Polymer Degradation and Stability 91 (2006) 1417e1423

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Review article

The physical properties of pressure sensitive rubber composites

M.H. El Eraki a, A.M.Y. El Lawindy a, H.H. Hassan b, W.E. Mahmoud a,*
a
Physics Department, Faculty of Science, Suez Canal University, Ismailia, Egypt
b
Physics Department, Faculty of Science, Cairo University, Giza, Egypt

Received 5 August 2005; received in revised form 11 October 2005; accepted 20 October 2005
Available online 1 December 2005

Abstract

Nitrile butadiene rubber, NBR, structural foam of different apparent densities was obtained by using different concentrations of foaming
agent, azodicarbonamide, ADC/K. The true stressestrain characteristics, in case of compression, of foamed samples after the application of
cyclic stressestrain were measured. The effect of the cyclic stressestrain on strain energy density of ADC/K foaming agent-filled NBR rubber
composites was studied. The mechanical parameters were found to depend on the foaming agent concentration and on the pre-cyclic fatigue
number. Results also indicated that the strain energy decreased with filler concentration.
The effects of the cyclic stressestrain on the conductivity of ADC/K foaming agent-filled NBR rubber composites were studied. The elec-
trical properties were found to depend on the foaming agent concentration, the strain amplitude and the number of stressestrain cycles of pre-
strain. This study was assisted by the currentevoltage characteristics which were measured under the effect of different compression ratios: 0%,
5%, 10%, 15%, 20%, 25% and 30%. The free current carrier mobility and the equilibrium concentration of charge carriers in the conduction
band were produced as functions of compressive strain. Results also indicate that there is a linear variation between pressure and conductivity for
all samples, which means that these samples can be used as a pressure sensor.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Foam; Hysteresis loss; Pre-strain; Pressure sensor

1. Introduction will certainly affect the structure of carbon black as well as

Most uses of rubber foam have been derived from the
desired combination of low density and some other physical
properties. The dependence of physical properties on some
parameters of polymeric materials is mainly empirical. On
the other hand, the articles reviewing foamed rubber physical
properties are few. In our previous work [1,2], the decrease of
both mechanical and electrical properties with foaming agent
concentration was correlated with the decrease of the volume
fraction of carbon black in the foamed rubber matrix. A linear
relationship between volume fraction of carbon black and
foaming agent concentration was found [1]. This result simpli-
fied the discussion of the mechanical properties in the light of
the continuum mechanics theory for compressible materials
[2]. The incorporation of gas cells inside rubber matrices
* Corresponding author. Tel.: þ20 101590167; fax: þ20 64381765.
E-mail address: w_e_mahmoud@yahoo.com (W.E. Mahmoud).
the cross-linking density in foamed rubber. The equilibrium
between retraction forces, which hold the rubber chains, and
the gas pressure experienced by a unit cross-sectional area
of the rubber matrix is responsible for such an effect. This
equilibrium is very sensitive to internal pressure exerted by
a suitable solvent or to an external pressure such as compres-
sion. The interest of the present work is to make a pressure
sensor made of conductive foamed rubber. Whenever such
materials are used as sensors, they are subjected to repeated
stressestrain cycles, and it becomes necessary to understand
how the electrical properties change with repeated mechanical
stressestrain cycles. In this work nitrile butadiene rubber,
NBR, is used because of its good electrical properties, due
to the polar CN group in its structure.
CN
(–CH2–CH CH–CH2)–(– CH2 –CH–)

0141-3910/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.10.009
1418 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423

Also fast extrusion furnace, FEF, carbon black with particle 8. ADC/K, as a foaming agent, was finally added and mixed
diameter 550 Å was used in this work because of its low for 8 min at different concentrations: 0, 2.5, 5 and 7.5 phr.
tendency to form aggregates in the rubber matrix in order to
minimize the relaxation time. Azodicarbonamide, ADC, was All these materials were supplied by Bayer Company
used as the blowing agent. Because of its high decomposition (USA).
temperature, the addition of a special accelerator, a melt salt, is The specimens were compression moulded into cylinders of
responsible for the decrease of the decomposition temperature. 1
104 m2 area and 0.01 m in height. The vulcanization was
conducted under a heated press (Karl Kolb, Germany) at
a pressure of P ¼ 0.40 MPa. Many trials were conducted to ob-
2. Experimental work
tain an optimum condition of temperature and time of vulca-
nization without the samples being collapsed. The optimum
Since the sample properties depend largely on the method
conditions of temperature and time were T ¼ 423 K and
of preparation i.e., the order of adding the materials and the
t ¼ 30 min, respectively. The vulcanized samples were shelf
time of mixing and processing, it is important that all samples
aged for 48 h before the test. The mixing time and vulcaniza-
should pass through the same procedure under the same cir-
tion conditions were fixed for all the samples. Brass electrodes
cumstance. Also the mastication conditions must be kept the
were attached to the parallel faces of the samples during vul-
same throughout mixing. This means that the size of rolls
canization. Material tester (Ametek, USA) was used in this
used, speed of revolution and ratio of revolution of the two
experiment. A digital force gauge (Hunter Spring ACCU
rolls of mill must be unchanged, where the variation of these
Force II, 0.01 N resolution, USA) of 50 N capacity was used
conditions causes variation in the viscosity.
to measure stress forces. In electrical measurements a digital
A two-roll mill (made in Egypt) of length, 0.3 m; radius,
electrometer (616 Kiethly, USA) and an RCL bridge (3531
0.15 m; speed of slow roll, 18 rpm; and gear ratio, 1.4 was
Z-Hitester, Hioki, Japan) were used.
used to prepare such composites at room temperature. Samples
of NBR compound were prepared according to the recipe shown
in Table 1. 3. Results and discussion
During the mixing process different ingredients were added
as follows: 3.1. True stressetrue strain characteristics

1. NBR was milled for 10 min after which stearic acid, used Fig. 1 represents the true stress vs. true strain characteristics
as a co-activator, was added and mixed for 5 min. measured at room temperature in the case of compression. It
2. Zinc oxide, used as an activator to enhance the action of was found that these curves are sensitive to the concentration
organic accelerators, was added and mixed for 7 min. of the foaming agent. It was also noticed that the stiffness of
3. FEF, carbon black, was added and mixed for 5 min. the samples decreases with increasing concentration of the
4. DOP, dioctyl phthalate oil, was added and mixed for foaming agent.
4 min. The modulus of elasticity, E, and strain energy density, W,
5. MBTS, dibenzthiazyl disulphide, as an ultra-accelerator, were determined, from the data of Fig. 1, and are presented in
was added and mixed for 3 min. Table 2.
6. PBN, phenyl-b-naphthyl amine, as an antioxidant, was From Table 2 it was found that G and W decrease monoton-
added and mixed for 3 min. ically; one may conclude that the increase of foaming agent
7. Sulphur, which acts as a vulcanizing agent, was added and concentration decreases the interfacial interaction between
mixed for 5 min. FEF carbon black and rubber matrix. This interaction would
decrease the effectiveness of the stress transfer from rubber
Table 1 and consequently decrease the work required to deform the
Ingredients of the investigated NBR rubber composites
Ingredients (phr)a Sample 4 N0 N2.5
N0 N2.5 N5 N7.5 N5 N7.5
3.5
NBR 100 100 100 100
True stress (MPa)

3
Stearic acid 2 2 2 2
2.5
Zinc oxide 5 5 5 5
FEF 70 70 70 70 2
DOPb 10 10 10 10
1.5
MBTSc 2 2 2 2
PBNd 1 1 1 1 1
Sulphur 2.5 2.5 2.5 2.5 0.5
ADC/K 0 2.5 5 7.5
0
a
Part per hundred parts of rubber by weight. 0 0.05 0.1 0.15 0.2 0.25 0.3
b
Dioctyl phthalate. True strain
c
MBTS is dibenzthiazyl disulphide.
d
PBN is phenyl-b-naphthyl amine, a possible carcinogenic compound. Fig. 1. The relation between true stress and true strain for all samples.
 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423 1419

Table 2 Table 3
The modulus of elasticity, G, and strain energy density, W, at different concen- The hysteresis loop area for first cycle for all samples
trations of foaming agent Sample Hysteresis loop
Sample E (MPa) W (MJ/m3) area (MJ/m3)
N0 5.5 8.0 N0 0.30
N2.5 3.6 6.2 N2.5 0.52
N5 2.6 5.6 N5 0.65
N7.5 2.0 4.2 N7.5 0.74

composites, in turn leading to a decrease in the modulus of

elasticity where the adhesion force between carbon black
and rubber decreases [1].
3.2. The effect of cyclic stressestrain on mechanical
properties
Fig. 2 represents the cyclic stressestrain curves, in the case
of compression, at room temperature (303 K) for all samples.
It was found that the hysteresis loop area increases with an in-
crease of foaming agent concentration. The values of hystere-
sis loop area for all samples for the first stressestrain cycle are
shown in Table 3.
From Table 3, it was found that samples with the highest
loading of foaming agent are the most sensitive towards
change in strain energy, hence exhibiting the highest hystere-
sis. This may be attributed to the loss of excess energy during
deformation in order to breakdown the existing carbon black
network. The higher hysteresis gives an indication of the
extent of energy loss, and hence the heat build-up during the
cyclic deformation [3].
In order to confirm such assumption, the Morrow energy
model [4] was examined. The model predicts the number of
fatigue cycles (Nf) in terms of plastic strain energy density
(Wp) as follows:
Nfm Wp ¼ C
where m is the fatigue exponent and C is the material ductility
coefficient. The Morrow energy model was found to fit well
the experimental data in Fig. 3, from which the fatigue expo-
nent is determined and is represented in Table 4.
Table 4 indicates that the fatigue exponent increases as the
foaming agent concentration increases. This means that as the
concentration of foaming agent increases, the energy required
to deform the carbon black network increases and in turn in-
creases the loss of energy during repeated stressestrain cycles.
Fig. 4 represents the relation between the modulus of elas-
ticity, E, as a function of the number of stressestrain cycles for
all samples. It was found that the modulus decreases as the
number of fatigue cycles increases up to a certain value; after
this the modulus becomes independent of the cyclic fatigue.
One can explain these phenomena in the following way: the
movement of the rubber chains affects the network structure of
carbon black. During compression two phenomena occur in
the system, breakdown of existing networks and reformation
of new networks. These two phenomena repeat themselves
during repeated stressestrain cycles. However, at low number
of cycles the breakdown process is more prominent compared
to the formation process. On the contrary at higher number
some carbon black rearrangements take place leading to the
formation of new networks. So at higher number of cycles
the formation and breakdown of carbon networks balance
each other, resulting in a marginal change in the modulus
against the number of repeated stressestrain cycles [5,6].
3.3. Effect of compressive strain on conductivity
Fig. 5 depicts the conductivity, s (U m)1, as a function of
ð1Þ compressive strain ratio. One notices that the effect of com-
pressive strain on the conductivity predominates up to z20%,
after that the conductivity becomes compression independent.
This may be attributed to the fact that two phenomena occur in
the system during compression: breakdown of the existing
conductive network and formation of a new one. At low com-
pression the breakdown process is more prominent compared
5.9 N0 N2.5

5.8 N5 N7.5
4 N0 N2.5

3.5
N5 N7.5 5.7
5.6
True stress (MPa)

3
5.5
Log W

2.5 5.4
2 5.3
1.5 5.2
5.1
1
5
0.5 4.9
0 0 0.5 1 1.5 2
0 0.05 0.1 0.15 0.2 0.25 0.3 Log N
True strain
Fig. 3. The relation between plastic strain energy and number of stressestrain
Fig. 2. The first cycle of stressestrain for all samples. cycles.
1420 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423

Table 4 1.6 N0 N2.5

The fitting parameter m for all samples 1.4 N5 N7.5
Sample m 1.2

σ (10-3 (Ω.m)-1)
N0 0.32 1
N2.5 0.54
0.8
N5 0.60
N7.5 0.74 0.6
0.4
0.2
to the formation process and the net result is a reduction in the 0
number of conductive networks. At higher compression, when 0 5 10 15 20 25 30 35 40
the strain is high, some carbon black rearrangements also take Compression strain amplitude (%)
place leading to the formation of new conductive networks. Fig. 5. The relation between measured conductivity and compression strain
Thus at high compression strain the formation and breakdown amplitude.
of conductive networks balance each other, resulting in mar-
ginal change in the conductivity against compression strain
amplitude [7]. where q is the trapping factor. Therefore, in the trap square law
To account for this behaviour at different compression region, the relation between J and V2 becomes
strain amplitudes, Fig. 6 shows the plot of the current, I, as
J ¼ 933o me V 2 =8qa2 ð4Þ
a function of the square of the applied voltage, V2. From the
figure it can be seen that, above 150 V, the behaviour is The free-carrier mobility, mo, can be calculated at different
non-linear, indicating space charge conduction. The current deformations using the experimental value of q, and the slope
density (J ) in the square law region is given by [8]: of (IeV2) plots, where q is the ratio between the current den-
sities at the beginning (I1) and at the end (I2) of the trap square
J ¼ 933o mo V 2 =8a2 ð2Þ law region. Also q is the ratio between the free electron con-
centrations, no, in the conduction band to the total electron
where mo is the free-carrier mobility, 3o the permittivity of density, no þ nt, nt being the density of trapped electron. Thus
free space, 3 the dielectric constant of the sample material,
measured at 1000 Hz, and a is the sample thickness. I1 =I2 ¼ q ¼ no =ðno þ nt Þ ð5Þ
The formation of space charge is due to the existence of
The equilibrium concentration of the charge carrier in the
some traps within those composites that can occur at particular
conduction band, no, can also be obtained using the relation
molecular sites and chain folds. When a trap level exists, the
ÿ

mobility is reduced by 1/q, and the effective electron drift no ¼ 33o q=qa2 Vtr ð6Þ
mobility, mo, in an insulator with traps is therefore
where q is the electron charge and Vtr is the voltage at which
me ¼ mo q ð3Þ the transition from the Ohmic to the square law regions takes
place. For one type of current carrier, the conductivity, s, is
given by
6 N0 N2.5
N5 N7.5
s ¼ qno mo ð7Þ

5 Table 5 presents the produced values of s (U m)1 and

sm (U m)1, where sm is the measured conductivity deter-
mined from the Ohmic region. A fair consistency between
4
measured and calculated conductivity is observed.
Figs. 7 and 8 depict the behaviour of mo (m2 V1 s1), and
E (MPa)

3 the calculated values of carrier concentration, no, at different

compression strain ratios. It is seen that no values are compres-
2 sion independent. It is interesting to note that only the varia-
tion of mo with compression is responsible for the observed
change in conductivity [9].
1

3.4. Effect of the number of stressestrain cycles

0 on resistivity
0 10 20 30 40 50 60
Number of cycles
Fig. 9 represents the variation of resistivity as a function of
Fig. 4. The relation between the modulus of elasticity and the number of the number of stressestrain cycles at fixed compression strain
stressestrain cycles. of about 15%.
 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423 1421

Table 5
3.5 0% 5% 10% 15% A comparison between measured and calculated conductivity at two different
(a) 20% 25% 30% compression strain amplitudes
3
Sample 3 ¼ 5% 3 ¼ 15%
2.5 s (U m)1 sm (U m)1 s (U m)1 sm (U m)1
N0 1.3
103 1.4
103 1.1
103 1.0
103
2
I (mA)

N2.5 8.1
104 8.3
104 9.1
104 9.2
104

N5 7.5
104 7.6
104 8.3
104 8.5
104
1.5
N7.5 6.1
104 6.5
104 7.0
104 7.0
104
1

0.5 For all samples the resistivity increases with the increase of
number of cycles, followed by a decrease, and attains a plateau
0 value. In fact maxima are observed in the plots of resistivity
0 2 4 6 8 10
vs. number of stressestrain cycles for all samples. However,
V2 (104V2)
the maximum is attained at fourth cycle for sample N0, whereas
3.5 it is observed at seventh cycle for sample N2.5, and for sam-
(b) 0% 5% 10% 15%
ples N5 and N7.5 it is observed at tenth cycle. The reason for
20% 25% 30%
3 this may be because during the initial stressestrain cycle the
breakdown of the conductive network becomes more predom-
2.5
inant for all the samples, and at higher number of stressestrain
2 cycles the rate of formation of conductive network becomes
I (mA)

faster and the formation and breakdown processes balance

1.5 each other, leading to a plateau in the plots of resistivity
1
against the number of stressestrain cycles [5].

0.5
3.5. Effect of pressure on conductivity
0
0 2 4 6 8 10 Fig. 10 depicts the conductivity as a function of time at
V2 (104V2) different values of applied pressure. The data of Fig. 10 can
be analysed with the aid of the equation given below [10,11]
3.5
(c) 0% 5% 10% 15%

3 20% 25% 30%

s ¼ gðt; T; fÞexpðVP=kTÞ ð8Þ
2.5
I (mA)

2 where P is the applied pressure, V the activation volume, and k

1.5 is the Boltzmann constant. The physical meaning of this
volume is associated with the region of the space where the
1
conduction event takes place; g is a function of the time t,
0.5 the temperature T, and the structure f.
0 An estimation of V can be obtained using the change in
0 2 4 6 8 10
s ¼ ds=dt when a pressure step is made over the sample at
V2 (104V2)

3.5 N0 N2.5
(d) 0% 5% 10% 15% 0.03
N5 N7.5
3 20% 25% 30%
0.025
2.5
µo (m2 V-1 s-1)

0.02
I (mA)

2
0.015
1.5

1 0.01

0.5 0.005

0 0
0 2 4 6 8 10 0 5 10 15 20 25 30 35 40
V2 (104V2) Compression strain amplitude (%)

Fig. 6. The IeV2 characteristic curves for samples (a) N0, (b) N2.5, (c) N5 and Fig. 7. The relation between free-carrier mobility and compression strain
(d) N7.5. amplitude.
1422 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423

N0 N2.5 1.8 N0 N2.5

P=0.2MPa
8 N5 N7.5 1.6 P=0.4MPa N5 N7.5
7 1.4 P=0.6MPa

σ (10-3 (Ω.m)-1)
P=0.8MPa
6 1.2
5 1
(m-3)

4 0.8
o

3 0.6
2 0.4

1 0.2
0
0
0 10 20 30 40 50 60 70
0 5 10 15 20 25 30 35 40
Time (min.)
Compression strain amplitude (%)

Fig. 8. The relation between number of free carriers and compression strain Fig. 10. The relation between measured conductivity and time at different val-
ues of applied pressures.
amplitude.

constant temperature and structure. Using Eq. (8), it is easy to

obtain
 
Table 6
d ln s =ðd ln PÞ ¼ P d ln s =dP ¼ PV=kT ð9Þ The activation volume for all samples under effect of pressure
Sample V (m3)
If an incremental step of pressure is made, a change in the
derivative of the conductivity can be measured. Then it has P ¼ 0.2 MPa P ¼ 0.4 MPa P ¼ 0.6 MPa
N0 1.9
1030 16.2
1030 260
1030

d ln s =ðd ln PÞzlnðs2 =s1 Þ=lnðP2 =P1 Þ
 
ð10Þ N2.5 23.4
1030 18.9
1030 8.3
1030
N5 35.0
1030 23.9
1030 12.7
1030
  N7.5 48.1
1030 29.5
1030 16.5
1030
where s2 and s1 are the derivatives before and after the change
in pressures P2 and P1, respectively. Table 6 represents the
activation volume for all samples under the effect of pressure.
From Table 6, it was found that as the foaming agent con-
centration increases the active volume increases causing a
decrease of the conductivity. It was also found that the active Table 7
volume varies with applied pressure. Hence, if a cubic unit is The space between carbon black aggregates for all samples under effect of
considered, a characteristic activation distance, a, is deter- pressure
mined and is presented in Table 7. Sample a (Å)
Following Table 7 one can notice that, for samples, N2.5, P ¼ 0.2 MPa P ¼ 0.4 MPa P ¼ 0.6 MPa
N5 and N7.5, as the pressure increased, the distance between
N0 1.2 2.5 6.4
carbon aggregates decreased. This indicates that the increase N2.5 7.6 7.0 6.6
in applied pressure leads to a decrease in hopping path and N5 9.0 8.8 7.3
N7.5 12.5 10.1 9.9

45 N0 N2.5
N5 N7.5
40

35

30
1.8
ρ (10 Ω.m)

N0 N2.5
25 1.6 N5 N7.5
3

1.4
20
σ (10-3 (Ω.m)-1)

1.2
15 1
10 0.8
0.6
5
0.4
0 0.2
0 10 20 30 40 50 60 0
Number of cycles 0 0.2 0.4 0.6 0.8 1
P (MPa)
Fig. 9. The relation between the measured resistivity and the number of
stressestrain cycles. Fig. 11. The relation between measured conductivity and applied pressure.
 M.H. El Eraki et al. / Polymer Degradation and Stability 91 (2006) 1417e1423
in turn leads to an increase in conductivity. For sample N0, as
the pressure increased the distance between carbon aggregates
increased. This indicates that the increase in applied pressure
leads to a desegregation of carbon black networks. This leads
to an increase in the hopping path and in turn leads to an
increase in resistivity.
Fig. 11 represents the relation between applied pressure and
measured conductivity for all samples. From the figure, it can
be found that these samples are linearly sensitive to the
applied pressures.
4. Conclusion
1. The modulus of elasticity, E, was found to be filler concen-
tration dependent. The effect of cyclic fatigue shows a
remarkable decrease of E until certain number after which
it has no effect.
2. Electrical conductivity depends on the amplitude of com-
pressive strain up to 20%, after that it becomes compres-
sion independent.
3. The carrier concentration in the conduction band was
found to be compression independent. The variation of
the free-carrier mobility was found to be sensitive to the
compressive strain amplitude up to 20%. Consequently,
the change in mobility is responsible for the change in
conductivity.
4. Electrical conductivity depends on the total number of
stressestrain cycles, where at low cycles the resistivity
1423
is increased due to rapid destruction of carbon black
networks, but at higher number of cycles the effect is
marginal because of the balance between destruction and
reformation of carbon networks.
5. The effect of pressure on the samples shows a change in
the hopping path between carbon black aggregates that
causes an increase in conductivity (samples N2.5, N5
and N7.5) or an increase in resistivity (sample N0).
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