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Effect of vulcanization temperature on curing characteristic, physical and mechanical

properties of natural rubber/palygorskite composites

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2017 IOP Conf. Ser.: Mater. Sci. Eng. 223 012017

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
1234567890

Effect of vulcanization temperature on curing characteristic, physical and

mechanical properties of natural rubber/palygorskite composites

K C Lee1, N A Md Yusoff 1, N Othman 1, 2, N A Mohamad Aini1

1
Polymer Engineering Program, School of Materials and Mineral Resources
Engneering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong
Tebal, Penang, Malaysia.
2
Cluster of Polymer Composite, Science Engineering Research Centre,
Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal,
Penang, Malaysia

Email : srnadras@usm.my

Abstract. This paper aims to determine the optimum vulcanization temperature on curing
characteristic, mechanical and physical properties of natural rubber/palygorskite composites.
Three variations of vulcanization temperature (140, 150 and 160°C) were conducted on the
samples. Cation-exchanged method used to treat the palygorskite. Rheological measurements
and mechanical testing (tear, tensile and fatique life) were conducted on the composites
sample. Scanning electron microscopy (SEM) was used to reveal the dispersion of palygorskite
in NR matrix. It was found that the scorch and cure time of NR/Palygorskite decrease with
increasing of vulcanization temperature. The tensile strength and fatigue life was optimum at
140°C and slightly decreased with the increasing of vulcanization temperature. The SEM
micrograph revealed the strength and weakness in the system. It can be concluded that the
optimum properties of NR/Palygorskite composites were at 140°C of vulcanization
temperature and most of the mechanical and physical properties were slightly decreased with
the increasing of vulcanization temperature.

1. Introduction
Natural rubber (NR) is a unique biomass extracted from a tropical plant (cis-1,4-polyisoprene)
and composed of carbon and hydrogen atoms only. The natural property, renewability which making it
carbon neural, environmental friendly and biodegradable, has boost its demand around the world [1].
Nowadays, usage of natural rubber alone in rubber product manufacturing is not practical and
economic anymore. Hence, the introduction of filler into the rubber compound has increased its
mechanical properties while reducing manufacturing cost. One of the earliest and common nanofiller
is carbon black that is relatively inert and stable materials [2]. However, with its current high price and
its adverse effect toward environmental and human body, many researchers encouraged to find an
ecofriendly alternative carbon black. Clay is identified as one of a good alternative for carbon black
and many studies have been carried out to improve the performance of clay in a nanocomposite.
Structurally, clays have different size and mineralogy compared to other fine-grained soils, which is
the behavior, is more to plastic when contain water and become harder when dried it [3]. Palygorskite
is a clay mineral type and a crystalline hydrated magnesium aluminium silicate mineral with needle

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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shape result in unique colloidal properties and give high surface area and porosity particles when
thermally activated [4-5]. The hydrophilic behavior of the palygorskite is incompatible and has a poor
dispersion in the hydrophobic polymer phase [6]. Therefore, the idea is the organoclay surface need to
undergo treatment such as cation exchange surfactant to improve the rubber-filler interaction when the
polarity of pure natural clay is modifed [7]. Zheng et al., (2004) [8] use trimethyloctadecylamine as
cation exchange agent to treat the organoclay and compound it with the rubber matrix at 175°C while
Rath et al., (2012) [9], use palygorskite as filler and compared the properties of the treated and
untreated nanocomposites at 120°C.
In the present study, the curing characteristic, physical and mechanical properties of the cation
treated palygorskite of the natural rubber composite were investigated under different vulcanization
temperature (140, 150 and 160°C). The properties of the NR/cation treated palygorskite composites
were analyzed and compared with NR/untreated palygorskite composites. Then, the dispersion of the
fillers in the rubber matrix was characterized using Field Emission Scanning Electron Microscopy
(FESEM) and performed on the fracture surface of the composite.

2. Experimental
2.1. Material
Natural rubber SMR 20 (cis-polyisoprene- the glass transition is -70°C and density of 0.91 g/mL at
room temperature), High Ammonia (HA) latex (60% total solid content and specific gravity is 0.95-
0.96), zinc oxide, stearic acid, tetramethylthiuram disulphide (TMTD), zinc diethyldithiocarbamate
(ZDEC) and sulphur was kindly provided by Zarm & Chemical Supplier Sdn Bhd. While antioxidant,
anchoid, octdecylamine, potassium hydroxide (KOH) and calcium chloride was supplied by Sigma
Aldrich (M) Sdn Bhd and used as received.

2.2. Methodology
2.2.1. Preparation of Palygorskite Clay.
20 g of clay was added into the 1000mL hot water (80°C) and stirred for 1h (300rpm). Later, mixed
hot solution with mixture of 7.5 g of dedocyltriethylamine and 4.2 mL HCl in 500 mL of water and
stirred at rpm 400 for another 1 h (80°C). The precipitate filtered and washed with hot distilled water
until reached pH7 and dried at 60°C for 36 h before used. After that, the 6 pphr palygorskite clay was
mixed with 3 pphr 10% KOH, 5 pphr anchoid and water and stirred for 2 h. Ball mill technique was
applied to the dispersion mixture for 2 days to produce aqueous suspension.

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IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
1234567890

2.2.2. Preparation of Master Batch.

200g of natural rubber latex was heated until it reached about 45 to 50°C and poured into the warm
latex 20 g of modified palygorskite clay by cation ions exchanged and continuously stirred for
15minutes at 60°C. Then, 10% of CaCl solution was used to co-coagulate the latex compound and
washed with excess distilled water until it reached pH 7. The coagulated latex was cut into small
pieces and dried in an oven at 100°C for 2 h.

2.2.3. Mixing and Rubber Compounding

Two rubber compounds with different type of filler in the same amount of loading (6pphr) were
prepared in semi efficient vulcanization (SEV) system based on summarized formulation (Table 1).
After mixing, the compounds undergone compression moulding in order to produce sheet and button
form of sample for testing with three different vulcanization temperatures.

Table 1. Formulation of rubber compounding

Ingredients Pphr
Gum compound Untreated Palygorskite Treated Palygorskite
Compound Compound
NR rubber 100 100 100
Stearic acid 2 2 2
ZnO 5 5 5
ZDEC 0.5 0.5 0.5
TMTD 1.5 1.5 1.5
Antioxidant 2 2 2
Sulphur 1.5 1.5 1.5
Palygorskite - 6 6

2.2.4. Characterization
Curing characteristics of the rubber compounds were carried out using Monsanto rheometer (140, 150
and 160°C) for 30 min at 25 dNm range of the torque. Tensile test was carried out according to ASTM
D412 while tear followed ASTM D624. Fatigue life test was carried out using a Monsanto fatigue to
failure tester (FTFT) with dumbbell samples BS type E subjected to cyclic strain 100rpm. The fatigue
life was calculated using Japanese Industrial Standard (JIS) average. Hardness test was performed
according to ASTM D2240 at room temperature. Swelling test was performed by soaking the sample
(30 x 5 x 2mm) in toluene until equilibrium for 72 h at room temperature. The rubber filler interaction,
Qf/Qg was calculated using Lorenz and Parks equation [10]. Compression set test is measured the
differences of original thickness and thickness after recovery expressed in percentage. FE-SEM was
carried out using Zeiss Supra 35V SEM instrument. The samples from the surfaces of tensile testing
were coated with a thin layer of gold palladium using a SEM sputter coater to prevent the occurrence
of superfluous.

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IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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3. Result and Discussion

3.1. Curing Characteristic
The curing characteristics of unfilled and filled compound with untreated palygorskite and cation
treated palygorskite obtained from rheometer graph are presented in Table 2. The results show the
different cure characteristics due to different type of filler added into rubber composites.

Table 2. Cure characteristics of different composites at different vulcanization temperature

Compound Temperature ML (dNm) MH (dNm) ts2 (min) t90 (min) Cure Index
(°C) (min-1)
Unfilled 140 0.14 6.32 3.75 7.14 29.5
150 0.15 6.03 2.04 4.43 41.84
160 0.11 5.65 1.28 1.99 140.85
Untreated 140 0.30 5.47 4.38 7.40 33.11
palygorskite 150 0.22 5.21 2.40 3.59 84.03
160 0.21 4.89 1.45 2.02 175.44
Cation 140 0.27 5.53 2.40 3.81 70.92
Treated 150 0.25 5.34 1.50 2.17 149.25
palygorskite 160 0.23 5.11 1.06 1.51 222.22

Higher value of minimum torque (ML) at temperature 140°C for all three compounds was recorded
and decreasing with increasing of vulcanization temperature. Theoretically, when curing temperature
arise, molecular chain has a tendency to absorbed the heat energy which produced during preheat stage
and allowed the molecules to have higher mobility which led to lowering the rubber viscosity. Apart
from that, the surface treatment also affected the minimum torque, ML of rubber compound due to the
present of hydroxyl group on the surface of untreated palygorskite tends to form agglomeration and
led to increase in ML of the compound [11]. The value maximum torque (MH) of cation treated
palygorskite/NR composites is higher compared to palygorskite/NR composites due to the formation
of hydrogen bonding between amino group in the cation exchange agent (octadecylamine) and
hydroxyl groups in the organoclay [12]. The presence of treated palygorskite reduced the scorch time
and cure time (t90) which accelerated the vulcanization prosess. This phenomenon is due to the cation
exchange treatment which improve the compatibility of rubber-filler interaction by reduced silanol
groups of palygorskite and able to homogenously distributed in the rubber matrix that leads the
formation of crosslinking also increase the rate of vulcanization. In contrast, untreated palygorskite is
incompatible with rubber matrices and have a high tendency to agglomerate, hence increase the scorch
time when more torque needed to shear the agglomeration of filler in the matrix. The surface of
hydrogen bond that absorbed basic accelerators and deactivate them is resulting in reducing rate of
vulcanization process [13]. Cation treated palygorskite has the highest cure rate index at increased
trend for 140, 150 and 160°C respectively and higher compare to the untreated palygorskite

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
1234567890

composite. Hence from the viewpoint of cure rate index, it has obeyed the theory like aforementioned
in cure time. Where the cation treated palygorskite has reduced silanol groups of palygorskite and
hence increases the rate of vulcanization, while for untreated palygorskite composites the acidic
hydroxyl, siloxane groups has absorbed the basic accelerators causing it to slow down the degree of
vulcanization. The low viscosity of the component tends to form a continuous phase [14].

3.2. Tensile Properties

Figure 1 shows tensile strength and elongation at break of unfilled NR, NR/untreated palygorskite and
NR/cation treated palygorskite composite at different vulcanization temperatures. The results show for
treated palygorskite composite a descreasing trend while for unfilled NR and untreated palygorskite
showed a quite same trend for 3 vulcanization temperatures. It can assume that, the high vulcanization
temperature has deteriorated the mechanical properties of the rubber composite. Besides that, overall
tensile strength of cation treated palygorskite is higher than untreated palygorskite rubber composite.
This is because of the surface treatment was enhance the mechanical properties of the rubber
composite by increase it compatibility and interfacial bonding with the rubber matrix at the same time
causing the elongation at break become limited . This treatment lower down the surface energy and
improves the wetting characteristic of the rubber matrix, and resulting in larger interlayer spacing.
Additionally, the cation can provide functional group that can initiate the polymerization of monomers
to improve the adhesion between the palygorskite and rubber matrix and the filler-rubber interaction
and its mechanical properties.

(a) (b)
Figure 1. The effect of unfilled NR, NR/Cation Treated and Untreated Palygorskite/NR composite at
different vulcanization temperature on (a) tensile strength (b) elongation at break.

The modulus showed higher value for treated palygorskite compared to untreated palygorskite in
increasing trend with increasing temperature. According to Olad (2011) [15], when added rigid filler
to the soft polymer matrix, it will carry the major ration of applied load to the polymer matrix under
stress condition, if the interfacial interaction between the filler and matrix is adequate [16]. The good

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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compatibility and the present of amine group on the surface of palygorskite has led to better
interaction of filler-matrix phase, resulting a higher stiffness. On the contrary untreated filler
composite will have high tendency to slippage since the compound just need to break the crosslinkage,
physical entanglement and matrix-matrix interaction compared to the treated palygorskite. The
modulus properties reduced might be due to deterioration of the rubber chains when increasing the
vulcanization temperature, resulting a phenomenon called chain scissoring.

(a) (b) (c)

Figure 2. Tensile modulus of rubber composites at different vulcanization temperature,

(a) Unfilled NR, (b)NR/ Cation Treated Palygorskite and (c) NR/untreated palygorskite

3.3. Tear Properties

Figure 3 shows the highest tear strength recorded at 150°C for NR/cation treated palygorskite. This
could be explained by the ability of the crosslinks and rubber chains to crystalline upon the applied of
tearing force which that turns the amorphous rubber into a semi crystalline material. This crystallite is
highly oriented and act like filler crosslinks. Furthermore, due to the local reinforcement of strain-
induced crystallites at highly strained crack tip, the crack growth resistance in natural rubber
increased, resulting higher tear strength [17].

Figure 3. Tear strength of unfilled NR, NR/cation treated palygorskite, and NR/palygorskite composites at
different vulcanization temperature

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
1234567890

Based on the result, unfilled NR shows the lowest tear strength at 140°C followed 150°C and
160°C respectively. It because of low resistance in the gum rubber that prevent the rubber from resist
the slippage that occurred due to the stress concentration compared to the composite filled with nano
filler which able to reinforce the compound and form a surrounding layer of immobilized polymer.

3.4. Fatigue Life Properties

Figure 4 illustrates that fatigue life increase from 140°C (92.39 kcycles) to 150°C (100.64 kcycles),
and decreased at temperature 160°C (86.17 kcycles). The decreasing of fatigue life properties from
150 to 160°C is due to the elevated temperature as stated by Gupta (2004) [18], where it was proven
that higher curing temperature is not only decreased the curing time but also decreased the properties
of the static strength and fatigue life. The fatigue to failure process involves initiation of microcracks
and propagation of microscales and naturally occurring flaws due to combination of factors such as
fillers, contaminants or void in the matrix, non-homogenous dispersed compound ingredients and
surface flaws [19-20]. Besides, the main reason that affects fatigue life properties is crosslink density,
which undergoes the reversion with increasing the vulcanization temperature. These crosslinks
comprise two general types, which are monosulphide and disulphide crosslinks, and polysulphide
crosslinks, which impart various properties to the rubber matrix. Polysulphide crosslink chain may
break at higher vulcanization temperature and formed monosulphide crosslink chain.

Figure 4. Fatigue life of Unfilled NR, NR/ untreated Palygorskite and NR/ Cation Treated Palygorskite
composite at different vulcanization temperature

Figure 5 shows the rubber-filler interaction, Qf/Qg values on different composites at different
vulcanization temperature. The higher values of the Qf/Qg, indicate the lower the rubber-filler
interaction.

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Innovation in Polymer Science and Technology 2016 (IPST 2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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Figure 5. Qf/Qg of NR/ untreated Palygorskite and NR/ Cation Treated Palygorskite composite at different
vulcanization temperature

The treated filler has better filler interaction than untreated filler composite due to the surface
modification that replaced by some quartenary ammonium compound with a long hydrophobic tail
enhances the compatibility between the filler and matrix. This method changes the behaviour of the
filler from hydrophilic filler to hydrophobic filler.

3.5. Hardness Properties

Figure 6 shows at 140°C, unfilled NR shows the highest hardness compared to NR/ cation treated
palygorskite and NR/ palygorskite, which reflects the lowest elongation at break 840% at the same
temperature. Such result indicates that, at 140°C, the rubber composites achieved an optimum curing
characteristic, where the results obtained was corresponded with one another. Besides temperature
140°C, cation treated palygorskite shows the highest hardness compared to the other two compounds.
This is due to lower surface energy and larger interlayer spacing of cation treated palygorskite, which
depends on presence of hydrophobic groups of surfactants, which enhanced the intercalate ability of
palygorskite while improving physical and mechanical properties [20]. Elevated cure temperature
produces a network with lower degree of crosslink density (thermal breakdown of monosulfide
crosslink) and an increase in the extent of sulfidic main chain modification cause a reduction in
modulus [21].

Figure 6. Hardness of unfilled NR, NR/ untreated palygorskite and NR/ cation treated palygorskite
composite at different vulcanization temperature.

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IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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3.6. Swelling Properties

Figure 7 shows the crosslink density of the compounds at different vulcanization temperature. The
crosslink density of the NR/ cation treated palygorskite composite samples was higher than NR/
palygorskite and unfilled NR composite at the same vulcanization temperature. This is because of
there are many crosslinks produced in the rubber matrix when rubber matrices are swelled in toluene.
The crosslink density showed a decreasing trend from 140 to 160°C. At vulcanization temperature of
140°C, highest values of crosslink density recorded which were 6.34 x 10-5 g/mol, 6.10 x 10-5 g/mol
and 6.88 x 10-5 g/mol of the crosslink density for unfilled NR, NR/ untreated palygorskite and cation
NR/ cation treated palygorskite composites respectively. Vulcanization temperature has significant
effect on crosslink structure. Optimum properties are obtained when curing is done at the lowest
possible temperature. However, to increase productivity, higher temperatures are frequently used.

Figure 7. Crosslink density of the unfilled NR, NR/ untreated Palygorskite and NR/ Cation Treated
Palygorskite composites at different vulcanization temperatures

3.7. Field Emission Scanning of Electron Microscope (FESEM)

Figure 8 shows the micrograph of tensile fracture surface of all three composite. Figure 8(a) shows
the image surface of natural rubber composite without filler. It clearly shows that the surface has a
small dot due to presence of additive like antioxidant, vulcanizing agent etc, which indicates that all
ingredients homogenously distributed in the rubber matrices. Furthermore, Figure 8(b) shows the
image of NR/palygorskite composite. The presence of needle shapes fillers shows homogenously
dispersed and adhered perfectly to the matrix. This might be due to the good processing parameter and
latex compounding method that allowed the palygorskite to reinforce the adjacent matrix and
enhanced physical and mechanical properties. In contrast, Figure 8(c) shows rougher surface of NR/
cation treated palygorskite composite compare to Figure 8(a) and (b). It obviously shows the
successfully effect of surface modification to improve the interaction with the presence of many tear
lines on the fracture surface. It was proven that the composite needed a high energy to break the chain
and it was designated the effect of better interaction between chains and has higher strength properties

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IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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[22]. Furthermore, the uniform tear lines in one direction presence on the NR/ cation treated
palygorskite composite shows that the modified palygorskite undergo isotropic failure.

(a) (b) (c)

Figure 8. FESEM micrograph at 500 X magnification of (a) unfilled NR, 5000 X magnification (b)NR/
untreated palygorskite composite and (c) NR/ cation treated palygorskite composite

4. Conclusion
The result of NR/ cation treated palygorskite composite cured at 140°C demonstrated the optimum
properties among others. These are corresponding with the expected outcome where the cation treated
palygorskite have enhanced the compatibility and homogeneity in the rubber matrix. The improvement
caused by the mobility of the rubber chains constrained. Furthermore, the investigation on morphology
of cation treated palygorskite give strong evident and positive impact of the cation treated palygorskite
to mechanical properties of rubber composite. Therefore, surface modification which using to
modified surface of palygorskite clay was enhanced the mechanical properties of the composites. This
method was improved filler – matrix interfacial interaction hence increases the mechanical properties.

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IOP Conf. Series: Materials Science and Engineering 223 (2017) 012017 doi:10.1088/1757-899X/223/1/012017
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