Journal of Composite Materials

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Dynamic mechanical thermal analysis and dielectric thermal analysis of siloxane rubber-based
composites filled with carbon black
Omar A Al-Hartomy, MA Ibrahim, Ahmed Al-Ghamdi, Nikolay Dishovsky, Milcho Ivanov, Mihail Mihaylov and Farid
El-Tantawy
Journal of Composite Materials 2012 46: 1765
DOI: 10.1177/0021998311425619
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JOURNAL OF
COMPOSITE
M AT E R I A L S

Article

Dynamic mechanical thermal analysis

and dielectric thermal analysis of siloxane
rubber-based composites filled with
carbon black

Journal of Composite Materials

46(14) 17651770
! The Author(s) 2011
Reprints and permissions:
sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0021998311425619
jcm.sagepub.com

Omar A Al-Hartomy1,2, MA Ibrahim3, Ahmed Al-Ghamdi2,

Nikolay Dishovsky4, Milcho Ivanov4, Mihail Mihaylov4
and Farid El-Tantawy5

Abstract
Siloxane rubber-based composites filled with furnace carbon black N 220 at various concentrations were investigated
by dynamic mechanical thermal analysis and dielectric thermal analysis. It was found that in the temperature interval
from 30 C to 100 C the increase in the amount of carbon black results in the increase in the storage modulus (E0 ) values,
as well as those of the mechanical loss angle tangent (tan d). The decrease in E0 and the increase in tan d in the interval from
40 C to 30 C was due to the process of the melting of the crystal structure of the siloxane rubber, formed during the
cooling of the tested samples. Dielectric thermal analysis showed that the increase in the amount of carbon black lead to
obtaining of vulcanizates with higher dielectric permittivity ("0 ), whose values decrease with the increase of frequency. The
research that was carried out showed that with the siloxane rubber-based composites the percolation threshold was
reached when the concentration of carbon black was 20 wt%.

Keywords
Siloxane rubber, carbon black, nanocomposites, mechanical properties, dielectric properties

Introduction
Siloxane elastomers are unusual synthetic polymers
whose backbone is composed of an inorganic repeating
unit, that is, silicon to oxygen bonds. In addition, the
silicon atoms are attached to organic groups, such as
methyl. The presence of the inorganic and organic
units gives siloxanes their unique properties and thermal
and chemical stability. At extreme temperatures the tensile strength, elongation, tear strength, and compression
set can be far superior to those of conventional rubbers.
Organic rubber (NR, SBR, BR, etc.) has a carbon to
carbon backbone which can make them susceptible to
ozone, UV, heat, and other aging factors that siloxane
rubber can withstand well. This makes it one of the
elastomers of choice in many extreme environments.1
Hence, siloxane-based micro- and nanocomposites
have received increasing attention in the recent years.24
With the development of electronic industry, some
special dielectric materials with high and/or low

dielectric permittivity are attracting a remarkable attention in academic and industrial elds. The dielectric
properties of the insulative materials could be adjusted
by dispersing dierent kinds of llers into polymer
matrices to form the polymer/ller composites. With
changing the concentration of llers, the dielectric
1
Department of Physics, Faculty of Science, University of Tabuk, 71491
Tabuk, Saudi Arabia
2
Department of Physics, Faculty of Science, King Abdulaziz University,
21589 Jeddah, Saudi Arabia
3
Department of Chemistry, Faculty of Science, University of Tabuk, 71491
Tabuk, Saudi Arabia
4
Department of Polymer Engineering, University of Chemical Technology
and Metallurgy, 1756 Sofia, Bulgaria
5
Department of Physics, Faculty of Science, Suez Canal University, Ismailia,
Egypt

Corresponding author:
Mihail Mihaylov, Department of Polymer Engineering, University of
Chemical Technology and Metallurgy, 1756 Sofia, Bulgaria
Email: m_c_mihaylov@abv.bg

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Journal of Composite Materials 46(14)

permittivity could be changed. When ller with low

dielectric permittivity is added into the polymers, the
composites with low dielectric permittivity could be
acquired. While the inorganic or organic llers with
high dielectric permittivity are added into the polymers,
composites with high dielectric permittivity should be
acquired.5
A variety of llers can be used in siloxane rubber to
change its mechanical and dielectric properties although
most are nonreinforcing and lower the tensile properties. Carbon black is generally well-known reinforcing
ller used to improve the mechanical properties and to
prevent their ultraviolet degradation.6 Blending siloxane rubber with carbon black gives the benet of light
weight, compared with blending ferrite in a rubber
matrix. In the same time the lling of siloxane rubber
with carbon black would lead to the formation of high
dielectric permittivity composites with good mechanical
properties.
Therefore, the attention has been focused on the
siloxane rubber blends comprising dierent amounts
of carbon black.
This article presents the results of dynamic mechanical thermal analysis and dielectric thermal analysis
of siloxane rubber-based nanocomposites, lled with
carbon black nanoparticles at various concentrations
of the ller.
On the ground of the said above it could be expected
that the nanocomposites based on siloxane rubber comprising carbon black would possess a number of interesting properties opening new opportunities for their
application.

Si 0, Si 10, Si 20, Si 30, Si 40, respectively were prepared.

The vulcanization process of the siloxane rubber-based
compounds was carried out in an electrically heated
hydraulic press using a special homemade mold at temperature 195 C and under pressure 150 kN/m2 for
60 min. The dimensions of the homemade mold used
are 200  200  2 mm.

Characterization and measurements

Dynamic mechanical thermal analysis. Dynamic
properties (storage modulus (E0 ) and mechanical loss
angle tangent (tan d) of the siloxane rubber-based vulcanizates were investigated using a Dynamic Mechanical
Thermal Analyzer Mk III system (Rheometric
Scientic). The data were obtained at 5 Hz frequency,
64 mm strain in the temperature range from 100 C to
100 C using a heating rate of 3 C/min under single cantilever bending mode. The dimensions of the investigated samples were as follows: width 10 mm, length
25 mm and the thickness measured using a micrometer
varied between 1 and 2 mm.

Dielectric thermal analysis. Dielectric properties (permittivity ("0 ) and dielectric loss angle tangent (DETA
tan d) were investigated using Dielectric Thermal
Analyzer (Rheometric Scientic) at four dierent frequencies (1 kHz, 10 kHz, 100 kHz, and 1 MHz) in the
temperature range between 20 C and 100 C on a
sample having a diameter approximately 32 mm and
1 mm thickness.

Results and discussion

Dynamic mechanical thermal analysis

Experimental
Materials
Siloxane rubber namely ELASTOSIL R 401/30 produced by Wacker Chemie AG with high temperature
cure, density at 25 C 1,1 g/cm3 and hardness of 30
Shore A was purchased from North Special Rubber
Corporation of Hengshui, Hebei Province, China.
Furnace carbon black namely N 220 with particle size
of about 20 nm used as conductive ller was received
from Alexandria trade Rubber Company, Alexandria,
Egypt.

Preparation of rubber nanocomposites

The mixing was accomplished in an open two-roll mill
under identical conditions of time, temperature, and nip
gap, with same sequence of mixing of all compounding
ingredients to avoid the eect of processing on physical
properties. Several batches with dierent concentration
of carbon black 0, 10, 20, 30 and 40 wt% abbreviated as

The properties obtained by DMTA were the storage

modulus (E0 ) and the mechanical loss angle tangent
(tan d).
Figure 1 shows the dependencies of the storage modulus (E0 ) as a function of temperature on siloxane
rubber-based composites containing dierent amounts
of carbon black. The gure clearly shows that in the
temperature interval from 100 C to 30 C there are
no considerable dierences in the storage modulus (E0 )
values depending on the ller concentration. More considerable dierences in the storage modulus (E0 ) are
observed in the temperature range between 30 C and
100 C. In this specic temperature interval the increase
in the amount of carbon black results in the increase in
storage modulus (E0 ). This eect is due to the stronger
interactions of the ller particles, which on its turn
leads to the restriction of the exibility of the rubber
segments, respectively to the increase in the storage
modulus (E0 ) values.7 Figure 1 also shows that in

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1767

Figure 1. Storage modulus (E0 ) dependency on the temperature

for siloxane rubber nanocomposites comprising different
amounts of carbon black.

Figure 3. Temperature dependence of the storage modulus (E0 )

for the composite Si 0 during the cooling or cooling followed by
heating of the sample.

Figure 2. Mechanical loss angle tangent (tan d) dependency on

the temperature for siloxane rubber nanocomposites comprising
different amounts of carbon black.

Figure 4. Frequency dependence of the dielectric permittivity

("0 ) at various filler content for the siloxane nanocomposites with
carbon black at 30 C.

the temperature interval from 40 C to 30 C the

storage modulus (E0 ) values of the tested composites
decrease sharply, regardless of the ller concentration.
Tan d being the ratio between the dynamic loss modulus (E00 ) and dynamic storage modulus (E0 ) (tan d E00 /
E0 ) illustrates the macromolecules mobility as well as the
phase transitions in the polymers.8
Figure 2 shows the dependencies of the mechanical
loss angle tangent (tan d) as a function of temperature
for the tested siloxane rubber-based composites comprising various amounts of carbon black. It is obvious
from the gure that in the temperature interval from
100 C to 30 C, the values of mechanical loss angle
tangent (tan d) similarly to those of the storage modulus
(E0 ) do not change signicantly depending on the ller
concentration.
In the temperature interval from 30 C to 100 C the
increase in the ller concentration leads to the increase
in the tan d values. It is possible that the lling of the

siloxane rubber with higher quantities of carbon black

prevents the formation of a quality vulcanization structure. As a result the tan d values increase with the
increase of temperature which is more pronounced
with the vulcanizates comprising 30 wt% and 40 wt%
carbon black.
Usually with elastomers like natural rubber (NR) or
styrene-butadiene rubber (SBR) in the temperature
interval from 50 C to 20 C decrease in the storage
modulus (E0 ) is observed as well as a prominent peak in
tan d, which corresponds to the glass transition temperature (Tg) of the elastomer. It is known that the glass
transition temperature of the siloxane rubber is considerably lower than 50 C (about 127 C) and the
changes in the storage modulus (E0 ) and tan d concerning the tested composites cannot be attributed to the
glass transition temperature of the polymer. The
decrease in the E0 values in the temperature interval
from 40 C to 30 C as well as the increase in tan d

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Journal of Composite Materials 46(14)

Figure 5. Dielectric permittivity vs temperature at various frequencies for the siloxane rubber composites comprising different
amounts of carbon black.

concerning the tested composites is due to the melting of

the crystal structure of the siloxane rubber that formed
during the cooling of the samples.9 This was proven by
the data of the storage modulus (E0 ) that were measured
during the cooling of the samples as well as during cooling followed by heating. (Figure 3). In the rst case
(indicated on Figure 3 as cooling) the measurements
are carried out during the cooling of the sample. In the
second case (indicated as cooling followed by

heating) the sample is rstly cooled till 100 C and

then the measurements are carried out during the heating of the sample till 0 C.
Figure 3 shows that the storage modulus (E0 ) values
increase at about 70 C when the measurement is
carried out during the cooling of the sample which
is an indication of a crystallization phase transition9 in
the tested siloxane rubber-based composites. When the
measurement is carried out during the heating of the

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Al-Hartomy et al.

1769

sample the storage modulus (E0 ) values decrease at

about 40 C, which is due to the melting of the already
formed crystal structure.

Dielectric thermal analysis

Figure 4 presents the dependencies of the dielectric permittivity as a function of the frequency for the siloxane
rubber vulcanizates, comprising various amounts of
carbon black at 30 C. It is clear from the gure that
with the increase in the ller concentration the values
of the dielectric permittivity ("0 ) increase at all tested
frequencies. Despite this fact, the values of the dielectric
permittivity ("0 ) of the vulcanizates comprising 10 wt%
carbon black (Si 10) are closer to those of the vulcanizates that do not contain ller (Si 0). In this case the
values of the dielectric permittivity ("0 ) depend on the
polymer matrix and they do not change signicantly
with the increase in the frequency or the ller concentration. It is also obvious from the gure that the percolation threshold has been reached by the vulcanizates
containing 20 wt% carbon black (Si 20) or in other
words the formation of electroconductive paths starts
at a concentration of the ller above 20 wt%. In this
case the dielectric permittivity ("0 ) value reaches up to
4.9  103 at 1 kHz. The lling of the siloxane rubber
with 30 wt% and 40 wt% carbon black leads to the
additional increase in the dielectric permittivity ("0 )
and its values are respectively 7.4  105 for the vulcanizates comprising 30 wt% ller (Si 30) and 8.9  106 for
the vulcanizates containing 40 wt% carbon black (Si
40). With vulcanizates containing 20, 30, 40 wt% the
dielectric permittivity ("0 ) decreases with the increase
in the frequency which is more pronounced at higher
concentrations of the used ller.
Figure 5 presents the dependencies of the dielectric
permittivity ("0 ) of the investigated siloxane rubberbased composites comprising various amounts of
carbon black as a function of temperature at frequencies
1 kHz, 10 kHz, 100 kHz, and 1 MHz. It is seen that with
the composites that do not contain a ller (Si 0), the
dielectric permittivity ("0 ) decreases with the increase
of temperature at all tested frequencies. This tendency
is kept with vulcanizates comprising 10 wt% carbon
black (Si 10) but with this concentration of the ller,
the dielectric permittivity ("0 ) values are considerably
higher. With vulcanizates comprising above 20 wt%
carbon black, however, the increase in temperature
does not lead to any considerable changes in the
values of the dielectric permittivity. Moreover, in
some cases the values of the dielectric permittivity
increase with the increase of temperature. As already
mentioned above, this means that the percolation
threshold is reached with the vulcanizates comprising
20 wt% carbon black.

Figure 6. Frequency dependence of the dielectric loss angle

tangent (DETA tan d) at various filler content for the siloxane
nanocomposites with carbon black at 30 C.

Figure 7. Frequency dependence of the dielectric loss angle

tangent (DETA tan d) at various filler content for the siloxane
nanocomposites with carbon black at 90 C.

Figure 6 shows the dependencies of the dielectric loss

angle tangent (DETA tan d) as a function of the frequency for the siloxane rubber-based vulcanizates, comprising various amounts of carbon black at 30 C. It can
be seen that the DETA tan d values are in agreement
with the data of the dielectric permittivity ("0 ) (Figures 4
and 5). The lowest values with regard to this index are
observed with vulcanizates that do not contain ller
(Si 0). DETA tan d values increase with the increasing
in the ller concentration. When the concentration of
carbon black is up to 20 wt% the increase in frequency
does not lead to any signicant changes in the values of
DETA tan d, whereas with vulcanizates comprising 30
or 40 wt% carbon black the increase in frequency leads
to the decrease in the DETA tan d values. The gure
also shows that with high concentrations of the ller and
a frequency 100 kHz and 1 MHz the DETA tan d values
are very close.

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Journal of Composite Materials 46(14)

Analyzing the dependencies of the dielectric loss

angle tangent (DETA tan d) as a function of the frequency at 90 C presented on Figure 7, it can be concluded that the higher temperatures do not have
signicant inuence on this variable.

Conclusion
(1) DMTA studies have been carried out on the
changes in storage modulus (E0 ) and the mechanical
loss angle tangent (tan d) as a function of temperature
and ller concentration for siloxane rubber-based
nanocomposites comprising furnace carbon black N
220 at various concentrations. It was found that in
the temperature interval from 100 C to 30 C
there are no signicant dierences with regard to E0
and tan d depending on the amount of the used ller.
In the temperature interval from 30 C to 100 C the
values of E0 and tan d increase parallel with the
increase in the ller concentration. The decrease in
E0 and the increase in tan d in the temperature interval
from 40 C to 30 C is due to the melting of the
crystal structure of siloxane rubber formed during
the cooling down of the tested samples.
(2) DFTA investigations were carried out to determine the dependences of dielectric permittivity ("0 ) and
dielectric loss angle tangent (DETA tan d) on temperature and on frequency of the siloxane rubber-based
nanocomposites comprising furnace carbon black
N220 at various concentrations. It was found that the
increase in the amount of carbon black results in the
increase of the dielectric permittivity ("0 ) and the dielectric loss angle tangent (DETA tan d), which is more
pronounced with concentrations of the ller above
20 wt%. When the concentration of carbon black is
above 20 wt%, both values decrease with the increase
in the frequency. With vulcanizates comprising up to 10
wt% the dielectric permittivity decreases with the
increase in temperature whereas with vulcanizates
comprising above 20 wt% ller, a slight increase in
the indications is observed. Considering all the abovementioned criteria, it can be concluded that the

percolation threshold of the tested siloxane rubberbased composites is reached when the concentration of
the carbon black is about 20 wt%.
Acknowledgments
The present research is a result of an international collaboration program between University of Tabuk, Tabuk, Kingdom
of Saudi Arabia and the University of Chemical Technology
and Metallurgy, Soa, Bulgaria. The authors gratefully
acknowledge the nancial support from the University of
Tabuk.

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