  uc t
with t 2:43.2 (exceeding the universal t 1:7 value) holds true for the systems with dispersed ller random distribution, but not for the PVCNi system. The percolation threshold uc depends on both particle shape and type of spatial
distribution (random or ordered). In contrast to the electrical conductivity, the concentration dependence of thermal
conductivity shows no jump in the percolation threshold region. For the description of the concentration dependence of
the electrical and thermal conductivity, the key parameter is the packing factor F. F takes into account the inuence of
conductive phase topology and particle shape on the electrical and thermal conductivity. 2002 Elsevier Science Ltd.
All rights reserved.

1. Introduction
Polymer composites lled with metal are of interest
for many elds of engineering. This interest arises from
the fact that the electrical characteristics of such composites are close to the properties of metals, whereas
the mechanical properties and processing methods are
typical for plastics [1,2]. The achievement of metallic
properties in such composites depends on many factors,
and it is just the possibility of controlling the electrical
and physical characteristics which determines the variety
of ranges of their application.
The transfer conditions of the electric charge and heat
ow determine the electrical and thermal conductivity
level in the heterogeneous polymer-ller system, in which
the conductive phase is formed by dispersed metallic or

Corresponding author. Tel.: +30-1-7722986; fax: +30-17722932.

E-mail address: ppissis@central.ntua.gr (P. Pissis).

carbon ller.The inuence of the type of polymer matrix

and ller on the electrical characteristics of the composite
has been studied in many works [37]. Although in some
publications it was observed that the percolation behavior of the conductive composite depends on both
ller particle shape and spatial distribution within the
polymer matrix, as a rule, the equations and models used
do not contain any parameters linked with the ller
particle shape and conductive phase topology [68].
Concerning the thermal conductivity of such composites,
in spite of several models for two-phase systems [9], there
are only a few publications on the study of the correlation between structure and thermal properties [10,11].
The lling of a polymer with metallic particles results
in an increase of both electrical and thermal conductivity of the composites obtained. Nevertheless, only in a
few papers the electrical and thermal properties of such
two-phase systems are compared with each other. For
example, the authors of [10] have found signicant differences in the electrical and thermal conductivity behavior of lled systems.

0014-3057/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
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In the present article, nickel and copper powders with

essentially dierent particle shapes (irregular, dendritic
for copper and almost spherical for nickel) were used as
conductive llers. Also, two types of polymers (thermoplastic poly(vinyl chloride) and thermosetting epoxy
resin) were used as matrices. The specimen preparation
conditions allow, in one case, a statistical distribution of
metallic particles to be obtained and, in the other case,
to form an ordered shell-structure. These conditions
allow a study of the inuence of both particle shape and
packing density (and, consequently, the conductive
phase topology) on the electrical and thermal conductivity of the composites.

2. Theoretical and phenomenological background

2.1. Structure and characteristic parameters of the conductive polymer system
When a polymer matrix having a conductivity rp is
lled with dispersed ller having a conductivity rf , the
composite prepared gains a conductivity value r. When
the volume ller fraction u reaches a critical value uc
(so-called percolation threshold), an innite conductive
cluster (IC) is formed and, consequently, the composite
becomes conductive [12]. As the ller concentration increases from uc to the lling limit F, the value of r increases rapidly over several orders of magnitude, from
the value rc at the percolation threshold to the maximal
value rm . Below the percolation threshold, the conductivity change is negligible and the conductivity of the
composite is equal to the polymer conductivity rp or
slightly higher. The typical dependence of the logarithm
of conductivity on the ller volume fraction is shown in
Fig. 1.
One of the most important characteristics of the llerpolymer composite is the ller packing factor F [13]. The
value of F depends on the particle shape and on the
possibility of the skeleton or chained structure formation [14]. The parameter F is a limit of system lling and
equal to the highest possible ller volume fraction at a
given type of packing:
F Vf =Vf Vp

where Vf is the volume occupied by the ller particles at

the highest possible ller fraction and Vp the volume
occupied by the polymer (space among ller particles).
For statistically packed monodispersed spherical particles of any size, F is equal to 0.64 [15]. F decreases in the
case of deviation of particle shape from the spherical
one, as well as in the case of formation of the volume
ller skeleton structure, due to increase of Vp . The use of
polydispersed ller particles results in the increase of

Fig. 1. Typical dependence of electrical conductivity (logarithm) on conductive ller volume content. The symbols are
explained in the text.

F[15]. As a rule, real llers have F values smaller than

0.64 [13,14]. Thus, the value of F characterizes the ller
phase topology taking into account the particle shape,
fractional size and spatial distribution of particles.
In the framework of the lattice model by Scher and
Zallen [16], the value of F is linked with the percolation
volume uc of conductive sites by the relation
uc Xc F

where Xc is a critical parameter, which has the meaning

of a site percolation probability. For any lattice type, Xc
and F have such values, that their product uc equals
approximately 0.16. Eq. (2) is valid also in the case
of randomly distributed conductive sites [3]. The model
by Scher and Zallen predicts an insulatorconductor
transition at a strict value of the critical volume of conductive sites uc . In real two-phase systems the sharp
conductivity increase occurs within the concentration
region uc1 < u < uc2 (Fig. 1) called the smearing region
[17]. This eect is a result of the nite conductivity of
phases and the nite size of clusters and sample. The
value of the critical parameter Xc is determined for lattice problems and for models having only one uc value.
For example, for random distribution of conductive
spheres in a non-conductive medium uc 0:16, F
0:64, Xc 0:25 [3].
According to Eq. (2), any change of the value of F,
connected with changes of particle shape or conductive
phase topology, results in a change of uc . Thus, the
packing factor F is a key parameter. Such an approach

Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

allows us to estimate the inuence of changes of the ller

particle geometry and of the conductive phase topology
on the percolation threshold value [18,19].
It should be pointed out that Eq. (2) does not hold
true when polymerconductive phase interactions exist.
In this case, the ller phase topology depends not only on
the ller phase geometry but also on the interfacial interaction at the polymer-ller boundary. Consequently,
the equation linking uc and F has a more complex nature
[19]. According to Wesslings thermodynamic model, in
this case the relationship between uc and F is not dened
by a constant, but includes parameters which reect the
interaction between phases 1 (polymer) and 2 (ller) [20].
For real systems, the value of uc2 can be estimated
only approximately. Therefore, the value of uc1 is mostly
selected as uc and it is considered that the conductivity
change is controlled by the same rule for both the
smearing region and the highly lled region [19]. If uc
equals uc1 the percolation threshold is determined as the
beginning of IC formation. In this case, the value of the
critical parameter Xc in Eq. (2) will be less than that for
the case uc uc2 . In this work uc uc1 is used.
Thus, the conductive system can be characterized by
the set of parameters F, uc and Xc , which are determined
by the system structure, and rp , rc , rm , which are the
parameters of conductivity.

2.2. The shell structure model

The formation of dispersed ller segregated structure
in the polymer matrix may be achieved by the following
technological methods: pressing the mixture of thermoplastic polymer powder having particle size D and of
conductive ller having particle size d, provided that
D  d [1,10,21,22]; extrusion or casting of a mixture of
incompatible polymers provided that only one polymer
contains conductive ller [2325]; lling the polymer
matrix with conductive and non-conductive llers simultaneously, having particle size d and d1 respectively,

1889

with d1 > d [2]. The segregated structure formation allows control of those properties susceptible to spatial
ller particle distribution (electrical and thermal conductivity, dielectric and magnetic properties).
For the rst time, the detailed calculations of the
percolation eects in the polymer system formed by hot
pressing a mixture of polymer powder (particle size D)
and nickel (particle size d, D > d) were carried out in
[21]. Later on, models were developed linking conductivity with the geometrical parameters of the composites
[3].
For systems having size of polymer and metal particles D and d respectively, the following model, demonstrating the conductive phase structure formation in the
segregated system, is proposed. Small metal particles
having size d are assumed to form shells around
randomly distributed large polymer particles (with size
D) in the initial mechanical mixture (Fig. 2). The ller
particles do not shift signicantly in the process of
pressing and only polymer particle deformations take
place. When the average distance between ller particles
(R) is larger than the polymer kernel size (R > D), the
ller particles form three-dimensional random distribution.
With the u value increasing, the ller particles ll up
the boundary between the polymer particles. When the
conductive cluster of ller particles contacting with each
other begins to form, conductivity appears at u uc1 . It
is important to mention that for the appearance of
conductivity it is not required that each polymer particle
is completely covered with a monolayer of metallic
particles in contact with each other. As is shown in Fig.
2b taken from [26], certain eective ller portion on the
polymer particle surface provides conductive cluster
appearance at u uc . Further increase of ller content
results in the increase of the number of layers n of metallic particles on the kernel surface and in the decrease
of the size L of the unlled region, L D  nd. The
schematic picture of the composite structure having shell
thickness equal to nd is shown in Fig. 2c.

Fig. 2. (a) Schematic representation of the assumed distribution of polymer and metal particles (having D and d sizes, respectively) for
mechanical mixtures of PVC/Ni; (b) the minimal polymer particle covering with metallic particles needed for conductivity arising in the
system [26]; (c) schematic representation of the shell structure model.

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For segregated systems, the ller phase may be characterized by two concentration values: an average u
calculated for the whole composite volume and a local
uloc reecting the real ller content in the place of localization [22]. Accordingly, such a lled system has
packing factor values F and Fs [14]. The F value is controlled by the packing of ller particles inside the shell
structure, similarly to the common random ller distribution, and is determined by particle shape, whereas the
Fs value is related to the very shell structure formation in
the polymer matrix volume. Evidently, uloc is larger than
u and Fs is less then F due to the larger Vp value (see Eq.
(1)). Such a composite macroheterogeneous structure is
convenient characterized by the structural coecient Ks
determining the ller segregation level during the shell
structure formation:
Ks uloc =u F =Fs

where t is a critical exponent equal to 1.61.9 [12,27].

However, often, this formal equation does not correspond to experimental results for conductive composites
containing dispersed llers. This is due to the fact that
this equation does not take into account the peculiarities
of the specic system structure (particle shape, polymer
ller interaction, existence of contact phenomena on
the particleparticle boundary, inuence of preparation
conditions on the volume distribution of conductive particles) [6,8,18,19,2730]. Eq. (6) may be written in normalized form as follows [18]:
r  rc =rm  rc u  uc =F  uc t

It follows from Eq. (7)

r rc rm  rc u  uc =F  uc t

where rc , rm , uc , F are parameters characterizing

properties of the specic system.

The geometry of the shell structure model implies [22]:

1=Ks 1  1  nd=D3

2.4. Thermal conductivity of the composites

4

where n is the number of ller layers in the shell structure. This implies that Ks is determined by the ratio of
the two parameters (D and d). As the polymer matrix is
lled and n increases, Fs increases towards F.
It follows from the model that, if the ller concentration has such a value that each polymer particle is
completely covered with a layer of ller particles, then,
after pressing, the number of layers in the shell structure
will be equal to two (n 2). In this case, the distribution
of particles inside the shell structure may be considered
as random [22]. This is a condition that Eq. (2) is satised. By combining Eqs. (2)(4) with each other, the
following expression is obtained for the percolation
threshold for shell structure:
ucs Xc Fs Xc F =Ks uc 1  1  nd=D3

Thus, the systems with segregated distribution of

metallic ller (in the form of shell structure) are characterized by Fs packing factor values and corresponding
ucs percolation threshold values. These values are signicantly lower than those for random ller distribution.
The model oered in this work diers from geometrical
shell structure models discussed in [3], which include
only geometrical parameters of shell structure and do
not consider the modication of the packing factor.
2.3. Electrical conductivity of the composites
The percolation theory oers the following expression
to describe the dependence of the electrical conductivity
on ller volume content in the u > uc region:
r
u  uc t

Several investigations of polymer composites with

dispersed llers show the absence of percolation behavior of the thermal conductivity k with increasing
dispersed ller concentration [911,31]. It should be
pointed out that, in order to explain the more steep rise
of k with increase of u than was predicted by the
equations used, the authors of [32,33] attempted to take
into account additional thermal conductivity related to
the IC appearance. However, the realistic ller geometric characteristics connected with the packing factor F
value have not been taken into account. The reason for
the percolation threshold absence is explained in [34].
This is due to the fact that the thermal conductivities of
the dispersed ller kf and of the polymer matrix kp are
comparable to each other, their ratio not being more
than 103 , whereas the ller electrical conductivity rf
is 1010 1020 times larger than the polymer conductivity
rp . The model [33] predicts the percolation threshold
appearance only if the ratio of ller conductivity to
polymer conductivity is larger than 105 . In fact, the percolation theory is applied only to systems having conductive sites (or bonds) in a non-conductive medium.
Several equations have been used to describe the
concentration dependence of thermal conductivity [9,11,
3133]. All of them provide values within the interval
from the largest two-phase system thermal conductivity
(the system may be represented as a parallel set of plates
(phases) extending in the direction of heat ow and
having thermal conductivities k1 and k2 )
kk k1 1  u k2 u

to the smallest thermal conductivity (the plates (phases)

are stacked in series with respect to the direction of heat
ow)

Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

1891

thermal conductivity of the composites increases from kp

to the largest kF value within the 0 < u < F concentration interval. An equation describing the concentration
dependence of thermal conductivity has been proposed
for that case in [34],
log k log kp log kF  log kp u=F N

13

Evidently, if F 1 and N 1, then Eq. (13) is identical

to Eq. (12) and the behavior of the system follows
Lichteneckers dependence. The value of F 1 means
that the second phase (ller phase) possesses such
properties that it lls up all composite volume at u F
(limit content), i. e. the ller content changes from 0 to 1
volume portion and kF kf . This case is realized for
systems having continuous second phase, for example,
alloys or solutions. If the second phase is a dispersed
ller, then the F value is taken into account by u=F ,
which also changes from 0 to 1.

Fig. 3. The two-phase system thermal conductivity depending

on the composition of the system: (1) the largest thermal conductivity kk calculated according to Eq. (9); (2) the smallest
thermal conductivity k? calculated according to Eq. (10); (3)
thermal conductivity according to Lichteneckers equation, Eq.
(12). For the calculation, the values of k1 and k2 have been xed
to 1 and 103 , respectively. Q is the direction of heat ow.

k? 1=1  u=k1 u=k2

10

where u is the content of plates with thermal conductivity k2 . In the case of the two-phase polymer composite
under investigation in this work, k1 kp and k2 kf .
These relationships are represented in Fig. 3. They have
been successfully used for thermal property analysis of
two-phase materials [35].
Lichtenecker proposed such a dependence, that the
same function describes both the conductivity and resistance: k f kp ; kf ; u; 1=k f 1=kp ; 1=kf ; u [36]. The
following function fullls the above conditions:
kuf
k k1u
p

11

Taking the logarithm, we get:

log k 1  u log kp u log kf
or
log k log kp log kf  log kp u

12

The expressions (9) and (10) presented in semi-logarithmic coordinates are symmetrical with respect to the
expression (12) (see Fig. 3).
Nevertheless, also Eqs. (9)(12) do not take into account the topological peculiarities of the systems lled
with dispersed ller. When such systems are lled, the

3. Experimental
Copper and carbonyl nickel particles with average size
of 100 and 10 lm, respectively, were used for the preparation of the composites.
The composites based on epoxy resin (ER) were prepared by mixing the copper or nickel powder with the
resin (bisphenol A diglycidyl ether) and hardener (diethylene triamine). After being mixed, the composites
were cast into a pan and cured for 2 h at 120C. To
prevent ller sedimentation and to ensure random spatial distribution within the polymer matrix, the pans
were rotated with a frequency of 1 s1 until the specimen
was cured. The ller spatial distribution was controlled
by optical microscopy and found to be uniform.
Powder fraction of 90120 lm particle fractional size
(average size 100 lm) was used for the preparation of
composites based on poly(vinyl chloride) (PVC). The
mixture of polymer and metallic powder was placed into
a hot die at 170 C and pressed after 1 min conditioning.
The specimens for measurements of electrical conductivity were prepared in the form of disks having 30
mm diameter and about 2 mm thickness and also in the
form of plates having 50  10  2 mm dimensions. DC
conductivity (r) values less than 102 104 S/m were
measured by the E6-13A teraohmmeter using disk specimens. At higher values of r, specimens in the form of
plates were used for conductivity measurements by the
four-electrodes method. This method allows the inuence
of electrode-specimen contact resistance to be eliminated.
The measurement scheme has been described in [18].
Thermal conductivity measurements were carried out
under stationary heat ow conditions with the ITEM1M instrument at 20 C, using disk specimens with 15
mm diameter and about 2 mm thickness.

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Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

The density of the composites was measured by the

hydrostatic weighing method and that of the metallic
powder by the pycnometer method. The densities of the
polymers and of the llers were as follows: qER 1:18,
qPVC 1:40, qCu 8:80, qNi 8:50 g/cm3 .
The packing density coecient F of llers (packing
factor) was determined by a method described in [13].
The metallic powder was placed in a glass cylinder and
was subjected to vibrational compression (the frequency
was 50 Hz and the amplitude 0.51.0 mm) [15]. The
value of packing factor F was calculated by the equation
F P =V qf

14

where P is the weight of ller, V the volume of ller in

the cylinder after vibrational compression, and qf the
density of ller particles.
Optical investigation of the structure of the composites was carried out by means of an optical microscope
Biolar in reection mode.

4. Results and discussion

4.1. Structural characteristics of the PVCNi composite
For the PVCNi system, the composite preparation
conditions result in the segregated ller distribution. The
structure of that composite, obtained by optical microscopy at ller contents below, equal and above the percolation threshold is shown in Fig. 4. Thus, the real
system shows good agreement with the model conception.
The dependence of the percolation threshold ucs on
D=d for the PVCNi composites, calculated according to
Eq. (5) for dierent values of n, is shown in Fig. 5. With
the values of the parameters of Eq. (5) D 100, d 10,
n 2 and uc 0:085, the calculation according to this
equation gives ucs 0:041 (see point in Fig. 5). This
value is in a good agreement with the experimental
percolation threshold value 0.040 (Table 1). From Eqs.
(3) and (4), Fs 0:25 is obtained for shell structure
versus F 0:51 for the statistically packed nickel powder (Table 1).
The dependence of the percolation threshold ucs
on D=d, calculated according to models developed by
Malliaris and Turner [21] and by Kusy [26] is also shown
in Fig. 5 (curves 5 and 6, respectively). Our results calculated by Eq. (5) for the three layers (n 3) shell
structure agree well with those predicted by the models.
However, in the region of small values of D=d D=d <
5, these models give too high ucs values.
4.2. Electrical conductivity of the composites
Using experimentally obtained values of composite
characteristics (u, uc , rc and Fsee Table 1) the

Fig. 4. Structure of a segregated composite PVCNi by optical microscopy. The ller content is (a) u < ucs , (b) u ucs ,
(c) u > ucs .

log r
u dependence was calculated according to Eq.

(8) and is shown in Fig. 6. The rm and t values shown in
Table 1 were then obtained by tting Eq. (8) to the experimental data of electrical conductivity of ER and
PVC lled with nickel and copper shown in the same
gure. Evidently, the conductivity values of ER and
PVC containing copper are close to each other, diering
only in the values of rm and of t. The uc percolation
threshold values equal 0.05 for both systems (curves 1
and 2). However, the same polymers lled with nickel
demonstrate dierent percolation behavior (curves 3 and

Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

1893

4). For the ER-Ni system, uc equals 0.085, while for the
PVCNi composite, uc equals 0.04. This eect is related
to the shell structure formation in the case of Ni particles, as discussed above.
The dierence in the percolation threshold values for
ERNi and ERCu is related to the particle shape inuence on the ller packing density, i.e. on the F value.
The experimentally determined packing factor equals
0.30 for copper ller particles, whereas it equals 0.51 for
nickel. The lower F value for copper is related to the
dendritic particle shape, whereas the F value for nickel
comes closer to the theoretical value for spheres, F
0:64.
The experimental conductivity values obtained with
the PVCCu, ERCu and ERNi systems are in a good
agreement with those calculated according to Eq. (8)
with values of the critical exponent t larger than the
universal value of tun 1:7 (see Fig. 6 and Table 1).
High t values have been found for many systems [6,8,
18,37] and various models explaining this eect have
been proposed [27,29,30]. These models assume that t
tun tadd , where the value of tadd is determined by dierent mechanisms (contribution of tunneling conductivity
or complex structure of conductive cluster skeleton with

Fig. 5. Dependence of percolation threshold uc on D/d ratio:

(14) calculation according to Eq. (5) with n 14, respectively; (5, 6) calculation according to models [21,26], respectively.

Table 1
The parameters characterizing the electrical conductivity of the composites
Composite

log rp (S/m)

log rc (S/m)

log rm (S/m)

uc

ERCu
PVCCu
ERNi
PVCNi

12.8
13.5
12.8
13.5

12.5
13.2
12.0
13.3

5.2
5.8
4.8
4.5

0.050
0.050
0.085
0.040

0.30
0.30
0.51
0.25

2.9
3.2
2.4

Fig. 6. The concentration dependence of the composite electrical conductivity: (1) PVCCu, (2) ERCu, (3) PVCNi, (4) ERNi.
Pointsexperimental results, solid linescalculation according to Eq. (15) for PVCNi composites and according to Eq. (8) for the
rest of composites, dotted linescalculation according to Eq. (8) with t 1:7.

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Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

the presence of necks, nodes and blobs). The authors of

[18] proposed the dynamic cluster model, where the
tadd term is not a constant but depends on conductive
ller concentration. In [37] the high values of the critical
index t obtained (around 7 and 10) are explained by the
fact that the critical exponent is anisotropic. Thus, for
the systems studied, the value of t > tun indicates a
complex structure of the conductive phase. In [29] it has
been shown that the value t 3, observed in many experiments [68], can be obtained within the mean eld
theory.
For the PVCNi composite, the concentration dependence of r does not obey the percolation Eq. (8) at
any t value. This can be explained if the ordered spatial
ller particle distribution and the shell structure formation process, dierent from statistical, are taken into
account. In this case, we use the equation of logarithmic
conductivity [19]:

shell structure formation. Good agreement of the calculated values with experimental results was achieved at
K 0:27 (Fig. 6).
Eq. (2) determines the correlation between the percolation threshold uc and the packing factor F via the
critical parameter Xc . As mentioned above, in real systems Xc can take dierent values due to the existence
of the smearing region in the percolation interval and,
consequently, of the several uc (for example, uc1 and
uc2 ) values. The experimentally determined F and uc
uc1 values give the value of Xc 0:17 for the PVCCu,
ERCu and ERNi systems studied in this work. The
same value is found for the packing of the ller particles
inside the shell structure. The coincidence of Xc values
for all systems indicates the absence of polymer-ller
interactions in these systems.
4.3. Thermal conductivity of the composites

log r log rc log rm  log rc u  uc =F  uc

15
Eq. (15) diers from Eq. (8) by the use of the logarithmic
conductivity log r instead of conductivity r. This difference results in the replacement of the critical exponent
t by the exponent k. The value of k is not a constant for
various composites and equals
k Kuc =u  uc 0:75

16

K is a value depending on the conductive phase topology. The topology, in turn, can be determined by the
extent of interactions between the host polymer and
ller surface [19] and by other factors, for example, by

The experimental dependence of thermal conductivity

on ller volume content for the composites studied is
shown in Fig. 7. The curves in the same gure have been
calculated according to Eq. (13). The experimental values of uF, kp and tted values of kF and N were used for
the calculation. These functions are linear (N 1:0),
except for PVCNi to be discussed later, and they are in
a good agreement with the experimental data. The parameters of Eqs. (12) and (13) are presented in Table 2.
Evidently, the experimental thermal conductivity values
of composites with copper are larger than the data
predicted by Eq. (12) (dotted lines), while the thermal
conductivity values of the composite ERNi are slightly
lower than the predicted values. The inuence of the

Fig. 7. Concentration dependence of the thermal conductivity of the composites: (1) PVCCu, (2) ERCu, (3) PVCNi, (4) ERNi.
Pointsexperimental results, solid linescalculation according to Eq. (13), dotted linescalculation according to Eq. (12).

Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

1895

Table 2
The parameters characterizing the thermal conductivity of the composites
Composite

log kp (Wt/m K)

log kF (Wt/m K)

log kf (Wt/m K)

ERCu
PVCCu
ERNi
PVCNi

0.64
0.78
0.64
0.78

0.55
0.46
0.58
0.09

2.59
2.59
1.95
1.95

1.0
1.0
1.0
1.3

packing factor accounts exactly for that observation. It

has been shown that, for composites lled with llers
having dierent F values, the thermal conductivity increases faster in the systems with the lower values of F
[11]. Such behavior is demonstrated by the composites
with copper (F 0:30) and with nickel (F 0:51). This
is due to the fact that, for the same u value, the particles
are closer to each other in the system with the smaller
F value. The following expression links the distance between particles R with the dispersed ller packing parameters [38,39]
R dF =u1=3  1

17

In such a system, the heat transfer from particle to

particle is easier because of thinner polymer layers between the particles. Thus, similar to the case of electrical
conductivity, the packing factor F is a key parameter
allowing account to be taken of the realistic geometrical
ller characteristics.
It also follows from Fig. 7 that the thermal conductivity of the polymer matrix kp has signicant inuence
on the thermal conductivity of the composites. Actually,
the thermal conductivity of the composites based on ER
is larger than that of the composites based on PVC within

the whole region of ller content. This fact is conrmation of the heat ow limitation by the transfer through
polymer layers between metallic ller particles. The same
eect was found in [31] for composites lled with mineral
llers and having two dierent polymers as a matrix.
The concentration dependence of thermal conductivity behaves signicantly dierent for the PVCNi composites (Fig. 7, curve 4). The dependence is not linear
(N 1:3) and grows rapidly in the region of small ller
concentration. Thus, the shell structure formation
having local ller concentration uloc results in more dense
ller packing inside the shell structure and in improvement of the heat transfer conditions. The authors of [10]
observed for the rst time the increased thermal conductivity of the systems with segregated ller structure.
They proposed to introduce the metallic conduction
coecient correction into the equation describing the
concentration dependence of thermal conductivity. In
our model, this is taken into account by the exponent N
in Eq. (13).
However, there exists an eect decreasing the predicted
thermal conductivity. Closer examination of the relationships presented in Fig. 7 shows that, when the ller
volume content u reaches the lling limit F, then k begins
to decrease. The polymer part density qp , determined by

Fig. 8. Polymer matrix density qp versus ller volume content u: (1) PVCCu, (2) ERCu, (3) PVCNi, (4) ERNi.

1896

qp q  uqf =1  u

Ye.P. Mamunya et al. / European Polymer Journal 38 (2002) 18871897

18

(where q and qf are the densities of composite and ller,

respectively) starts decreasing when the ller concentration reaches values close to F (Fig. 8). This is due to
the fact that air inclusions occupy a part of the composite volume. The high viscosity of highly lled composites makes the process of mixture homogenization
dicult in composites with ne ller and/or in composites obtained by pressing. This leads to accumulation
of non-destroyed aggregates of ller particles containing
air. The air thermal conductivity is one order of magnitude lower than that of the polymer. The presence of
air inclusions is the reason for the thermal conductivity
decrease at high ller volume fractions. Thus, technological problems do not allow the realization of high
thermal conductivity at high ller contents. At the same
time, the air inclusions do not inuence the electrical
conductivity of the composites, since both polymer part
and air inclusions are non-conductive media.

5. Conclusions
The results obtained with the investigated metal-lled
polymer systems allow us to draw the following conclusions.
1. In explaining the concentration dependence of electrical and thermal conductivity, the packing factor
F is a key parameter, taking into account the inuence of conductive phase topology and particle shape
on the electrical conductivity r and thermal conductivity k.
2. The percolation threshold value uc depends on the
particle shape and on the kind of the spatial distribution of the particles (random or segregated) and is
connected to F. Due to absence of polymer-ller interactions, a linear relationship is observed between
the percolation threshold and the packing factor,
uc Xc F . The critical parameter Xc was found experimentally to be Xc 0:17.
3. The percolation theory equation r
u  uc t holds
true with t 2:43.2 (exceeding the universal t 1:7
value) for systems with random distribution of dispersed ller in the polymer matrix.
4. Pressing the mixture of polymer and metallic powders having particle sizes D and d, respectively (assuming D  d), allows the formation of a shell
structure having a low percolation threshold value.
For such systems, the percolation equation r
u 
uc t does not hold true at any t value.
5. In contrast to electrical conductivity, the concentration dependence of thermal conductivity does not
show the percolation behavior. The composite thermal conductivity (at certain ller concentration u)

depends on ller conductivity, polymer matrix conductivity and F. However, it is dicult to realize a
high thermal conductivity near the lling limit
(u ! F ) because of the porosity of the composites.
Thus, the shape and the spatial distribution of dispersed ller particles are the important factors controlling the electrical and thermal properties of metal-lled
polymer systems.

Acknowledgements
This work was supported by the project INTAS-971936, by DIGICYT (Grant PB94-0049), and by the
program Archimedes, ICCS, NTUA.

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