Charge Transport Properties in Carbon

Black/Polymer Composites
G. C. PSARRAS
Department of Materials Science, School of Natural Sciences, University of Patras, Patras 26504, Greece

Received 1 March 2007; accepted 27 June 2007

DOI: 10.1002/polb.21278
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: The charge transport properties of polymer matrix–carbon black compo-

sites are investigated in this study. Direct current conductivity is examined with
varying parameters: the temperature and the conductive filler content. Conductivity
data are analyzed by means of percolation theory, and both percolation threshold and
critical exponent are determined at each of the examined temperatures. The tempera-
ture dependence of conductivity and the agreement of experimental results with the
variable range hopping model reveal hopping conduction as the predominant trans-
port mechanism, below and in the vicinity of the critical concentration of carbon
black particles. At higher concentrations, the contribution of hopping transport to the
overall conductivity is reduced and a balance between hopping and conduction via ge-
ometrical contact occurs. VC 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45:

2535–2545, 2007
Keywords: charge transport; composites; disorder; percolation

INTRODUCTION tromagnetic interference shielding systems, radio

Amorphous thermosetting polymer matrices,
such as different types of epoxy resins, have been
extensively used1–4 for the fabrication of compos-
ite materials, because of their good adhesion
with reinforcing elements, enhanced thermal sta-
bility, resistance to chemical attack, and resist-
ance to degradation under the influence of corro-
sive environment.5 The majority of the applica-
tions of the epoxy resin composites refer to the
field of the aerospace and automobile industry,
where the reinforced systems are in the form of
composite laminates incorporating long continu-
ous fibers, and are employed as load-bearing
structural elements.4 On the other hand there is
a variety of applications, where epoxy resins
filled with conductive inclusions are used as elec-
Correspondence to: G. C. Psarras (E-mail: G.C.Psarras@
upatras.gr)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 45, 2535–2545 (2007)
V
C 2007 Wiley Periodicals, Inc.
frequency interference shielding systems, and for
the dissipation of electrostatic charges from rotat-
ing and wearing members, or in the field of
microelectronics between adjacent planes of mul-
tilayers printed circuits board.6–8
Polymers are in principle electrical insulators,
since their concentration of free charge carriers
is very low. High values of conductivity in poly-
mer matrix composite systems can be achieved
by incorporating conductive fillers, such as car-
bon black (CB) particles, carbon fibers, metallic
fillers in the form of powder or short fibers, and
intrinsically conductive polymers.9–14 The elec-
trical response of these systems has been widely
investigated under the influence of both dc and
ac electrical field.9–16 Examining the relaxation
phenomena and the direct current (dc) conduct-
ance provides insight information with respect
to molecular mobility, polarization, and conduc-
tivity mechanisms.16–20
Polymer matrix composites with conductive
inclusions are highly heterogeneous mixtures,
2535
2536 PSARRAS
since the electrical properties of their constitu-
ents are widely deviating. Furthermore, these
systems are regarded as disordered solids, by
being nonmetals with no perfect crystal lattice.21
The intrinsic heterogeneity of the systems is
considered as responsible for the occurrence of a
relaxation process known as interfacial polariza-
tion (IP) or Maxwell-Wagner-Sillars (MWS)
effect. The origin of the MWS effect lies in the
accumulation of free charges at the interface of
the constituents, while the presence of the
charges is arising from the stage of material
processing.22,23
Transport properties of polymer matrix–con-
ductive inclusion composites are in a large
extent governed by the amount of the dispersed
phase and the characteristics of its distribution
in the host medium.22,24–26 The presence of con-
ductive particles, in an insulating material,
alters the electrical conductivity of the compos-
ite system. For low values of the conductive fil-
ler content, the dc conductivity remains at the
level of the unfilled insulating matrix. Increas-
ing the concentration of the conductive phase
results in a gradual increase of the system’s dc
conductivity. As the conductive load is further
increased, an abrupt and significant increase of
conductivity is observed at a critical value of the
filler content.27–29 The critical concentration or
percolation threshold is a crucial parameter
determining the insulator to conductor or semi-
conductor transition. The insulator to conductor
transition, which can be considered as a critical
phenomenon, is described by means of percola-
tion theory according to the relation,
r
ðv  vc Þt ð1Þ
where vc is the critical concentration or volume
fraction of the conductive phase and t a critical
exponent.27,28 According to classical percolation
theory, at the critical concentration of the filler
a physical path is formed inside the composite,
through which the current can flow percolating
the whole system.27,28 Although, percolation
theory is able to predict the nonlinear transition
from the insulating to the conductive state, less
information can be extracted for the occurred
mechanisms of conduction, by simple considera-
tion of the dependence of conductivity upon filler
volume fraction. In the classical percolation
theory,27,28 the conduction mechanism is totally
attributed to the formation, at the percolation
threshold, of an infinite network inside the com-
posite, where the particles or the clusters which
account for this network are all in geometrical
contact.
A large part of the available studies concern-
ing electrical conduction in polymer matrix par-
ticulate composites employs CB particles as the
reinforcing material because of their ability to
lend high values of electrical conductivity to an
insulating polymer. The majority of the experi-
mental and theoretical investigations are carried
out inside the scheme of percolation theory at
ambient temperature.11,13,17,30
In this study the dc conductivity of composite
systems consisting of an epoxy resin and CB
particles is investigated, with varying parame-
ters—the conductive phase content and temper-
ature. Conductivity varies with the filler con-
tent, and at a certain concentration of the filler
a sharp increase is recorded. Experimental data
are analyzed by means of percolation theory,
and both percolation threshold and critical expo-
nent are determined at each of the examined
temperatures. Furthermore, aiming to investi-
gate the physical origin of the occurred conduct-
ance mechanisms below, at, and above the per-
colation threshold, the temperature dependence
of conductivity and the applicability of the vari-
able range hopping (VRH) model are also exam-
ined.
EXPERIMENTAL
A commercially available bisphenol type epoxy
resin (D.E.R 321, Dow Chemicals) was used as a
prepolymer, with an epoxy equivalent 182–192
and viscosity 500–700 mPa s at 25 8C. As curing
agent, a cycloaliphatic amine (Chemmammine
CA7 Henkel) at 30 phr (parts per hundred) was
employed. While the earlier systems were still
in the liquid state, various amounts of CB pow-
der were added, under continuous stirring, for
the production of the composite samples. Com-
posite systems were then poured into, circular
disk form, suitable molds. The employed curing
procedure involved initial curing at 40 8C for 24
h followed by postcuring at 100 8C for 48 h. CB
powder, commercially available by Sigma-
Aldrich, with density 2.1 g/cm3, was used after
drying at 100 8C for 48 h, without any treat-
ment and surface modification. Prior to the fab-
rication of the composite systems, the employed
CB was characterized by means of X-ray powder
diffraction (XRD) and its morphology was exam-
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb

Figure 1. (a) XRD spectrum and (b) SEM image of
the employed CB particles.
ined by means of scanning electron microscopy
(SEM) (Fig. 1). XRD analysis was performed
with a Philips (Eindhoven, The Netherlands,
model 1830/40 instrument), using Cu Ka radia-
tion (40 kV and 30 mA) and a Ni filter with a
scanning speed of 0.0058 2h/s. The time constant
was set at 2 s. SEM images were obtained via a
JEOL JSM-5200 instrument. The glass transi-
tion temperature of the polymer matrix was
determined by means of differential scanning
calorimetry via a Diamont DSC (Perkin-Elmer)
device. Sample was placed in an aluminum cru-
cible, and an empty aluminum crucible served
as a reference. The employed heating rate was
10 8C/min.
The CB particles content in the produced
specimens was varying from 0 to 35 phr or from
0% to 15.41% in volume fraction. dc conductivity
measurements were performed using the High-
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
CARBON BLACK/POLYMER COMPOSITES 2537
Resistance Meter 4339B of Agilent Technologies,
according to ASTM D 257-99(2005) specifica-
tions. Specimens were measured without and
with a silver paste coating; no significant varia-
tions between the conductivity values of the
coated and the uncoated samples were observed.
Results presented in this study are from the
uncoated specimens. The test cell was a three
terminal guarded system constructed according
to the ASTM D 150-98(2004) specifications.15,31
The use of a third electrode (guard) is not man-
datory in the case of dc measurements. How-
ever, its presence minimizes the interference
from spurious paths and prevents surface leak-
age currents from being added into measure-
ments. Temperature was varied from ambient to
180 8C.
RESULTS
CBs are finely divided carbon particles produced
by hydrocarbon dehydrogenation.32 CBs are
used in several technological applications as a
filler, to modify the mechanical, electrical, and
optical properties of the materials in which they
are dispersed.33 The microcrystalline structure
and the morphology of the employed CB par-
ticles are presented in Figure 1. The recorded
peaks in the XRD graph [Fig. 1(a)] coincide with
those of graphite,34 implying that CBs are com-
posed of small graphite layers in which the car-
bon atoms keep the same arrangement and
atomic positions as in graphite. Figure 1(b) illus-
trates the morphology of the CB particles. It is
obvious that their shape cannot be considered as
spherical or even spheroid. In the literature
there are studies13,30 where the shape of the
particles defines a type of ‘‘structure,’’ relating
thus the shape of the CBs to the physical per-
formance of the composites. The more spherical-
like an isolated CB particle is, the ‘‘lower’’ its
structure is considered to be.30
In Figure 2 the thermal response of the epoxy
resin matrix is depicted. Analysis of the thermo-
graph allows the determination of the polymer’s
glass transition temperature (Tg), which was
found to be 194.5 8C.
The dc conductivity, of all the examined sys-
tems, as a function of CB volume fraction, at
temperatures varying from 30 to 180 8C, is
shown in Figure 3. The CB volume fraction de-
pendence of conductivity assigns three distinct
regions for all the examined temperatures. In
2538 PSARRAS
Figure 2. DSC thermograph of the employed as a
matrix epoxy resin.
the first region, corresponding to the region
prior to the transition zone, the values of con-
ductivity are kept low and are slightly increas-
ing with CB content. The second region is the
transition zone, and an abrupt and sharp
increase of conductivity is recorded. In the third
region, after the transition zone, the values of
conductivity show significant proximity, appear-
ing almost unaffected from the variations in
both the CB volume fraction and temperature.
From Figure 3 it is evident that in the examined
set of composites, the transition from insulating
to conducting or semiconducting behavior has
been achieved, since a very narrow variation of
CB volume fraction (less than 3%) alters the
conductivity values by, almost, 5 orders of mag-
nitude. The critical concentration or percolation
threshold of this transition is expected to lie in
Figure 3. dc conductivity of the composites as a
function of the CB particles volume fraction at: (*)
30 8C, (~) 60 8C, (&) 100 8C, (^) 140 8C, and (!)
180 8C.
Figure 4. Log–log plot of conductivity versus (v 
vc) at (a) 30 8C and (b) 140 8C.
this narrow zone. In the first region, below per-
colation threshold, the influence of temperature
is more pronounced, while in the vicinity of per-
colation threshold is less evident, and finally in
the region of high CB content the influence of
temperature can be considered as negligible.
The critical concentration or percolation
threshold has been evaluated by fitting experi-
mental data according eq 1 in a log–log plot
(Fig. 4). It is well accepted in the litera-
ture12,13,35,36 that dc conductivity data, in the vi-
cinity and above the percolation threshold, can
be analyzed via the scaling law of eq 1. The
occurring linear relation logrdc
t[log(v  vc)]
allows the determination of the critical volume
fraction (vc) and the critical exponent (t). The
obtained values for all the examined tempera-
tures are listed in Table 1. It is interesting to
note that the value of the critical concentration
or percolation threshold (vc) appears to be unaf-
fected from temperature, while the values of (t)
are diminishing as the temperature is increas-
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
 CARBON BLACK/POLYMER COMPOSITES 2539

Table 1. Percolation Threshold vc and Critical Table 2. The Concentration of CB Particles for
Exponent t as Derived by Fitting Experimental Data All the Examined Systems and the Corresponding
Via Eq 1, at Each of the Examined Temperatures Values of Activation Energy and Parameter T0 as
Resulted from Eqs 2 and 4, respectively
h (8C) t vc (%)
CB Volume
30 1.54 CB (phr) Fraction (%) EA (eV) T0 (K)
60 1.43
100 1.39 9.65 0 0 0.311 1.10 3 109
140 1.37 5 2.69 0.280 7.39 3 108
180 1.31 10 5.37 0.262 5.66 3 108
15 7.81 0.235 3.75 3 108
18 8.96 0.228 3.31 3 108
ing. The temperature variation of the exponent 20 10.10 0.071 5.53 3 106
(t) is related to the occurring conduction mecha- 23 11.03 0.067 4.46 3 106
nism and to possible interactions between the 25 11.82 0.044 1.19 3 106
constituents of the composite. Thus, the result- 30 13.77 0.036 7.15 3 105
ing changes of (t) with temperature, is an indi- 35 15.41 0.035 6.19 3 105
cation for the presence of a thermally activated
conduction process and modifications in the mann constant. By employing eq 2 and the plots
kinetics of the constituent phases and the inter- in Figure 5, the activation energy of each of the
face of the system. examined systems can be easily determined. The
Figure 5 provides plots of dc conductivity as a obtained values are listed in Table 2. It is evident
function of reciprocal temperature for all the that the activation energy values are decreasing
examined systems. Experimental data can be, as the conductive phase content increases. Acti-
satisfactory, described by a linear fit revealing vation energy reflects the microstructure of the
thus an Arrhenius-type behavior. The tempera- composites being a function of the mean radius
ture dependence of conductivity can be of conductive particles or agglomerates and the
expressed by the following equation mean interparticle separation.37 Thus, the forma-
  tion of conductive clusters inside the specimens
EA
rdc ðTÞ ¼ r exp 
0
ð2Þ and the reduction of interparticle separation by
kB T increasing the volume fraction of the conductive
phase results in diminishing the corresponding
where r0 is conductivity at infinite temperature, values of activation energy.
a parameter lightly dependent on temperature,
EA is the activation energy and kB the Boltz-

DISCUSSION

Conductivity Data and Percolation

Figure 5. dc conductivity versus the reciprocal of
temperature of the composites with: (l) 0, (~) 5, (n)
10, (^) 15, (^) 18, (!) 20, (!) 23, (1) 25, (~) 30,
and (&) 35 phr in CB content.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
It is well known and documented28,29 that the
conductivity of heterogeneous mixtures varies
with the conductive filler content. The way that
conductivity alters with the concentration of the
inclusions is the main question regarding the dc
electrical response of these composites. Although
percolation theory was initially dealing with the
penetration of a liquid in a porous medium, eq 1
provides a universal mathematical treatment for
the insulator to conductor transition in electri-
cally binary systems. In classical percolation
theory, where the conductive inclusions are con-
sidered as noninteracting to each other and ran-
domly dispersed within the matrix, the critical
exponent and the percolation threshold are only
2540 PSARRAS
depending on the dimensionality of the process
and the geometrical factors of the inclusions,
respectively. Statistical or classical percolation
theory describes the transition from the state of
limited links between conductive sites to the
state where the number of the links forms an in-
finite conductive cluster (ICC) or network, pro-
viding a static approach of the phenomenon.
The percolation threshold is defined as the criti-
cal volume fraction separating these two states.
The formation of the infinite cluster is not due
to any dynamic agglomeration, but due to the
random position of occupied sites, and the con-
duction of charge carriers is ought to the physi-
cal contacts between the conductive elements of
the network. In the field of percolation theory
and in close relation to the theory of critical
phenomena, many models have been developed
and proposed.28,30,38 The available models are
mainly focused on the prediction of the quanti-
ties included in eq 1, namely (i) the composite
system’s conductivity, (ii) the critical concentra-
tion of the conductive filler, and (iii) the critical
exponent. By the years, experimental stud-
ies12,28,35 accumulated deviations between data
and theoretical predictions of the static
approach. The occurred discrepancies concern
both the value of percolation threshold and the
critical exponent. In many cases, the experimen-
tally determined values of percolation thresh-
old12,28,35 have been found to be lower than the
theoretically predicted ones. In a particulate
polymer matrix composite system, the conduc-
tive inclusions are regarded as randomly
arranged conductive points. According to classi-
cal percolation approach, critical concentration
corresponds to the minimum necessary links
between conductive points for the occurrence of
a conductive path or infinite cluster through the
whole system. Under this point of view, the
lower values of percolation threshold, which are
experimentally determined, can be considered as
indicative for the presence of a conduction mech-
anism where the physical contact between con-
ductive elements is not prerequisite.
In binary mixtures with randomly dispersed
conductive particles, the value of percolation
threshold is affected by the shape, size distribu-
tion, and possible preferential orientation,
because of the influence of an external field, of
the dispersed particles.29 In the examined set of
specimens, the applied field, the shape, size and
distribution of the CB particles, as well as the
manufacturing procedure were the same in all
cases, thus minimizing the influence of the ear-
lier factors.
Conductivity data, from all the studied sys-
tems, presented in Figure 3 appear to be in ac-
cordance with percolation theory. At each of the
examined temperatures, a sharp, stepwise tran-
sition from the low conductivity regime to the
high conductivity regime is present. The power
law of percolation theory satisfactorily describes
the variation of the composites conductivity with
the CB particles volume fraction, above the per-
colation threshold (Fig. 4). The critical concen-
tration remains unaffected by temperature in
the examined range, being equal to 9.65% in vol-
ume fraction. The temperature independence of
the critical concentration is in agreement with
results from different systems, the electrical
response of which can be described by means of
percolation theory.12,36 The experimentally
determined value of percolation threshold differs
from the theoretically predicted one of 16% in
volume fraction, for a composite system consist-
ing of conductive hard spheres dispersed within
an insulating matrix.27 Furthermore, experi-
mentally determined critical concentrations, in
polymer matrix–CB particles composites, vary
from less than 1% to almost 40% in volume frac-
tion.11,30,39–46 These deviations have been attrib-
uted to the shape and morphology of the dis-
persed particles and the molding condi-
tions.11,30,42
The elaborated values of critical exponent (t),
in the examined temperature range, are all
lower than the predicted, from percolation
theory, universal value t ¼ 2, for a 3D conduc-
tion process. Critical exponent has been found to
deviate from its own universal value in a lot of
studies available in the literature.12,30,35 Besides
the dimensionality of the conduction process,
the values of the critical exponent are related to
the composition of the composite system, the
type of the conduction mechanism, the differ-
ence between a perfect lattice of spherical inclu-
sions and a real polymer–CB particles system,
the possible interactions between the phases of
the composite, the degree of dispersion of the fil-
ler, and the method of fabrication.28,35 In a
model proposed by Balberg,30 deviations of both
the percolation threshold and the critical expo-
nent from universal values are directly related
to the shape, the orientation, and the dispersion
of the CB particles. The proposed rule states
that the lower the structure of CB particles is,
the higher the t values are. Thus, the high
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb

structure of the employed CB particles [Fig.
1(b)] and the obtained values of t (Table 1)
appear to be in accordance with the previous
rule.
All the aforementioned suggestions concern
the discrepancy of the experimentally deter-
mined values of t from its own universal value
under constant temperature. In this study the
derived values of the critical exponent are all
less than 2 and, furthermore, they are monot-
onically diminishing as temperature increases.
It is possible that the temperature variation of
the exponent t involves the occurred types of
conduction mechanisms in the examined sys-
tems. Reghu et al.36 in a study concerning perco-
lation in polyaniline–PMMA networks provide
support to the aforementioned point, since the
critical exponent of their system at room tem-
perature takes the value t ¼ 1.33, while at 10 K
takes the value t ¼ 1.99, indicating transport in
three dimensions. The observed variation was
attributed to thermally induced hopping trans-
port between disconnected (or weakly connected)
parts of the network.36
The dynamic nature of disordered systems, as
resulted by the preparation procedure and the
occurring interactions between the insulating
matrix and the conductive filler, as well as
between adjacent charged particles can be con-
sidered as responsible for the observed differen-
ces between the experimentally determined
behavior and the statistical percolation
approach.
The applicability of percolation theory and in
particular of eq 1 on experimental data (Figs. 3
and 4) provides little information with respect to
the occurring conduction mechanism or mecha-
nisms. To determine the dominating conduction
mechanism in the prepared systems, the tem-
perature dependence of conductivity has been
examined below, in the vicinity, and above the
percolation threshold.
Temperature Dependence of Conductivity
Electrical conductivity in disordered systems is
associated with a variety of phenomena, such as
localization effects, hopping transport, and per-
colation via a formed physical network.47,48 The
occurrence of a specific conduction mechanism
depends on different parameters, including the
strength of disorder, the geometrical characteris-
tics of the inclusions, the particle–particle inter-
actions, the extent of aggregation of filler par-
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
CARBON BLACK/POLYMER COMPOSITES 2541
ticles, and the rheological behavior of the ma-
trix.28,35 The observed electrical response is, in
many cases, the result of the simultaneous influ-
ence of more than one parameter, making it dif-
ficult to explain all experimental results with
the aid of a single model. The type of the con-
duction mechanism and the nature of the con-
tact between conductive particles or clusters can
be assigned by examining the influence of tem-
perature on the dc conductivity of the system.
Equation 2 is valid only for insulators and semi-
conductors, extrapolating conductivity to zero
when temperature tends to zero. On the other
hand in systems exhibiting metallic type conduc-
tion rdc tends to a finite value as T ? 0, conduc-
tion process is not thermally activated, and thus
not characterized by an activation energy. In
that case the temperature dependence of con-
ductivity cannot be described via eq 2.
The temperature dependence of conductivity
for all the examined composites appears to be in
agreement with eq 2 (Fig. 5). Systems with CB
volume fraction below the critical concentration
are more affected by temperature. Their conduc-
tivity attains low values, although it is increas-
ing up to two orders of magnitude with tempera-
ture. In the low conductivity regime, the
recorded electrical response reflects the insulat-
ing nature of the matrix and is only gradually
influenced by the presence of the conductive fil-
ler. However, the enhanced heterogeneity of the
systems is responsible for the occurrence of IP
or MWS effect, which as stated previously, is
associated with the accumulation of mobile
charge carriers at the interface of the systems.
IP is observed not only in composite polymeric
materials but also in polymers, because of the
presence of additives, plasticizers, or even
impurities, which make these systems heteroge-
neous.23 When an electric field is applied, car-
riers are forced to migrate following the field
direction, resulting in both the formation of
dipoles on the surface of the inclusions and con-
tributing to the limited conductivity of the com-
posites. Under the influence of a dc field,
charges drift over relatively larger distances,
compared with those ones imposed by an ac
field. As temperature is increased, the whole
process is facilitated due to the provided excess
of thermal energy. The curves produced by eq 2
in Figure 5 are almost parallel between them
for the systems with CB content up to 15 phr,
indicating the common nature of the transport
process.
2542 PSARRAS
In the vicinity of percolation threshold, at the
transition zone, conductivity values are increas-
ing abruptly signifying the insulator to conduc-
tor transition (Figs. 3 and 5). Conductivity
becomes less temperature-dependent and activa-
tion energy is considerably reduced. In the high
conductivity zone, beyond threshold, the influ-
ence of temperature can be reasonably consid-
ered as negligible and activation energies are
further reduced, being almost equal between
them, while approaching zero (Table 2). The
temperature-independent values of conductivity
could be related to the occurrence of a different
type of charge transport process. Furthermore,
the close to zero values of activation energy are
diminishing the applicability of eq 2, signifying
a less thermally activated conduction process,
which can be attributed to the presence of an
extra or cooperative conduction mechanism.
From Figures 3 and 5 it is clear that the factor,
mainly, affecting conductivity below the critical
concentration is the temperature, while above
the threshold the influence of temperature
becomes less significant and conductivity attains
rather constant values.
However, it is evident from Figure 5 that ex-
perimental data are in agreement with eq 2 for
the whole set of the examined specimens. Even
in the high conductivity region, where the val-
ues of activation energy are reduced, the valid-
ity of eq 2 still holds.
This fact offers a secondary indication for the
absence of an ICC through which carriers can
flow penetrating the whole system. If the con-
ductive particles were in geometrical contact
inside the insulating matrix, a continuum perco-
lation path should exist through the entire sys-
tem, and thus the metallic type conduction
should be expected to be the dominating mecha-
nism. In that case rdc should tend to a finite
value as T ? 0 and eq 2 should be far from
being applicable on experimental data.
Charge Transport Mechanisms
Since metallic type conduction is not the domi-
nating process, even at concentrations of CB
particles higher than the percolation threshold,
further analysis should be carried out to investi-
gate the type of the occurring charge transport
mechanisms.
The intensity of the temperature effect upon
dc conductivity varies from region to region, or
in other words below, at, and above the critical
concentration. The insulating origin of the
under study, composite systems, as well as their
classification as disordered materials, implies
hopping as a possible inherent charge transport
mechanism. The term hopping refers to sudden
displacement of a charge carrier from one posi-
tion to another neighboring and, in general,
includes both jumps over a potential barrier and
quantum mechanical tunnelling.49,50 According
to the VRH mechanism, originally proposed by
Mott,51,52 charge carriers move (hop) from a
localized state to a nearby localized state of dif-
ferent energy, or to a localized state of similar
energy with spatial separation from the initial
site. The dependence on temperature of dc con-
ductivity follows the formula
  c 
T0
rðTÞ ¼ r0 exp  ð3Þ
T
where the parameter r0 can be considered as
the limiting value of conductivity at infinite
temperature, T0 is the characteristic tempera-
ture that determines the thermally activated
hopping among localized states at different ener-
gies and considered as a measure of disor-
der,47,53 and the exponent c is related to the
dimensionality d of the transport process via c
¼ 1/(11d), where d ¼ 1,2,3.
The applicability of the VRH model is exam-
ined by plotting the experimental results in the
form of log rT1/2 ¼ f(Tc) (Fig. 6). In general the
least square fitted curves provide a first hand
indication, not only of the nature of the charge
Figure 6. dc conductivity data for the composites
with (l) 0, (~) 5, (n) 10, (^) 15, (^) 18, (!) 20, (!) 23,
(1) 25, (~) 30, and (&) 35 phr in CB content, as
described by the VRH model for a 3D transport process.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb

transport mechanism but also of the dimension-
ality of the process. In this study, c is assumed
to be equal to 1/4 for two reasons: (i) the exam-
ined systems are bulk polymer specimens incor-
porating randomly distributed conductive par-
ticles; hence, it is reasonable to consider that
they are characterized by a 3D conduction pro-
cess, (ii) the quality factor R2 describing the lin-
ear fit is closer to unity when c ¼ 1/4 is
employed rather than c ¼ 1/3 (Fig. 6). In Figure
6 data are well described by linear curves, indi-
cating hopping as the origin of the recorded con-
duction process. The values of the parameter T0,
derived from the linear fits of Figure 6, are
listed in Table 2.
Activation energy and the parameter T0 as a
function of the CB particles volume fraction are
depicted in Figure 7. In both diagrams, a transi-
tion from high-to-low values with increasing CB
volume fraction is evident. The recorded transi-
tion appears in the same narrow CB content
Figure 7. (a) Activation energy and (b) the parame-
ter T0, as a function of the CB volume fraction for all
the examined systems.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
CARBON BLACK/POLYMER COMPOSITES 2543
range in both diagrams [Fig. 7(a,b)] as in Figure
3 as well. The insulator to conductor transition
is presented in a new form. In Figure 7(a) the
stepwise variation of activation energy, from val-
ues over 0.3 eV to values actually independent
from the CB concentration very close to zero,
reveals the cooperation of a second conduction
process beyond percolation threshold. The
increased number of particles in geometrical
contact enhances the circuit-like charge trans-
port inside the composites.
Systems with concentration of CB particles
lower than the critical value exhibit high values
of T0 reflecting their limited conductivity. As the
CB content is increasing, T0 values are dimin-
ishing up to 4 orders of magnitude. This is in
agreement with experimental results from dif-
ferent systems with varying conductivity.54–57
Furthermore, the parameter T0 is considered as
a measure of the degree of disorder.47,53 Thus,
the high values of T0 are in accordance with the
stochastic nature of the examined composite
mixtures, as resulted by the amorphous matrix,
the absence of a regular arrangement of the
inclusions and the presence of crosslinks,
agglomerates, and conductive clusters dead
ends.57,58
Regarding the electrical properties of the
composites three different, in conductivity, areas
can be identified. The first one is composed by a
set of clusters, not being in physical contact
with all of them. Each cluster is consisting of a
number of connected conductive sites, and its
conductance appears to be higher than the over-
all conductance of the composite. The second
area corresponds to the space between abutting
isolated clusters. Conductivity of this region is
significantly lower than the corresponding of the
clusters and of the same order of magnitude
with the overall conductivity of the composite.
Finally, the third area has very low conductivity
and is composed of the polymer matrix. The sec-
ond area is controlling the conductance of the
whole system, since an infinite cluster has not
been formed in composites, and the space
between clusters restricts or facilitates the
charge transport, by being dependent upon the
concentration and the arrangement of conduc-
tive particles.
Inside the conductive clusters, metallic type
conduction is expected to occur, while hopping
conductivity characterizes charge transport
mechanisms at the other two areas. At low con-
centrations of CB particles, below threshold,
2544 PSARRAS
hopping conductivity is the predominant pro-
cess. By increasing the CB particles content, the
conductive ‘‘islands’’ become larger and the
space between adjacent clusters is diminishing.
Thus, the area of metallic type conduction is
extending, and at the same time hopping con-
duction is facilitated, both processes can be
regarded as responsible for the sharp increase of
conductivity in the transition zone. As the CB
volume fraction is further increased, the coun-
terpart contribution of hopping conduction is
reduced. However, at concentrations higher than
the critical zone, conductivity values do not alter
significantly, with CB content approaching a
rather constant value. The upper limit of con-
ductivity, for the examined set of composites,
reflects a kind of balance between the synergetic
charge transport mechanisms, determined by a
limiting value of the separation space between
adjacent conductive clusters. The existence of
such a limiting value of the separating space is
supported by the variation of both activation
energy and conductivity with the CB content
[Figs. 3 and 7(a)], and could be attributed to the
presence of a polymer layer around each conduc-
tive cluster. It is reasonable to suggest that the
thickness of this layer varies with the CB par-
ticles volume fraction, tending to a minimum
value, which could be related to the structure of
the employed inclusions and the soaking of the
particles by the polymer host medium during
the composites preparation procedure. Hence,
besides the conductive particles concentration,
the physicochemical properties of the systems,
such as matrix viscosity, wettability of CB par-
ticles and specific interface free energy can be
proved very important factors for the electrical
performance of the composites, by controlling
the formation of extensive or locally restricted
conductive paths and the thickness of the layer
between adjacent conductive areas.
CONCLUSIONS
The dc transport properties of polymer matrix–
CB particles composites have been investigated
in this study. Conductivity data were analyzed
by means of percolation theory, and both perco-
lation threshold and critical exponent were
determined at each of the examined tempera-
tures. Percolation threshold appears not be
influenced by temperature, while the critical
exponent is diminishing with temperature. The
temperature dependence of conductivity and the
applicability of the VRH model were employed
to reveal the charge transport mechanisms
below, at, and above the critical concentration of
CB particles. Below percolation threshold and in
the vicinity of the transition zone, hopping con-
ductivity can be considered as the dominating
charge transport mechanism. At concentrations
of the conductive filler higher than the critical
one, the conductivity of the systems tends to
attain constant values. As the CB content is
increased, more particles are in geometrical con-
tact and a second conduction mechanism occurs.
The contribution of hopping transport to the
overall conductivity is reduced, and a balance
between hopping and conduction via geometrical
contact is established.
The author thanks P. Koutsoukos (Department of
Chemical Engineering, University of Patras, Greece)
and M. Orkoula (Department of Pharmacy, University
of Patras, Greece) for providing access to X-ray dif-
fraction and scanning electron microscopy facilities.
REFERENCES AND NOTES
1. Varma, I. K.; Gupta, V. G. In Comprehensive Com-
posite Materials; Kelly, A.; Zweben, C., Eds.; Elsev-
ier: Amsterdam, 2000; Vol. 2, Chapter 2.01, pp 1–56.
2. Hull, D.; Clyne, T. W. In An Introduction to Com-
posite Materials; Cambridge University Press:
Cambridge, 1996; pp 30–34.
3. Daniel, I. M.; Ishai, O. In Engineering Mechanics
of Composite Materials; Oxford University Press:
Oxford, 1994; pp 30–32.
4. Schwartz, M. M. In Composite Materials Hand-
book; McGraw-Hill: New York, 1984; Chapters 3, 7.
5. Ellis, B. In Chemistry and Technology of Epoxy
Resins; Blackie Academic & Professional, Chap-
man & Hall: London, 1993; pp 303–324.
6. Delmonte, J. In Metal/Polymer Composites; Van
Nostrand Reinhold: New York, 1990; Chapters
2, 4.
7. Xiangcheng, L.; Chung, D. D. L. Compos B 1999,
30, 227.
8. Chung, D. D. L.; Zweben, C. In Comprehensive
Composite Materials; Kelly, A.; Zweben, C., Eds.;
Elsevier: Amsterdam, 2000; Vol. 6, Chapter 6.38,
pp 1–20.
9. Capaccioli, S.; Lucchesi, M.; Rolla, P. A.; Ruggeri,
G. J Phys: Condens Matter 1998, 10, 5595.
10. Tsangaris, G. M.; Psarras, G. C.; Manolakaki, E.
Adv Comp Lett 1999, 8, 25.
11. Jäger, K.-M.; McQueen, D. H.; Tchmutin, I. A.;
Ryvkina, N. G.; Klüppel, M. J Phys D: Appl Phys
2001, 34, 2699.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb

12. Barrau, S.; Demont, P.; Peigney, A.; Laurent, C.;
Lacabanne, C. Macromolecules 2003, 35, 5187.
13. Toker, D.; Azulay, D.; Shimoni, N.; Balberg, I.;
Millo, O. Phys Rev B 2003, 68, 041403(R).
14. Dang, Z.-M.; Nan, C.-W.; Xie, D.; Tjong, S. C.
Appl Phys Lett 2004, 85, 97.
15. Psarras, G. C.; Manolakaki, E.; Tsangaris, G. M.
Compos A 2002, 33, 375.
16. Psarras, G. C.; Manolakaki, E.; Tsangaris, G. M.
Compos A 2003, 34, 1187.
17. Singh, V.; Tiwari, A. N.; Kulkarni, A. R. Mater
Sci Eng B 1996, 41, 310.
18. Singh, V.; Kulkarni, A. R.; Rama Mohan, T. R. J
Appl Polym Sci 2003, 90, 3602.
19. Nucci, A. M.; Nicolau, A.; Martini, E. M. A.;
Samios, D. Eur Polym J 2006, 42, 195.
20. Guskos, N.; Anagnostakis, E. A.; Likodimos, V.;
Bodziony, T.; Typek, J.; Maryniak, M.; Narkie-
wicz, U.; Kucharewicz, I. J Appl Phys 2005, 97,
024304.
21. Schrøder, T. B.; Dyre, J. C. Phys Chem Chem
Phys 2002, 4, 3173.
22. Van Beek, L. K. H. In Progress in Dielectrics;
Birks, J. B., Ed.; Heywood Books: London, 1967;
pp 69–110.
23. Tsangaris, G. M.; Psarras, G. C.; Kouloumbi, N. J
Mater Sci 1998, 33, 2027.
24. Tsangaris, G. M.; Psarras, G. C.; Kouloumbi, N.
Mater Sci Technol 1996, 12, 533.
25. Tsangaris, G. M.; Psarras, G. C. J Mater Sci
1999, 34, 2151.
26. Tunker, E.; Serdyuk, Y. V.; Gubanski, S. M. IEEE
Trans Diel El Insul 2002, 9, 809.
27. Zallen, R. The Physics of Amorphous Solids;
Wiley: New York, 2004; Chapter 4, pp 153–203.
28. Lux, F. J Mater Sci 1993, 28, 285.
29. Roldughin, V. I.; Vysotskii, V. V. Progr Org Coat
2000, 39, 81.
30. Balberg, I. Carbon 2002, 40, 139.
31. Tsangaris, G. M.; Psarras, G. C.; Kontopoulos, A.
J. J Non-Cryst Solids 1991, 31, 1164.
32. Dresselhaus, M. S.; Dresselhaus, G.; Eklund, P.
C.; Saito, R.; Endo, M. In Carbon Nanotubes:
Preparation and Properties; Ebbesen, T. W., Ed.;
CRC Press: Boca Raton, 1997; pp 16–17.
33. Donet, J. B.; Bansal, R. C.; Wang, M. J. In Car-
bon Black; Marcel Dekker: New York, 1993; pp
90–147, 271–287.
34. JCPDS-International Centre for Diffraction Data,
1996.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
CARBON BLACK/POLYMER COMPOSITES 2545
35. Connor, M. T.; Roy, S.; Ezquerra, T. A.; Baltá;
Calleja, F. J Phys Rev B 1998, 57, 2286.
36. Reghu, M.; Yoon, C. O.; Yang, C. Y.; Moses, D.;
Smith, P.; Heeger, A. J Phys Rev B 1994, 50,
13931.
37. Banerjee, S.; Chakravorty, D. J Appl Phys 1998,
84, 799.
38. Pury, P. A.; Cáceres, M. O.; Phys Rev B 1997, 55,
38413848.
39. Adriaanse, L. J.; Reedijk, J. A.; Teunissen, P. A.
A.; Brom, H. B.; Michels, M. A. J.; Brokken-Zijp,
J. C. M. Phys Rev Lett 1997, 78, 1755.
40. Celzard, A.; McRae, E.; Marêché, J. F.; Furdin, G.
J Appl Phys 1998, 83, 1410.
41. Wu, J.; McLachlan, D. S. Phys A: Stat Mech Appl
1997, 241, 360.
42. Foulger, S. H. J Appl Polym Sci 1999, 72, 1573.
43. Xia, J.; Pan, Y.; Shen, L.; Yi, S.; Xiao, S. Y. J
Mater Sci 2000, 35, 6145.
44. Wiśniewski, G. Synth Met 2000, 109, 295.
45. Jäger, K.-M.; McQueen, D. H. Polymer 2001, 42,
9575.
46. Elimat, Z. M. J Phys D: Appl Phys 2006, 39,
2824.
47. Mandal, P.; Neumann, A.; Jansen, A. G. M.;
Wyder, P. Phys Rev B 1997, 55, 452.
48. Dyre, J. C. J Appl Phys 1988, 64, 2456.
49. Böttger, H.; Bryskin, U. V. In Hopping Conduc-
tion in Solids; Verlag Akademie: Berlin, 1985; pp
169–213.
50. Long, A. R. In Hopping Transport in Solids; Pol-
lak, M.; Shklovskii, B., Eds.; Elsevier: Amster-
dam, 1991; pp 207–231.
51. Mott, N. F. In Metal–Insulator Transitions; Taylor
& Francis: London, 1990; pp 50–54, 146–148.
52. Mott, N. F. In Conduction in Non-Crystalline
Materials; Clarendon Press: Oxford, 1987; pp
157–160.
53. Joo, J.; Long, S. M.; Pouget, J. P.; Oh, E. J.; Mac-
Diarmid, A. G.; Epstein, A. J Phys Rev B 1998,
57, 9567.
54. Aguilar-Hernández, J.; Potje-Kamloth, K. J Phys
D: Appl Phys 2001, 34, 1700.
55. Zuo, F.; Angelopoulos, M.; MacDiarmin, A. G.;
Epstein, A. J Phys Rev B 1989, 39, 3570.
56. Dutta, P.; Biswas, S.; Ghosh, M.; De, S. K.; Chat-
terjee, S. Synth Met 2001, 122, 455.
57. Psarras, G. C. Compos A 2006, 37, 1545.
58. Maddison, D. S.; Tansley, T. L. J Appl Phys 1992,
72, 4677.