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Electric modulus-based analysis of the dielectric relaxation in carbon black

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 JOURNAL OF APPLIED PHYSICS 107, 124111 共2010兲

Electric modulus-based analysis of the dielectric relaxation in carbon black

loaded polymer composites
J. Belattar,1 M. P. F. Graça,2 L. C. Costa,2 M. E. Achour,1 and C. Brosseau3
1
Département de Physique, Laboratoire des Systèmes des Télécommunications et d’Ingénierie de la
Décision, Faculté des Sciences, Université Ibn Tofail, BP 133, 14000 Kénitra, Morocco
2
Department of Physics and I3N, Universidade de Aveiro, 3810-193 Aveiro, Portugal
3
Université Européenne de Bretagne, Université de Brest, Lab-STICC and Département de Physique, CS
93837, 6 avenue Le Gorgeu, 29238 Brest Cedex 3, France
共Received 20 March 2010; accepted 15 May 2010; published online 25 June 2010兲
A thorough investigation of the ac electrical properties of carbon black 共CB兲 mixed into ethylene
butylacrylate copolymer has been conducted using ac impedance spectroscopy in the frequency
range 10 Hz–100 kHz and over the temperature range of 150 共Tg − 48 K兲 – 319 共Tg + 121 K兲 K. For
this investigation, a series of eight samples were prepared with various filler contents above the
percolation threshold. Using the electric modulus formalism it has been found that the Cole–Cole
equation of dielectric relaxation expressed in the electric modulus form is capable of quantitatively
describing the experimental data from which we extract the relaxation time and a parameter ␣ which
gauges the broadening of the loss spectrum. The small values of ␣ ranging from 0.06 to 0.10 suggest
a behavior close to the state of a single relaxation time. Furthermore, the relaxation time as a
function of temperature is characterized by an Arrhenius behavior. While the effective activation
energy is on the order of 60 meV and is insensitive to CB volume fraction, the Arrhenius prefactor
is found to strongly depend on this volume fraction. The observed relaxation mechanism does not
result simply from thermally activated dipolar interactions but is a collective cooperative effect of
the CB mesostructure. © 2010 American Institute of Physics. 关doi:10.1063/1.3452366兴

I. INTRODUCTION class of materials has a permittivity behavior which is sensi-

Models of the frequency-dependent effective permittiv-
ity, ␧共␻兲 where ␻ denotes the angular frequency, of various
types of heterostructures have been intensively studied, but
in many cases a fundamental understanding of these effects
remain poorly understood although a considerable progress
has been done recently in Refs. 1 and 2. In particular the
effects of disorder on relaxation mechanisms have not been
studied systematically. Due to the complexity of the physical
disorder, standard numerical approaches are often inappli-
cable to fully represent the actual microstructure. Since there
are several uncertain factors controlling the intrinsic random-
ness and phase connectedness, it is difficult to reach robust
conclusions from the numerical perspective. In general, spa-
tial disorder may be regarded as being slow in comparison to
electronic time scales. On the other hand, some “simplified”
analytic techniques specific to heterostructures are available
and allow to treat “averaged,” or apparent properties of ma-
terials. The fundamental question of how the microscopic
degrees of freedom, i.e., many-body interactions, changes as
the state variables are varied has remained largely unex-
plored. Although little is yet certain about the properties of
these degrees of freedom, work is ongoing to study them3,4
and to control the through improved materials and fabrica-
tion. One recent example of this situation is the dielectric
relaxation observed in nanocomposites, in which nanopar-
ticles are incorporated into a polymer matrix.5 Carbon black
共CB兲 loaded polymers have attracted special attention from
several groups, both as an archetypal model system, and be-
cause of their technologically useful applications. This broad
tive to interface effects6–8 and may behave in a complicated
way as the filler content is varied.9–14 It is the interplay of the
collective dynamical properties of the polymer chains and
the CB particles mesostructure that creates the rich physics
predicted and observed that makes these particulate hetero-
structures interesting in their own right. The continued inter-
est in CB filled polymers extends well beyond the physical
description of ␧共␻兲. The field has been a testing ground for
analytical, semianalytical, and different numerical tech-
niques. One line of research investigates if the state of the
carbonaceous phase in CB filled polymer composites is nor-
mal metal, insulator, or somewhere in between of these.5
Although computational modeling can describe how wave
and charge transport occur in simple models of
heterostructures,3,15,16 computational results can vary widely.
A more technical point is in order. Broadband ac imped-
ance spectroscopy is routinely used for the dielectric mea-
surements in disordered and amorphous materials.2,17–19 In
the range 10– 107 Hz, the usual method of studying dielec-
tric relaxation in these materials is to prepare a disk-shaped
sample with thin-film metal electrodes deposited on its two
parallel faces. An ac bridge is used to measure the conduc-
tance G and capacitance C of the sample as a function of
frequency F = ␻ / 2␲. The material can be regarded as an
equivalent circuit of impedance Z = 共G + iC␻兲−1. Apart from
geometric parameters the real part of the complex conductiv-
ity ␴ = ␴⬘ − i␴⬙ and the real part of the complex permittivity
␧ = ␧⬘ − i␧⬙ are proportional to G and C, respectively. Thus,
the measurements give ␧ and ␴ = i␻␧0␧. Another way to ana-
lyze the raw experimental data is in terms of the electric

0021-8979/2010/107共12兲/124111/6/$30.00 107, 124111-1 © 2010 American Institute of Physics

124111-2 Belattar et al.
modulus defined as the inverse of ␧, i.e., M = 1 / ␧ = ␧⬘ / 共␧⬘2
+ ␧⬙2兲 + i␧⬙ / 共␧⬘2 + ␧⬙2兲 = M ⬘ + iM ⬙, as first introduced by Mc-
Crum et al. in their standard book on relaxation in polymers,
and later extensively developed by Macedo et al.1 Recent
reports in the literature have illustrated the interest of using
the M-formalism for analyzing electrical relaxation
processes.20,21 Herein we describe experiments which ex-
plore the applicability of the M-formalism on a Cole–Cole
共CC兲-type relaxation process in CB filled polymers.
A key feature behind the remarkable progress in elec-
tronics applications has been the ability to modulate the con-
ductivity of CB loaded polymers at will, passing from an
insulating state to a conducting 共percolating兲 state. Percola-
tion effects have been widely studied in a large variety of
materials across a wide swath of scientific communities, in-
cluding granular and polymeric composites.17,22 The corre-
sponding mechanical, electronic, transport, and magnetic
properties of percolating networks are strongly affected by
the system percolation. The standard percolation theory is
usually featured by a conductor-insulator transition in a two-
component composite, where one of the constituents pro-
vides a conductive path through the insulating matrix, large-
scale properties being often independent of specific details of
the preparation techniques and of the materials employed
共universality兲. A reported conducting-to-insulating transition
with CB volume fraction ␾c in CB filled polymer composites
has been much discussed, with several proposed
explanations.12,13,17,23,24 Among the properties in these mate-
rials long debated were the nature of the percolating state and
the still ambiguous divergence of correlation length at
percolation.23 It is well known that a percolation transition
can be claimed to exist in connected networks, formed by
conductive filler particles, that span the sample when several
critical exponents associated with critical composition fluc-
tuations have been determined.22,23 Some authors, however,
have questioned the generality of such an assumption.24
In the present paper, we report the results of a careful
analysis of experimental data to extract information about
the dielectric relaxation in CB loaded polymer composites
above ␾c. Our approach is motivated by a broad range of
technologically important applications which require highly
loaded 共well above ␾c兲 CB polymer composites, e.g., elec-
tromagnetic shielding.7,25 For these applications, our under-
standing of the dielectric relaxation mechanisms depends
sensitively on the CB mesostructure. Evaluations of models
and theory of these mechanisms is predominantly made
through comparison with experimental data and a set of phe-
nomenological parameters. Our purpose is twofold. First of
all, we want to study systematically the effects of the CB
content and temperature on the frequency response of the
electric modulus and check if the CC equation applies. The
frequency dependence of M has been discussed theoretically
for the case of hybrid composite systems consisting of epoxy
resin-metal powder-aramid fibers.21 Without the theoretical
description given in Ref. 21, Adohi and Brosseau19 already
addressed the problem of dielectric relaxation in silicon di-
oxide loaded epoxy resin composites. They found that add-
ing silicon dioxide particles in the polymeric matrix in-
creases the effective permittivity of the material, a
J. Appl. Phys. 107, 124111 共2010兲
phenomenon most likely due to charges trapped in the filler
particles. Their conclusion was based on the quantitative
comparison of their measurements to theoretical calculations
of M based on the Havriliak–Negami 共HN兲 dielectric re-
sponse. A part of the motivation for this study came from
prior observations of a non-Debye dipolar behavior in pre-
percolative samples of amine-cured epoxy resins loaded with
CB.9 Second, an Arrhenius-type behavior is evidenced for
the relaxation time with effective activation energy of the
order of 60 meV. The likely origin of the relaxation mecha-
nism as well as the possible influence of temperature is dis-
cussed.
The remaining sections are organized as follows. In Sec.
II, we describe the sample preparation, dc conductivity char-
acterization, and electromagnetic measurement. In Sec. III,
the results of the effective permittivity measurements, their
plots in terms of the M-formalism, their fits, and the CB
content and temperature dependences of the relaxation time
are shown. Finally, in Sec. IV, we discuss our results in light
of the existing literature and present our conclusions.
II. EXPERIMENTAL DETAILS
For the present study, we used CB particles 共Raven
7000兲 obtained from the Columbian Chemicals Co. The av-
erage size of the primary CB particles is about 11 nm and the
mean size of the primary aggregates is of order 150 nm.26
The density of the CB particles is 1.89 g cm−3 and the spe-
cific surface area 共NSA兲 is 639 m2 g−1. Poly共ethylene-co-
butylacrylate兲, ethylene butylacrylate EBA, 共FA3030兲, with
⬇4 mol % butyl acrylate was provided by Borealis AB, Swe-
den. This EBA is currently used in semiconducting layers of
high-voltage cables. The butylacrylate monomer contains bu-
tylester side groups providing a certain polarity and a rela-
tively low crystallinity 共⬇20 vol %兲. The density of the EBA
copolymer is 0.923 g cm−3. The glass transition temperature
of the neat polymer is Tg = 198 K and the enthalpic peak of
the melting range is at 370 K. Nominal CB volume fractions,
␾, between 0% and 22% was incorporated in the polymer
matrix. Samples were fabricated by mechanical mixing, we
refer to Ref. 14 for experimental details of the sample prepa-
ration procedure.
The electrical resistance for the eight samples of various
compositions has been measured in the temperature range
from 80 to 350 K. All dc conductivity 共␴dc兲 measurements
were performed on the composite samples using a standard
four-probe method with a Keithley 617 electrometer. As pre-
viously mentioned, the samples are circular disks with typi-
cal thickness 1 mm and diameter 10 mm. Prior to measure-
ment, the circular surfaces of the samples were polished and
covered with a thin layer of H20E Epotek silver epoxy,
manufactured by Epoxy Technology, to serve as electrodes.
Conduction was Ohmic. To ensure that the results reported
herein were due to the bulk composite materials, and not
from the silver paint electrodes, control experiments with a
contactless configuration were employed to eliminate the
possibility that Schottky barriers at the contacts influence the
data. Direct evidence for the percolation transition comes
from ␴dc versus ␾ characteristics. The abrupt change in this
124111-3 Belattar et al. J. Appl. Phys. 107, 124111 共2010兲

10
20 (a) 12.40 vol %

M''(x10 )
13.00 vol %

-5
15.82 vol %
15 18.91 vol %
15
M ' ( x10 )
19.93 vol %
-5 187 K
199 K 10
10 230 K 10 15 10 15 20
236 K -5
265 K M'(x10 )
5 281 K
295 K FIG. 3. Isothermal plot of M ⬙ vs M ⬘ for Raven 7000-EBA samples at room
319 K
0 temperature. CB volume fractions are shown in each curve.
2 3 4
10 10 10
F (Hz) V0 is the input signal 共兩V0兩 = 1 V兲, and Vf and Vq denote the
in-phase and out-of-phase components of the measured sig-
10 (b) 187 K
nal, respectively. In the frequency range from 10 Hz to 100
199 K
230 K kHz the effective complex electric modulus M of the com-
M'' ( x 10 )

8 236 K
-5

265 K
281 K
6 295 K
319 K
4
2 found elsewhere.28
2 3
10 10 10
F (Hz)
FIG. 1. 共a兲 Plot of the real part of the electric modulus, M ⬘, of the Raven
7000-EBA sample 共␾ = 12.4 vol %兲 as a function of frequency for different
values of temperature. 共b兲 Same as in 共a兲 for the imaginary part M ⬙.
characteristics at ␾ = ␾c and the corresponding critical expo-
nents s and t are unambiguous evidence of a percolation
transition. The values of the room temperature dc conductiv-
ity of the neat polymer matrix and CB powder are
10−14 ⍀−1 m−1 and 350 ⍀−1 m−1, respectively. The values
of the percolation threshold, ␾c, is ⬇11 vol %. This value is
notably higher than that of Raven 7000-DGEBF samples
共␾c = 2.75 vol %兲,8,9 but is comparable to values reported by
Jäger et al. in a series of acetylene black-EBA composites.27
For the experiments reported here, the electromagnetic
measurements were conducted in a previously described
setup using a lock-in amplifier 共SR850 DSP兲.28 Typically, the
in-phase resistive component and out-of-phase capacitive
component of the sample signal are measured. This is fol-
lowed by the calculation of the real and imaginary compo-
nents of the effective complex impedance Z = 共Ri共VfV0 − Vf2
− V2q兲 − ␻C2i R2i VqV0 / 共1 + ␻2C2i R2i 兲共Vf2 + V2q兲兲 − i共VqV0Ri
+ ␻C2i R2i 共VfV0 − Vf2 − V2q兲 / 共1 + ␻2C2i R2i 兲共Vf2 + V2q兲兲. This expres-
sion is obtained when the sample impedance is in series with
a known resistance 共1 k⍀兲 which is in parallel with the
lock-in input impedance. Ri represents the equivalent resis-
tance of the lock-in input resistance 共100 M⍀兲 and the
known resistance, Ci is the lock-in input capacitance 共15 pF兲,
M''(x10 )
posite samples is extracted from M = C0 / 共C − i␻−1R−1兲, where
C0 = ␧0A / s with A and s being the surface area and the thick-
ness of the sample, respectively. The experimental data span
the temperature, T, range from about 150 共Tg − 48 K兲 to 319
共Tg + 121 K兲 K. More details on the measurements can be
4
III. RESULTS
A. Temperature and CB volume fraction dependencies
of the electric modulus spectra
The temperature evolution of the effective electric
modulus spectra of a specific sample, having nominal CB
volume fraction equal to 12%, are shown in Fig. 1. The top
panel describes the real part of the electric modulus M ⬘. The
bottom panel corresponds to the imaginary part M ⬙. Exami-
nation of these figures yields the following initial observa-
tions: 共i兲 the value of M ⬘ at 10 kHz is about 2 10−4 and is of
the same order as those observed in similar materials;1 共ii兲 a
local and rounded maximum, i.e., the peak loss, is observed
in the spectral profile of M ⬙ corresponding to a specific value
of frequency Fmax. Interestingly, the amplitude of this maxi-
mum is nearly the same. 共iii兲 This maximum is red-shifted
upon heating from low temperatures. However, the shift be-
comes significant only for T ⱖ Tg + 50 K as seen by compar-
ing the symbols in Fig. 1共b兲; and 共iv兲 the spectral profile of
M ⬙ has a clear asymmetry.
In Fig. 2, we plot M ⬘ and M ⬙ as temperature is varied
from below to above Tg. We observe that M s = M ⬘共␻ → 0兲 is
invariant as T is changed and note that the range of the
vertical axis containing the maximum of M ⬙ is small. Figure
3 compares the room temperature values of M ⬘ and M ⬙ as a
function of CB volume fraction. All visible relaxation peaks
show a leveling off with increasing ␾. We note also that M s
is invariant as ␾ is changed while with increasing ␾, while
M ⬁⬘ = M ⬘共␻ → ⬁兲 shows a pronounced reduction by 1 order of

10 187 K 230 K magnitude.

-5

199 K 236 K
265 K
281 K
Figure 4 compares M max ⬙ = M ⬙共F = Fmax兲 and M max ⬘
5 295 K = M ⬘共F = Fmax兲 as temperature is varied for the typical
319 K

10
sample corresponding to a CB content of 19.93 vol %. The
0 5 15 20 25
-5 experimental adapt show a power-law dependence contained
M'(x10 )
in the relation M max ⬘ 兲k2共␾,T兲. This relation
⬙ = k1共␾ , T兲共M max
FIG. 2. Plot of M ⬙ vs M ⬘ for a Raven 7000-EBA sample 共␾ = 12.4 vol %兲. holds for any CB filling explored. It should also be noted that
Temperatures are shown in each curve. this power-law dependence is qualitatively similar from
124111-4 Belattar et al. J. Appl. Phys. 107, 124111 共2010兲

160 K 0 12.40 vol %

181 K

-10.92
203 K
-1 13.01 vol %
222 K 15.82 vol %
-2 18.91 vol %
ln M max

ln(
)(S)
19.93 vol %
-3
''

240 K
-11.00
-5
278 K

-11.08
-11.00 -10.90 -10.80 -6 Tg
'
ln M max
3 4 5 6 7 8
3
FIG. 4. Plot of M max ⬙ vs M max ⬘ for a Raven 7000-EBA sample 共␾ 10 /T (K )
-1

= 19.9 vol %兲. Symbols correspond to different values of temperature. The

⬙
solid line shows the power-law dependence contained in the relation M max
⬘ 兲k2共␾,T兲 with k1 = 0.28 and k2 = 0.89.
= k1共␾ , T兲共M max
those of previous experiments on Raven 7000-DGEBF
samples, albeit expressed within the effective permittivity
formalism.9
B. CC modeling
The unsymmetrical profile of M ⬙ indicates that the
simple exponential 共Debye兲 is inappropriate to describe he
relaxation and should be replaced by a frequency-dependent
electric modulus M共␻兲 = M ⬁⬘ 关1 − 兰⬁0 exp共−j␻t兲共−d␾ / dt兲dt兴,
where ␾共t兲 denotes the electric field relaxation function.1
Our goal now is to assess the level of accuracy we can expect
for the value of M according to the CC model. One of the
most popular ansatz for the relaxation in dielectric materials
is given by the CC phenomenology.1,29,30 Figure 5 shows an
example of the M ⬙ vs M ⬘ data along with a simulation 共line兲
based on the CC modeling for the electric modulus. The
basic functional form of M is well known and can
be expressed as M ⬘ = M ⬁⬘ M sA关AM s + 共M ⬁⬘ − M s兲cos ␸兴 /
关A2M s2 + 2A共M ⬁⬘ − M s兲M s cos ␸ + 共M ⬁⬘ − M s兲2兴, and M⬙
10 (a)
M (x10 )
-5
FIG. 6. An Arrhenius plot of the relaxation time in Raven 7000-EBA
samples. The solid lines are fits with an Arrhenius temperature dependence
for the apparent relaxation time ␶. The numbers in the graph indicate the
value of the CB loading.
= M ⬁⬘ M sA关共M ⬁⬘ − M s兲sin ␸兴 / 关A2M s2 + 2A共M ⬁⬘ − M s兲M s cos ␸
+ 共M ⬁⬘ − M s兲2兴, where M ⬁⬘ = 1 / ␧⬁⬘ is a measure of the
“strength” of the electric field relaxation, M s = 1 / ␧s
with ␧s denoting the static 共␻ = 0兲 permittivity,
A = 关1 + 2共␻␶兲1−␣ sin ␲␣ / 2 + 共␻␶兲2共1−␣兲兴1/2, and ␸
= tan−1关共␻␶兲1−␣ cos ␲␣ / 2 / 共1 + 共␻␶兲1−␣ sin ␲␣ / 2兲兴. We per-
formed a fit to the data using the above equations for M ⬘ and
M ⬙ from which we extract the parameter ␣ which gauges the
broadening of the loss spectrum. The values obtained for ␣
are in the range 0.06–0.10 and suggest a behavior close to
the state of a single relaxation time.1,2,21 The free parameters
in the fit are M ⬁⬘ , M s, ␣, and ␶, and the quantity we are most
interested in, namely ␶共␾ , T兲. It is immediately apparent
from the comparison of the data with the CC dielectric func-
tion that they are in good agreement with their respective
simulations. For the series of electric modulus spectra, a set
of Arrhenius relaxation time 共prefactor and effective activa-
tion energy兲 were used. Figure 6 displays the relaxation time
that best fit the experimental M spectra plotted versus the
inverse of temperature. The straight line in Fig. 6, except as
we approach Tg, corresponds to an activated thermal relax-

ation time. The data sets have similar apparent activation

5 energy, i.e., 60⫾ 14 meV. In the fitting process, the Arrhen-
''

ius parameters were varied until simulations of the quality

10 4 8 12 16 displayed in Fig. 5 were obtained for each nominal tempera-
' -5
M (x10 ) ture and CB volume fraction. The best parameters were those
that minimized the chi-square error between the experiment
and simulation. Equally good fits were obtained for a range
(b)
15 15 of effective activation energies and prefactors with errors
corresponding to within ⫾5%. We note further that the pref-
M (x10 )

actor is commonly on the order of 10−3 s. Whereas there are

M (x10 )

10 10
-5
-5

many studies focusing on the details of the activation energy

and the microscopic processes for dielectric relaxation,1 the
5 5
''
'

fundamental physics of the prefactor is not revealed. Another

remarkable feature is that in experiments which probe the
10 2 00
10 10
3
10
4 temperature dependence of ␶ we do not observe any signifi-
log(F) (Hz) cant change in behavior below and above Tg. This point will
be discussed in Sec. IV.
FIG. 5. 共a兲 CC plot of the complex electric modulus of the Raven 7000-
EBA sample 共␾ = 13.0 vol %兲. T = 175 K. The solid line is a fit to the CC IV. DISCUSSION AND CONCLUSIONS
equation. The fit parameters are: M s = 10−7, M ⬁⬘ = 1.9 10−4, ␣ = 0.06, and ␶
= 4.1 ms. 共b兲 Plot of M ⬘ and M ⬙ as a function of frequency for the same We continue with a discussion of some general features
sample. of our approach and a comparison of our results to the rel-
124111-5 Belattar et al.
evant literature. Although first-principles calculations and
further experiments are needed to fully understand the di-
electric relaxation mechanisms, some conclusions can be
drawn from our observations. In this paper we presented a
detailed analysis of electric modulus spectra of CB filled
polymers that allowed us to characterize the dielectric relax-
ation for different CB contents on the conducting side of the
percolation transition. The CC equation fitting to the M共F兲
data in the interval Tg − 48 K ⬍ T ⬍ Tg + 121 K gives small
values of the parameter ␣. The above results can be rational-
ized by considering a behavior close to the state of a single
relaxation time. These results are in apparent contrast to
those of Tsangaris and co-workers21 who reported a study of
the electric modulus of hybrid composite systems consisting
of epox-resin-metal powder-aramid fibers with alternative
fitting equations, i.e., Davidson–Cole 共DC兲 and HN. These
authors found that interfacial polarization is best described
by the DC approach because of the asymmetric distribution
of relaxation times, and only in the system with the higher
heterogeneity 共greater filler content兲 must the HN approach
be used. Some comments have to be made yet about the
evolution of M with filler content. While the above analysis
of the electric modulus strongly suggests that the CB meso-
structure, i.e., the filler-filler and filler-amorphous chains in-
teractions, is an important element, it was found that the CB
particles distribution within the matrix plays an important
role in the viscoelastic properties of similar composites
above ␾c, not only in the solid but also in the molten state.27
Indeed, in these materials filler particles concentrate in the
amorphous regions of the polymer, which are also butyl
acrylate-rich regions. Jäger et al.27 have argued that, below
the melting rage of the similar CB filled EBA samples, the
electron transport mechanism occurs through gaps between
CB aggregates with a variable gap width distribution
It is also interesting to compare the kinetic parameters
for relaxation in these samples with those of the literature.
For the ranges of CB content and temperature explored, the
apparent activation energy is almost constant, whereas the
prefactor changes from 7 ⫻ 10−3 to 4 ⫻ 10−4 s, i.e., by a fac-
tor greater than 18, as the CB volume fraction increases from
12.4% to 19.9%. The associated prefactors are unusually
high. Similar behavior, i.e., long trapping time, has been re-
ported for bulk silicate filled carboxylated nitrile rubber. We
suggest that the absence of difference in activation energy of
the relaxation time and the large values of the prefactor for
the different samples investigated are an indication of the
dynamically heterogeneous nature of CB aggregates within
the polymer matrix. It is interesting to compare the results
obtained here with the activation energies for the dc conduc-
tivity which were found to be in the range 8.6–19.1 meV.28 A
common view is that in dipolar materials undergoing a glass
transition, there are fundamental differences between the re-
sponses below and above Tg. Below Tg the loss maxima are
broader and their temperature dependence typically follows
the Vogel–Tammam–Fulcher 共VTF兲 “law” for the slowing
down of relaxation processes found in many amorphous ma-
terials, ␶ ⬀ exp关W / k共T − T0兲兴, where k is the Boltzmann con-
stant, and T0 is an ordering temperature below Tg whose
significance has remained unclear 共there is no microscopic
J. Appl. Phys. 107, 124111 共2010兲
prescription to calculate T0兲. If we regard that the VTF law
describes a thermally activated process where the W is ap-
proaching infinity at T0, W is directly related to the activation
energy. The above empirical VTF law has been experimen-
tally observed in a variety of supercooled organic liquids,
spin glasses, polymers, and is characteristic of cooperative
relaxations.31,32 In practice, the VTF law holds only for tem-
perature somewhat above T0 and the singularity is not actu-
ally observed. Above Tg the maxima are narrower and the
maximum loss frequency follows the Arrhenius temperature
dependence, ␶ ⬀ exp共w / kT兲, where w is an activation energy.
Thus, for T ⬇ Tg, we would expect a crossover between the
Arrhenius and VTF regimes. Such transition is not observed
here. As CB loaded EBA composites are semicrystalline, in-
trinsic inhomogeneities such as the PE-rich crystallites with
no CB particles inside, play also a crucial role in the dielec-
tric response. We are currently measuring the ac electrical
properties of these samples in thermal cycling and isothermal
annealing experiments to further explore how the CB aggre-
gates rearrange in time-and temperature-dependent pro-
cesses.
To summarize, we have studied dielectric relaxation in
CB filled polymer composites and have reported experimen-
tal data of the electric modulus extracted from impedance
spectroscopy. Relaxation time, a bulk probe, is currently
measurable in a broad temperature interval from below Tg to
above Tg. Relaxation time associated to the peak imaginary
part of M can be changed in wide range by variation in CB
volume fraction as well as by state parameters, e.g., T. We
found that the phenomenological CC equation reproduces the
general trend seen experimentally in M共␻兲. An examination
of the CB content of the relaxation time has enabled us to
draw further conclusions. As pointed out in the context of
other experiments, the observed relaxation mechanism does
not result simply from thermally activated dipolar interac-
tions but is a collective cooperative effect of the CB mesos-
tructure. It is natural to expect that our conclusions should be
applicable to other types of percolative CB filled polymers.
C atoms can be coaxed into several topologies to make ma-
terials with unique properties, i.e., CB particles and fibers,
graphene sheets. The inherent charge transport characteristics
and the factors that limit the charge carrier mobility differ
significantly between the various C nanostructures reflecting,
on the one hand, the electronic dimensionality of the struc-
tures, and, on the other hand, the achievable dimensions of
the respective ␲-systems. Bonding between C and other ele-
ments can easily be changed by chemical reactions and
physical interactions. Plastic C nanoelectronics is a forefront
research area with cross-fertilization between the materials
science, chemistry, physics, nanotechnology, and engineering
communities.33 In a manner entirely analogous to the current
investigation, we are motivated to explore the dielectric re-
laxation behavior in these potentially rich materials.
ACKNOWLEDGMENTS
The authors are grateful to F. Carmona, CRPP, Univer-
sité Bordeaux I, France for providing us with the samples.
Our work at Brest was supported by Lab-STICC which is
Unité Mixte de Recherche CNRS 3192.
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