Polymer Testing 28 (2009) 812

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

Comparison of the mechanical properties at similar hardness level of

natural rubber lled with various reinforcing-llers
N. Rattanasom a, b, *, S. Prasertsri c, T. Ruangritnumchai c
a

Institute of Science and Technology for Research and Development, Mahidol University, Salaya, Nakhon Pathom 73170, Thailand
Centre for Rubber Research and Technology, Mahidol University, Salaya, Nakhon Pathom 73170, Thailand
c
Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 6 June 2008
Accepted 13 August 2008

Commercially, the alteration of a rubber formulation is usually made in such a way as to

keep the hardness of the rubber product constant. This is because a specic hardness of the
rubber product sets the limit to its practical applications. Therefore, in this paper, natural
rubber (NR) vulcanizates containing various llers were prepared to have the same
hardness level, and their mechanical properties were compared and related to the degree
of ller dispersion. The results show that higher amounts of carbon black (CB) and silica
are needed for CB- and silica-lled natural rubber vulcanizates to achieve the same
hardness value as a NR vulcanizate containing 6 phr of montmorillonite clay. At equal
loading of llers, clay-lled vulcanizate exhibits higher modulus, hardness, tensile strength
and compression set, but lower heat build-up resistance and crack growth resistance than
those of the vulcanizates containing conventional llers. For the vulcanizate having the
same hardness value, CB-lled vulcanizate gives the better overall mechanical properties
followed by the clay-lled and silica-lled vulcanizates, respectively. The explanation is
given as the better dispersion of carbon black, as can be seen in the SEM micrograph.
2008 Elsevier Ltd. All rights reserved.

Keywords:
Natural rubber
Silica
Carbon black
Clay
Mechanical properties
Filler dispersion

1. Introduction
Natural rubber (NR) exhibits outstanding properties
such as green strength and tensile strength because it can
crystallize spontaneously when it is strained. However,
some properties of natural rubber such as modulus, hardness and abrasion resistance need to be improved for some
specic applications. Carbon black and silica are the
conventional reinforcing-llers used to enhance the
mechanical properties of various rubbers. In general,
a carbon black-reinforced rubber exhibits higher modulus
than a silica-reinforced one. However, silica provides
a unique combination of tear strength, aging resistance and
adhesion properties [1].

In recent years, nanoclays have attracted much attention because of their ability to enhance the mechanical
properties of rubber vulcanizates [29]. The improvement
in properties can be achieved at remarkably low clay
content (less than 10 phr) if the clay silicate layers are able
to disperse into the polymer matrix at the nanoscale level
[7,8]. It has been reported that the incorporation of a small
amount of clay gives rise to a more rigid material, which is
reected in a marked increase of hardness and modulus.
The nanocomposites of natural rubber have been found to
give optimum tensile strength and tear strength when
containing 58 phr of organomodied montmorillonite [9].
Although, the effect of types of ller on the properties of
rubber vulcanizates has been extensively investigated at

* Corresponding author. Institute of Science and Technology for Research and Development, Mahidol University, Salaya, Nakhon Pathom 73170, Thailand.
Tel.: 66 81 4313039; fax: 66 2 4410511.
E-mail address: stnrt@mahidol.ac.th (N. Rattanasom).
0142-9418/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2008.08.004

N. Rattanasom et al. / Polymer Testing 28 (2009) 812

equal loading [911], it is also interesting to elucidate the

effect of types of ller on the mechanical properties of the
vulcanizates at the same hardness level. This is because
a specic hardness is required for numerous industrial
products. In this study, vulcanizates having the same
hardness were prepared by adjusting the amount of each
ller. Then, the mechanical properties of the vulcanizates
were determined. Also, the mechanical properties of
natural rubber vulcanizates lled with equal amounts of
carbon black, silica and montmorillonite clay (6 phr) were
compared. The degree of ller dispersion of all vulcanizates
was also examined and related to their properties.
2. Experimental
2.1. Preparation of rubber/clay composite
Concentrated natural rubber latex (60% dry rubber
content, high ammonia) and the clay (Na-montmorillonite), with a cationic exchange capacity of 119 meq/100 g
were used to prepare the rubber/clay composite. Concentrated NR latex was diluted with water to 30% dry rubber
content. The amount of clay used was calculated such that
the dried natural rubber would contain 6 phr of clay. The
clay suspension was prepared before mixing with NR latex.
The clay was added into the excess water (2 g per 100 ml of
water) and was stirred vigorously for 4 h in order to achieve
good dispersion of the silicate layers in the medium. Then,
the mixture of clay suspension and NR latex was stirred
gently for 30 min. Thereafter, the mixture was cast in
a stainless steel tray and left at room temperature for a day.
Finally, it was further dried in an oven at 50  C. The rubber/
clay obtained was further mixed with other ingredients to
prepare the rubber compound.
2.2. Preparation of NR compounds and NR vulcanizates
The compound formulations are given in Table 1. The
conventional llers used in this experiment were carbon
black (N330) and precipitated silica (Hisil-233). The samples
were designated as gum, C6, CB6, CB14, S6, S35. The letters
C, CB and S refer to clay, carbon black and silica, respectively. The number followed the letters indicates the amount
of ller in phr. The gum sample was prepared for comparing

Table 1
NR compound formulations
Ingredients

Gum

C6

CB6

CB14

S6

S35

NR
Clay
Carbon black (N330)
Silica (Hisil-233)
Zinc oxide
Stearic acid
CBSa
TMTDb
Sulfur
PEGc

100

5
2
1
0.1
2

100
6

5
2
1
0.1
2

100

5
2
1
0.1
2

100

14

5
2
1
0.1
2

100

6
5
2
1
0.1
2
2

100

35
5
2
1
0.1
2
2

a
b
c

N-Cyclohexyl-2-benzothiazolesulfenamide.
Tetramethylthiuram disulde.
Polyethylene glycol.

properties with those of the lled samples. All ingredients,

except the curatives, were mixed with rubber (or rubber/
clay) in a laboratory-size internal mixer at a set temperature
of 50  C with a rotor speed of 50 rpm and a ll factor of 0.7.
The total mixing time in the internal mixer was 5.5 min.
After discharging, the compound was mixed on a two rollmill for 1 min. Then, the curatives were added and further
mixed for 4 min. Finally, 10 end-roll passes were made
before sheeting off. The compounds were nally compression molded at 150  C. The cure time used for preparing the
NR vulcanizates was the time at which the rheometer torque
increased to 90% of the total torque change on the cure curve.
The mechanical properties, hardness, tensile strength, tear
strength, heat build-up resistance and crack growth resistance, were measured on vulcanizates, a) containing equal
amounts of conventional llers and montmorillonite clay
(6 phr), and b) containing different amounts of each ller
such as to give the same hardness level.
2.3. Mechanical property measurement
The hardness was measured using a Wallace Shore A
durometer, according to ISO 7619-1. Compression molded
sheets having a thickness of about 1.2 mm were used for
tear and tensile testing. Tear and tensile properties of the
specimens were measured following ISO 34-1 and ISO 37,
respectively. Crescent test pieces were used for determining the tear strength. The measurements were carried
out using an Instron Universal Tester (Model 4301) with
a crosshead speed of 500 mm/min and initial clamp separation of 65 mm. The values of tear and tensile properties
were the average of 45 specimens.
The heat build-up and crack growth resistance of the
vulcanizates were measured, in accordance with ISO 4666
and ISO 132 using Goodrich exometer and De Mattia type
machines, respectively. Dynamic compression set was
evaluated using the same specimens as for heat build-up
testing. The original height of the specimen was measured
prior to heat build-up testing and the specimen was left at
25  C for 1 h after the heat build-up test. Thereafter, its nal
height was measured and the compression set was calculated using the following equation.

Dynamic compression set%

Ho  Hf




Ho  100

where Ho original height (mm).

Hf nal height (mm).
The fracture surfaces of the vulcanizates were examined
using a scanning electron microscope (SEM, JEOL JSM6301) in order to view the degree of ller dispersion. The
samples were sputtered with gold before examination to
prevent charging on the surface.
3. Results and discussion
Hardness and 300% modulus of all vulcanizates are
illustrated in Figs. 1 and 2, respectively. As expected, the
gum gives the lowest hardness and modulus while hardness and modulus increase noticeably when 6 phr of clay is
added to the NR. At equal amounts of ller, the clay-lled
vulcanizate exhibits the highest stiffness, followed by

10

N. Rattanasom et al. / Polymer Testing 28 (2009) 812

35

Tensile strength (MPa)

Hardness (Shore A)

60

55

50

45

40

30
25
20
15
10
5
0

Gum

C6

CB6

CB14

S6

S35

Gum

C6

CB6

CB14

S6

S35

Fig. 1. Hardness of NR vulcanizates lled with various llers at various

contents.

Fig. 3. Tensile strength of NR vulcanizates lled with various llers at

various contents.

CB-lled and silica-lled, respectively. In addition, the

results show that 14 phr of CB or 35 phr of silica is required
for the vulcanizates to reach the same hardness level as the
vulcanizate containing 6 phr of clay. Compared to CB,
a higher amount of silica is needed in order to achieve the
same hardness level as the clay-lled vulcanizate. This is
thought to be due to the decrease in crosslink density when
high silica loading is used. In a previous study, crosslink
density of NR vulcanizates gradually decreases when silica
loading is more than 20 phr [12]. The explanation is given
as the adsorption of zinc complex on the silica surface, thus
lowering the sulfur vulcanization efciency.
Tensile strength of all vulcanizates is shown in Fig. 3. As
can be seen, clay-lled vulcanizate exhibits the highest
tensile strength while tensile strength of the other vulcanizates is not much different. Likewise, tensile strength of gum
and lled NR vulcanizates containing 50 phr of CB is shown to
be similar [13]. The strain induced crystallization is known to
be responsible for the high strength of gum NR vulcanizates.
Fig. 4 displays the tear strength of various NR vulcanizates. The gum exhibits the lowest tear strength while the
vulcanizates having equal amounts of llers give similar
tear strength. Although, it is established that spherical
particles can blunt the crack tip more effectively than the
plate-shaped ller having high aspect ratio particles [14],
such a small amount of CB and silica (6 phr) used in this
experiment may not be sufcient to effectively blunt the
tear tip. However, the tear strength of CB- and silica-lled
NR vulcanizates markedly increases when they were
prepared to have similar hardness to that of clay-lled

vulcanizate. At similar hardness level, CB-lled sample

exhibits similar tear strength to that of silica-lled
vulcanizate, but much higher than that of the clay-lled
vulcanizate. The higher amount of llers in CB- and
silica-lled vulcanizates may obstruct the tear path more
effectively than that for the clay-lled vulcanizate. It has
also been reported that if the clay platelets are aligned in
the perpendicular direction to the applied force, the stress
may be concentrated at the sharp edges of particles and
promote earlier failure compared to spherical llers [14].
Crack growth resistance, expressed as the length of
crack growth (lower length of crack growth indicates
higher crack growth resistance), is shown in Fig. 5. In this
experiment, the gum exhibits the highest crack growth
resistance. The explanation is given as its lower modulus
resulting in the lower stress concentration at its crack tip
[13,15]. For the vulcanizates having equal amounts of ller,
clay-lled vulcanizate shows the lowest crack growth
resistance followed by CB- and silica-lled vulcanizates,
respectively. It is apparent that these results correspond
well with their moduli. The highest modulus of C6 leads to
the highest stress concentration at its crack tip compared to
CB6 and S6. On the other hand, a decrease in crack growth
resistance is observed for S35 although its modulus is
similar to that of C6 and CB14. It is thought that the lower
crack growth resistance of S35 results from its poor silica
dispersion or lower ller-rubber interaction, which
overrides the effect of the modulus.
The fracture surfaces of NR vulcanizates lled with
various llers are illustrated in Fig. 6. As can be seen, the
180

Tear strength (N/mm)

300% Modulus (MPa)

0
Gum

C6

CB6

CB14

S6

S35

Fig. 2. 300% Modulus of NR vulcanizates lled with various llers at various

contents.

150
120
90
60
30
0

Gum

C6

CB6

CB14

S6

S35

Fig. 4. Tear strength of NR vulcanizates lled with various llers at various

contents.

Lenght of crack growth (mm)

N. Rattanasom et al. / Polymer Testing 28 (2009) 812

16

12

Gum

C6

CB6

CB14

S6

S35

Fig. 5. Crack growth resistance at 20 kilocycles of NR vulcanizates lled with

various llers at various contents.

11

dispersion of various llers in NR is not much different

when using 6 phr of ller. However, at the same hardness level, S35 has the poorest ller dispersion because
the aggregate of silica can be readily observed in
Fig. 6(e). It has been also shown in the previous study
that lled rubber vulcanizate having poor silica dispersion exhibits lower crack growth resistance despite its
lower modulus compared to other vulcanizates [12].
Dynamic compression set results for various NR vulcanizates are shown in Fig. 7. It is evident that compression
set is low for the gum. When a low loading of CB or silica
(6 phr) is added, the compression set is not signicantly
changed. Nevertheless, clay-lled vulcanizate gives somewhat higher compression set than that of CB- and silicalled vulcanizates when equal amounts of llers are used.
At the same hardness level, silica-lled vulcanizate (S35)

Fig. 6. SEM micrographs of NR vulcanizates lled with various llers at various contents; (a) C6, (b) CB6, (c) S6, (d) CB14 and (e) S35.

N. Rattanasom et al. / Polymer Testing 28 (2009) 812

12

10

Heat buildup (C)

Compression set (%)

12

4
3
2
1
0
Gum

C6

CB6

CB14

S6

S35

8
6
4
2
0

Gum

C6

CB6

CB14

S6

S35

Fig. 7. Dynamic compression set of NR vulcanizates lled with various llers

at various contents.

Fig. 8. Heat build-up of NR vulcanizates lled with various llers at various

contents.

shows the highest compression set when compared to that

of C6 and CB14. This is attributed to the poor ller-rubber
interaction or poor ller dispersion when the silica loading
is high. Another possible explanation is the decrease in
crosslink density when silica loading is high. This result
also agrees well with the previous study showing that the
dynamic compression set tends to increase when the silica
loading is more than 30 phr [12].
It can be seen in Fig. 8 that heat build-up of the vulcanizates containing a small amount of ller is not much
different from that of the gum. However, it should be noted
that the clay-lled sample shows slightly higher heat buildup than CB-lled and silica-lled vulcanizates when using
equal amounts of ller. When higher amounts of CB or silica
is added to prepare vulcanizates with similar hardness to
that of C6, CB-lled sample (CB14) exhibits the same heat
build-up value as that of C6, while heat build-up of silicalled sample (S35) increases considerably. The possible
explanation is also given as the combined effects of the
poor silica dispersion and lower crosslink density of silicalled sample when a high amount of silica is loaded. Heat
build-up of a vulcanizate is reported to increase with
decreasing crosslink density [13].

At the same hardness value, CB-lled vulcanizate gives the

better overall mechanical properties followed by the claylled and silica-lled vulcanizates, respectively. The poor
silica dispersion and lower crosslink density of silica-lled
vulcanizate (S35) are thought to be the causes of its poorer
properties compared to the other vulcanizates.

4. Conclusions
The results show that modulus, hardness and tear
strength of NR lled with conventional llers and clay are
superior to those of the gum. Hardness and modulus
increase noticeably when 6 phr of clay is added. At equal
loading of llers, clay-lled NR vulcanizate exhibits higher
modulus, hardness, tensile strength compression set but
lower heat build-up resistance and crack growth resistance
than those of NR vulcanizates containing conventional
llers. However, their tear strength is not much different.
Compared to CB, a higher amount of silica is needed to
achieve the same hardness as that of the clay-lled sample.

Acknowledgements
The authors gratefully acknowledge Mr. Woothichai
Thaicharoen for providing the clay/rubber composite used
in this experiment. Sincere appreciation is extended to staff
of National Metal and Materials Technology Center for
carrying out the SEM measurement.
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