Temperature and frequency dependent

rheological behaviour of carbon black filled

natural rubber
X.-L. Hu1, W.-B. Luo*1, X. Liu1, M. Li1, Y.-J. Huang2 and J.-L. Bu2
The temperature and frequency dependent viscoelasticity of carbon black filled rubber is
investigated. Temperature sweep and frequency sweep dynamic mechanical analysis tests are
performed to investigate the frequency dependent glass transition temperature and to identify the
thermorheological nature of the material. The test results show that master curves of dynamical
properties can be constructed by horizontal shifts along the frequency axis alone and cover a
frequency range of 21 decades, verifying the material’s thermorheological simplicity. This
simplicity is confirmed by van Gurp–Palmen and Cole–Cole plots. Moreover, the temperature
dependence of the shift factor is modelled well by both the Williams–Landel–Ferry equation and
the Arrhenius equation.
Keywords: Rubber, Dynamic mechanical properties, Shift factor, van Gurp–Palmen plot, Cole–Cole plot, Thermorheological simplicity

Introduction extrapolation is necessary for predicting properties at

Natural rubber is one of the most important elastomers,
and its properties are usually improved by the incorpora-
tion of carbon black (CB) or silica of varying surface
chemistry and aggregate size/aspect ratio to suit the
application concerned.1 Carbon black filled rubbers are
widely used as engineering materials owing to their
excellent performance in terms of vibration and shock
dampening, elimination of structural noise and resistance
to corrosion by acids and erosion by solids such as ores.
Study of the mechanical properties of CB filled rubber
is crucial for structure design. The main features of CB
filled rubber in this regard are its high elasticity, high
degree of damping and high elongation at failure. Many
constitutive models have been proposed to reproduce
the complex mechanical behaviour of filled rubbers,
which includes hyperelasticity,2,3 viscoelasticity,4,5 the
Mullins effect6 and the Payne effect.7,8
The viscoelastic properties of materials are often
determined either with static measurements such as step
load creep or relaxation and slow ramp loading
procedures or with steady state oscillation tests. The
latter approach is usually referred to as dynamic
mechanical analysis (DMA) or dynamic mechanical
thermal analysis. Dynamic viscoelasticity over a wide
frequency range is crucial for rubber component design
when the components are subject to an oscillatory load.
However, DMA measurements usually provide data
only for load frequencies ,100 Hz, and therefore,
frequencies over 100 Hz. In this regard, time/frequency–
temperature superposition (TTS/fTS) has proved to be a
useful technique, extending the time/frequency spectrum
by making measurements at different temperatures and
constructing master curves according to the Williams–
Landel–Ferry (WLF) or Arrhenius transformations.9
In the present study, CB filled rubber strip specimens
were loaded with harmonic deformations at different
temperatures, and the steady state stress responses for
frequency sweep were evaluated in terms of storage
modulus and loss modulus. The temperature and
frequency dependent dynamic moduli were then dis-
cussed and modelled.
Laboratory study
Background of DMA
Assume that a linear viscoelastic solid is loaded with a
sinusoidal strain
eðtÞ~e0 eivt (1)
where e0 is the strain amplitude, v is the angular
frequency of the strain oscillation and t is the elapsed
time. The steady state dynamic stress response to the
oscillatory strain is
s~E  ðivÞeðtÞ (2)

1
College of Civil Engineering and Mechanics, Xiangtan University,
Here, E* is the complex modulus of the material and
Xiangtan 411105, China can be decomposed into its real and imaginary parts
2
Zhuzhou Times New Material Technology Co., Ltd, Zhuzhou 412007, E’ðvÞ andE’’ðvÞ, respectively, as
China
*Corresponding author, email luowenbo@xtu.edu.cn E  ðivÞ~E’ðvÞziE’’ðvÞ~jE  ðivÞjeidðvÞ (3)

ß Institute of Materials, Minerals and Mining 2013

Published by Maney on behalf of the Institute
Received 12 November 2012; accepted 24 May 2013
416 DOI 10.1179/1743289813Y.0000000060 Plastics, Rubber and Composites 2013 VOL 42 NO 10

1 Loss tangent tand of CB filled rubber as function of
temperature at various frequencies from 1 to 50 Hz
n at maximum. The peak tand criterion appears most
where the absolute value jE  ðivÞj~ ½E’ðvÞ2 z
½E’’ðvÞ2 g1=2 , and tandðvÞ~E’’ðvÞ=E’ðvÞ. The real part
E’ðvÞ is called the storage modulus, which measures the
stored energy, and the imaginary part E’’ðvÞ is called the
loss modulus, which measures the energy dissipated in a
loading cycle. The angle d(v) is the phase lag of the
stress with respect to the strain input; tand(v) is called
the loss tangent.
Material
The thin rectangular strips, 35 mm long and 7 mm wide,
used for the DMA tests were cut from a 2 mm thick
vulcanised rubber sheet provided by Zhuzhou Times
New Material Technology Co., Ltd, China. The
formulation of the rubber compound was as follows:
100 phr (parts per hundred rubber) natural rubber
(Thailand RRS3), 20 phr CB (N550), 5 phr zinc oxide,
5 phr antioxidant, 2?5 phr sulphur (200 meshes per
square inch), 2 phr stearic acid, 2 phr microcrystalline
wax, 2 phr solid coumarone resin and 1?4 phr vulcanisa-
tion activator.
Measurements by DMA
In order to investigate the dynamic viscoelasticity of the
CB filled rubber, dynamic mechanical tests were carried
out with a Gabo Eplexor 500N instrument working in
the tensile mode. Temperature sweep tests and isother-
mal frequency sweep tests were performed. In order to
exclude the Mullins effect, that is, softening during the
first few deformation cycles, all specimens were
mechanically preconditioned. The specimens were then
sinusoidally stretched under a prestrain of 0?4% and a
superimposed dynamic strain amplitude of 0?1%, which
maintain the measurement in the linear viscoelastic
region.
The temperature sweep tests were planned to explore
the frequency dependent glass transition temperature Tg
of the material. They were carried out from 28 to 0uC,
using a ramp rate of 2 K min21, and repeated at
Table 1 Values of Tg at different frequencies measured by DMA temperature sweeps
f/Hz 1 2 3 5
Tg/K 222.05 223.85 224.75 225.75
Hu et al. Rheological behaviour of CB filled natural rubber
frequencies f5v/2p of 1, 2, 3, 5, 10, 15, 20, 30 and
50 Hz.
The isothermal frequency sweep tests were conducted
in the range from 0?01 to 100 Hz and repeated at various
temperatures ranging from 270 to 50uC, with an
interval of 10 K; a further test was added at 245uC,
near Tg. The stress responses to the strain excitations in
these isothermal frequency sweep measurements were
recorded automatically, and E’, E’’ and tand were
calculated from these measurements.
Results and discussion
Temperature sweep DMA is often used to determine the
glass transition temperature Tg of a material because of
the sharp drop in storage modulus E9 and corresponding
increase in dissipative loss, manifested by a sharp rise
in loss modulus E0 or loss tangent tand that occur at Tg.
The criterion for determining Tg from DMA data is
usually the temperature at which either E0 or tand is
frequently in the literature,10 and we will use it in this
study.
Figure 1 shows the temperature sweep test results for
the loss tangent tand at various frequencies from 1 to
50 Hz. It is evident that the peak tand, and therefore Tg,
varies as a function of frequency, with increasing test
frequency causing a shift of Tg to higher temperatures.
Table 1 shows the values of Tg at different frequencies.
The activation energy Ea for the glass transition can
be obtained by an Arrhenius type relationship between
the experimental frequency f and Tg (in kelvin) as
follows
 
Ea
f ~f0 exp { (4)
RTg
where f0 is a frequency coefficient, and R is the universal
gas constant. Taking the natural logarithm of equa-
tion (4) yields
Ea 1
ln f ~ln f0 { (5)
R Tg
which reveals that there is a linear relationship between
ln f and 1/Tg. Figure 2 shows the Arrhenius plot of ln f
versus 1/Tg. Fitting equation (5) with the test data in this
figure gives a line with an adjusted R square R250?9875,
and Ea is determined to be 173?415 kJ mol21 by the line
gradient.
The left hand panels of Figs. 3–5 show isothermal
frequency sweep test results for E9, E0 and tand res-
pectively as functions of the test temperature and
frequency. These data reveal that higher frequencies
result in higher storage and loss moduli except at very
low temperatures.
According to fTS, plots of the dynamic property E9
versus logarithmic frequency at different temperatures
can be shifted horizontally along the logarithmic
frequency axis and superimposed to form a master
curve, with plots of E0 and tand behaving similarly.
10 15 20 30 50
228.45 228.45 229.75 230.15 231.55
Plastics, Rubber and Composites 2013 VOL 42 NO 10 417
Hu et al. Rheological behaviour of CB filled natural rubber

E’’ðv,T Þ~E’’ðaT v,Tref Þ (7)

tandðv,T Þ~tandðaT v,Tref Þ (8)

2 Arrhenius plot for glass transition temperature Tg and
frequency f
Materials whose rheological properties can be shifted by
TTS/fTS to produce a smooth master curve are termed
thermorheologically simple materials. Such thermorheo-
logical simplicity can be expressed as follows
E’ðv,T Þ~E’ðaT v,Tref Þ
where aT is known as the horizontal shift factor, Tref is
the reference temperature and T is the temperature at
which aT is to be determined.
To construct a master curve by applying the TTS/fTS
concept in the present study, Tref was selected as 30uC,
and the rheological data at all the other temperatures
were shifted with respect to frequency until the curves
merged into a single smooth function. The horizontal
shift distance required at each temperature to form the
master curve is described by the shift factor aT. A plot of
the experimentally determined values of logaT versus
temperature is shown by the symbols in Fig. 6. The
constructed master curves for the dynamic moduli and
the loss factor are shown in the right hand panels of
Figs. 3–5. It can be seen that the master curves
characterise the dynamic mechanical behaviour over a
frequency range of 21 decades. The applicability of fTS
indicates that the dynamic viscoelastic behaviour of CB
filled rubber is thermorheologically simple.
There are two principal approaches to the description
of the temperature dependence of the shift factor aT,
(6) namely, the WLF equation11 and the Arrhenius relation-
ship.12 The WLF equation is

3 Storage modulus E9 of CB filled rubber as function of angular frequency v at various temperatures (left) and corre-
sponding master curve (right)

4 Loss modulus E0 of CB filled rubber as function of angular frequency v at various temperatures (left) and correspond-
ing master curve (right)

418 Plastics, Rubber and Composites 2013 VOL 42 NO 10

 Hu et al. Rheological behaviour of CB filled natural rubber

5 Loss tangent tand of CB filled rubber as function of angular frequency v at various temperatures (left) and corre-
sponding master curve (right)

{C1 ðT{Tref Þ 1 Ea
log aT ~ (9) C1 ~ :
C2 zðT{Tref Þ 2 303 RTref
in which C1 and C2 are empirically determined material
parameters that depend on the type of polymer (note Substituting the value of Ea (173?415 kJ mol21) into
here that log is the logarithm to base 10, not the natural equation (10) gives the temperature dependence of the
logarithm as used in equation (5)). It is well documented shift factor aT shown by the full curve in Fig. 6.
that the WLF equation describes the effect of tempera- Surprisingly, this is in good agreement with the test
ture on the shift factor quite well for many polymers data and the WLF fit, although it is generally acknowl-
near Tg. Fitting equation (9) with the experimental data edged13 that the Arrhenius relationship is only valid for
gives the dashed curve in Fig. 6, with C1525?52 and the temperature range below Tg, whereas the WLF
C25265?32K. equation is applicable to the temperature range above
The Arrhenius relationship has the form Tg.
  In order to further verify the thermorheological
1 Ea 1 1 simplicity of CB filled rubber, the van Gurp–Palmen
log aT ~ : { (10)
2 303 R T Tref plot and the Cole–Cole plot are presented. Van Gurp
and Palmen14 proposed an approach to the verification
where the activation energy Ea can be determined from of the TTS principle in which they plotted the phase lag
the DMA temperature sweep tests at various frequen- d versus the absolute value of the complex modulus jE  j
cies, as shown in Figs. 1 and 2. Comparison of and found that isothermal frequency curves merge into a
equations (9) and (10) shows that the WLF form common curve if TTS holds. This method of plotting
coincides with the Arrhenius form if eliminates the need to shift data along the frequency axis
C2 ~Tref and yields temperature independent curves when TTS
holds. Therefore, any breakdown of TTS can easily be
and seen from the van Gurp–Palmen plot,15,16 which has
proved to be a very sensitive instrument for the detection
of thermorheological simplicity. Equivalent conclusions
have also been drawn by others, including Mavridis and
Shroff,17 who used the loss tangent tand instead of the
phase lag d itself. The Cole–Cole plot18 describes the
time dependent dynamic viscoelastic moduli by plotting
E0 versus E9. In the conventional Cole–Cole plot, E0 and
E9 are plotted on linear axes, while the modified Cole–
Cole plot uses logarithmic axes.19,20
The van Gurp–Palmen and Cole–Cole plots for the
test data in Figs. 3–5 are shown in Figs. 7 and 8
respectively. It can be seen from both plots that no data
manipulation is required to superimpose the isothermal
frequency sweep curves as a single curve. Thus, the two
plots provide positive evidence that CB filled rubber is
thermorheologically simple in the considered tempera-
ture range.

6 Experimentally determined temperature shift factor log Conclusions

aT versus temperature, fit to WLF equation and curve The dynamic mechanical properties of CB filled vul-
predicted by Arrhenius model canised natural rubber were investigated by temperature

Plastics, Rubber and Composites 2013 VOL 42 NO 10 419

Hu et al. Rheological behaviour of CB filled natural rubber
7 Van Gurp–Palmen plot of phase lag d versus absolute
value of complex modulus jE  j at various temperatures
sweep and isothermal frequency sweep tests, and the
frequency–temperature superposition principle was
applied to construct master curves from the isothermal
frequency sweep measurements at various temperatures.
It was shown that the filled rubber behaves in a
thermorheologically simple manner and that the master
curves characterise its dynamic mechanical behaviour
over a frequency range of 21 decades. This thermo-
rheological simplicity of the material was also confirmed
by the van Gurp–Palmen and Cole–Cole plots.
Furthermore, the shift factors used to construct the
master curves for the storage modulus, loss modulus and
loss tangent were shown to satisfy both the William–
Landel–Ferry equation and the Arrhenius relationship.
Acknowledgements
This work was supported by the NSFC (grant
no. 11172256), the Hunan Provincial Science and
Technology Programme (grant no. 2012FJ4061), the
Hunan Provincial Innovation Foundation for
Postgraduates (grant no. CX2012B258) and the Aid
Programme for Science and Technology Innovative
Research Teams in Higher Educational Institutions of
Hunan Province, China.
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