Polymer Testing 37 (2014) 156e162

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

Material properties

Study on the ageing characteristics of oil palm ash reinforced

natural rubber composites by introducing a liquid epoxidized
natural rubber coating technique
Zhong Xian Ooi, Hanafi Ismail*, Azhar Abu Bakar
Division of Polymer Engineering, School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia,
Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Oil Palm Ash (OPA), coated with a Liquid Epoxidized Natural Rubber (LENR), was prepared
Received 2 April 2014 prior to compounding with natural rubber and other curing ingredients, using a laboratory
Accepted 12 May 2014 two-roll mill. Owing to better interfacial adhesion between the LENR coating layer and the
Available online 21 May 2014
OPA particles, the tensile strength and elongation at break of the LENR-coated OPA showed
higher retention than non-coated OPA filled natural rubber composites after being sub-
Keywords:
jected to thermal ageing at 100
C for two days. Thermogravimetric Analysis (TGA) indi-
Oil palm ash
cated that the thermal stability of LENR-coated OPA filled natural rubber composites was
Liquid epoxidized natural rubber
Natural rubber
higher than that of non-coated OPA filled natural rubber composites. However, this phe-
Ageing nomenon only occurred from ambient temperature up to the temperature at which the
Thermogravimetric analysis LENR coating phase started to decompose.
© 2014 Published by Elsevier Ltd.

1. Introduction According to our previous work [2,3], the utilization of

The utilization of by-products or waste in rubber com-
posites to reduce the compounding cost, and/or alter the
appearance and properties of rubber products, has gained
the attention of many rubber technologists. Malaysia's oil
palm industry has grown phenomenally over the past few
decades and is currently one of the world's largest pro-
ducers and exporters of palm oil commodities [1]. Despite
its benefits, the oil palm industry also creates severe
disposal problems, where industrial by-products, such as
oil palm trunks/fronds, empty fruit bunches, etc., are sent
to landfill sites. The current oil palm processing industry
utilizes oil palm biomass, combusted at high temperatures,
as alternative cheap fuel to generate electricity. However,
such efforts generate another by-product, known as Oil
Palm Ash (OPA), which has no commercial value; as yet.
* Corresponding author. Tel.: þ604 5996113; fax: þ604 5941011.
E-mail addresses: ihanafi@usm.my, profhanafi@gmail.com (H. Ismail).
OPA has been shown to increase the tensile properties of
natural rubber composites. Moreover, the optimum tensile
strength of OPA filled natural rubber composites could be
further enhanced to 5.6%, by applying a surface treatment
of Liquid Epoxidized Natural Rubber (LENR) coated onto the
OPA particles, prior to compounding with natural rubber.
This process is also beneficial for heat and oxidative sta-
bility improvement. However, the actual thermal proper-
ties and ageing characteristics of LENR-coated OPA filled NR
composites are still unknown.
Epoxidized Natural Rubber (ENR) is formed as a chem-
ically modified natural rubber through a reaction of natural
rubber with peroxycarboxylic acid to attach the new
chemical functional group to, known as an epoxide group,
within isoprene units [4]. Theoretically, the existence of
epoxide groups in ENR exhibits better thermal resistance
than natural rubber, as reported by Pongtanayut et al. [5];
where the degradation onset temperatures for ENR and NR
are 358
C and 331
C, respectively. The LENR, which was

http://dx.doi.org/10.1016/j.polymertesting.2014.05.003
0142-9418/© 2014 Published by Elsevier Ltd.
 Z.X. Ooi et al. / Polymer Testing 37 (2014) 156e162
used as a surface coating on the OPA particles in this study,
might affect the thermal properties of OPA filled natural
rubber composites.
The objective of this article is to extend our research
work in order to assess ageing resistance, as well as the
morphology, of natural rubber composites filled with OPA
after LENR surface coating was applied, compared to non-
coated OPA filled NR composites. Furthermore, the ther-
mal stability of LENR-coated OPA and non-coated OPA filled
natural rubber composites was also analysed using Ther-
mogravimetric Analysis (TGA).
2. Experimental
2.1. Materials
SMR L grade natural rubber, which was purchased from
Zarm Scientific & Supplies (M) Sdn. Bhd., was used as the
matrix. The Oil Palm Ash (OPA) filler was collected from
United Oil Palm Mill, Penang, Malaysia. Prior to ENR
coating, raw OPA particles were sieved to a 75 mm mesh
size and dried in a vacuum oven at 80
C for 24 hours to
expel moisture. Other curing ingredients, including zinc
oxide, stearic acid, N-Isopropyl-N0 -phenyl-p-phenylenedi-
amine (IPPD), N-cyclohexyl-2-benzothiazole sulfenamide
(CBS) and sulphur, were provided by Bayer (M) Ltd., and
used as received.
2.2. ENR coating
10% wt/v ENR solution (LENR) was prepared by stirring
the ENR-50 (supplied by Zarm Scientific & Supplies (M)
Sdn. Bhd.) in toluene (purchased from Sigma Aldrich (M)
Sdn. Bhd.) until the ENR-50 was fully dissolved. The OPA
particles were mixed and stirred using a mechanical stirrer
for one hour at room temperature, and then transferred to
an Elma ultrasonic vibrator (model Transsonic Digital S) for
another 30 minutes, to ensure that all OPA particles were
optimally coated by ENR. The LENR-coated OPA was filtered
and dried in an oven at 60
C until constant weight was
obtained.
2.3. Preparation of OPA filled NR composites
The OPA loadings used were 0.5, 1, 3, 7, and 9 phr. The
detailed formulation used is shown in Table 1. Mixing of
raw materials was done using a conventional laboratory
Table 1
Formulation of Oil Palm Ash (OPA) filled natural rubber
composites.
Material Compound (phra)
NR (SMR L) 100
Zinc oxide 1.5
Stearic acid 1.5
IPPD 2.0
CBS 1.9
Sulphur 1.6
b
OPA 0, 0.5, 1, 3, 7, 9
a
Parts per hundred parts of rubber.
b
Same phr loading for raw OPA and LOPA-coated OPA.
157
sized two-roll mill (model XK 160). A total mixing time of
about 20 minutes was chosen to avoid premature
vulcanisation of excess heat generated during com-
pounding. Mixing sequences were kept constant for all
mixes. Curing characteristics, such as scorch time (ts2),
cure time (tc90) and maximum torque (MH) of OPA filled
NR composites, were determined using a Monsanto
Moving Die Rheometer (model MDR 2000) according to
ISO 3417 at 150
C, followed by compression moulding at
150
C; according to their respective tc90 values. The
moulded sheets were conditioned in desiccators for
24 hours prior to further testing. The LENR-coated OPA
was designated as LOPA and compounded in the same
manner as non-coated OPA filled natural rubber com-
posites (control).
2.4. Retention properties under ageing condition
For the tensile tests, dumbbell shaped specimens were
cut from a moulded sheet with a thickness of about 2 mm.
In order to evaluate property retention of non-coated OPA
and LENR-coated OPA filled NR composites after ageing,
five dumbbell shaped specimens were placed in an oven
with an air-circulating system, at an operating temperature
of 100
C for 48 hours (according to ISO 188). The tensile
properties of both aged and unaged specimens were
determined in the same manner, and compared. Tensile
testing was conducted according to ISO 37 using a universal
tensile testing machine (model Instron 3366) with a
crosshead speed of 500 mm/min. Data for tensile strength,
elongation at break, and tensile modulus (M100 and M300)
was evaluated from stress-strain determinations and
average values for each compound were recorded. The
retained percentage values of tensile properties were
calculated according to Equation (1).
Valueaged
Retentionð%Þ ¼  100 (1)
Valueunaged
2.5. Fourier Transform Infra-Red (FT-IR) spectroscopy
FTIR was used to observe possible changes to the
chemical characteristics of both non-coated OPA and LENR-
coated OPA filled NR composites, before and after thermal
ageing. FTIR spectra were obtained and recorded using a
Perkins Elmer spectrometer (USA) in the range of 550 cm1
to 4000 cm1 at a resolution of 4 cm1. For each spectrum,
16 scans were co-added.
2.6. Scanning electron microscopy (SEM)
Tensile fractured surfaces of non-modified OPA and
CTAB-modified OPA filled NR vulcanisates were scanned
using a scanning electron microscope (FESEM: model Zeiss
Supra 35 VP). The fractured specimens were mounted on
aluminium stubs and sputter-coated with a thin layer of
gold-palladium in order to avoid electrostatic charge and
poor resolution during examination. The SEM images were
used to study the mode of fracture and support the changes
in ageing characteristics.
158 Z.X. Ooi et al. / Polymer Testing 37 (2014) 156e162

2.7. Thermogravimetric Analysis (TGA)

In order to evaluate the thermal stability of non-

modified OPA and CTAB-modified OPA filled NR compos-
ites, Thermogravimetric Analysis (TGA) was performed
using a Perkins Elmer Pyris 6 thermogravimetric analyser. A
small amount (~10 mg) of specimen was taken for the
analysis. Weight loss was measured as a function of tem-
perature, whereby the sample was heated from 30
C to
600
C, at a heating rate of 10
C/min in a nitrogen atmo-
sphere. The TGA curve was recorded in order to study the
thermal stability of the OPA filled NR composites.

3. Results and discussion

Fig. 1. FT-IR spectra of 7 phr OPA filled natural rubber composites (a) before,
3.1. Tensile retention and (b) after thermal ageing.

Table 2 shows the tensile properties of non-coated OPA

and LENR-coated OPA filled natural rubber composites, Meanwhile, the peak at 1598 cm1 corresponded to the
before and after thermal ageing at 100
C for two days. The C]C bond [2,8]. However, those peaks were clearly
coating layer of LENR on the OPA particles led to better attenuated after being subjected to thermal ageing in both
adhesion in the natural rubber matrix, resulting in OPA filled and LENR-coated OPA filled natural rubber
improvement of both tensile strength and elongation at composites. The reduction of both peaks proved that the
break before thermal ageing. After being subjected to degradation of natural rubber occurred after thermal
thermal ageing, the tensile strength and elongation at ageing, where scissoring of main chain as well as sulphide
break of LENR-coated OPA filled natural rubber composites
still exhibited a higher value, while tensile modulus
showed a lower value than non-coated OPA filled natural
rubber composites. The higher values of tensile strength
and elongation at break for LENR-coated OPA filled natural
rubber composites over non-coated OPA filled natural
rubber composites provide clear evidence of the benefit of
the LENR coating method; where not only did it improve
the tensile strength and elongation at break before thermal
ageing, but also after thermal ageing.
The degradation of non-coated OPA and LENR-coated
OPA filled natural rubber composites was further proved
by the Fourier Transform Infra Red (FT-IR) analysis (as
shown in Figs. 1 and 2). The most prominent changes of
FT-IR peaks are highlighted with an eclipse in both figures.
According to previous work by Ooi et al. [6] and Murgic
and Jelencic [7], the peak at around 1539 cm1 was
attributed to the SeSeC]N bond, which resulted from the Fig. 2. FT-IR spectra of 7 phr LENR-coated OPA filled natural rubber com-
vulcanization reaction of CBS accelerator and sulphur. posites (a) before, and (b) after thermal ageing.

Table 2
Retained tensile properties of non-coated OPA and LENR-coated OPA filled natural rubber composites after thermal ageing at 100
C for two days.

Sample code Before ageing After ageing

a a a
Tensile strength (MPa) Elongation at break (%) M100 (MPa) Tensile strength (MPa) Elongation at break (%) M100 (MPa)

Gum NR 21.8 1049 0.656 2.1 (9.6) 231 (22) 0.941 (143)
NR/OPA0.5 21.9 1054 0.676 2.2 (10.0) 248 (24) 1.010 (149)
NR/OPA1 25.2 1127 0.690 2.6 (10.3) 283 (25) 1.029 (149)
NR/OPA3 23.9 1114 0.703 2.4 (10.0) 274 (25) 1.129 (161)
NR/OPA7 23.2 1086 0.746 2.9 (12.5) 293 (27) 1.182 (158)
NR/OPA9 23.1 1069 0.761 2.7 (11.7) 251 (23) 1.237 (163)
NR/LOPA0.5 24.5 1089 0.65 2.4 (9.7) 238 (22) 0.975 (150)
NR/LOPA1 26.6 1145 0.66 2.7 (10.0) 285 (25) 1.003 (152)
NR/LOPA3 25.1 1123 0.66 2.7 (10.8) 293 (26) 1.014 (153)
NR/LOPA7 24.7 1107 0.69 3.5 (14.1) 350 (32) 1.059 (155)
NR/LOPA9 23.4 1097 0.70 3.7 (16.0) 410 (37) 1.084 (156)
a
The retention percentages after thermal ageing are indicated in brackets.
 Z.X. Ooi et al. / Polymer Testing 37 (2014) 156e162 159

Fig. 3. SEM images of (a) 0.5 phr non-coated OPA, and (b) 0.5 phr LENR-coated OPA filled natural rubber composites before thermal ageing.

crosslinks occurred when exposed to a higher thermal
condition. According to literature reported by Gelling [9],
the semi-Efficient Vulcanization (semi-EV) and Efficient
Vulcanization (EV) systems of gum ENR have comparable
tensile retention to that of gum natural rubber when
exposed to thermal ageing conditions. This indicates that
ENR and NR would exhibit similar chemical structure
changes and their properties would change in the same
manner after ageing.
Therefore, the FT-IR spectra of LENR-coated OPA filled
natural rubber composites clearly show no significant
changes compared to the non-coated OPA filled natural
rubber composites. However, based on the retention per-
centages after thermal ageing (which are summarized in
brackets in Table 2), the formation of the LENR coating layer
onto the OPA particles played a significant role in contrib-
uting to better retention values of LENR-coated OPA filled
natural rubber composites in thermal ageing conditions. As
described in previous work [3], the coating of LENR onto
OPA particles improved interfacial adhesion by forming
bridging rubber within OPA surface's porous and the nat-
ural rubber matrix. Consequently, the stress was efficiently
transferred from the natural rubber matrix when an
external force was applied to it. This led to a higher retained
tensile strength and elongation at break; even after un-
dergoing a severe thermal ageing process.
As anticipated, the trend for tensile modulus was the
reverse of the tensile strength and elongation at break. The
tensile modulus shifted to a higher value, whereby the
retention percentage was more than 100%, regardless of the
OPA filled natural rubber composites used or gum natural
rubber composites, since the degradation process only
affected the rubber portion [10]. The tensile modulus
typically increased as a result of macroradicals forming in
the rubber composites, thus leading to hardening and
increased brittleness [11,12]. The retention of tensile
modulus for LENR-coated OPA filled natural rubber com-
posites was lower than that of non-coated OPA composite.
This result could be related to the higher retention of
elongation at break.
3.2. Morphological studies
Figs. 3e6 portray the fractured surfaces of non-coated
OPA and LENR-coated OPA filled natural rubber compos-
ites at 0.5 phr and 7 phr loadings. Before thermal ageing,
the LENR-coated OPA was well-embedded (as enlarged in
white circles) in the natural matrix when compared to the

Fig. 4. SEM images of (a) 0.5 phr non-coated OPA, and (b) 0.5 phr LENR-coated OPA filled natural rubber composites after thermal ageing at 100
C for two days.
160 Z.X. Ooi et al. / Polymer Testing 37 (2014) 156e162

Fig. 5. SEM images of (a) 7.0 phr non-coated OPA, and (b) 7.0 phr LENR-coated OPA filled natural rubber composites before thermal ageing. Adapted from
previous work (Ooi et al., 2014).

non-coated OPA ones (as shown in Figs. 3 and 5). Even after
being subjected to thermal ageing at 100
C for two days,
the LENR-coated OPA was still well-embedded in the nat-
ural rubber matrix and the rubber bridging was observable
after the tensile test (as highlighted with white circles in
Figs. 4b and 6b). In the case of non-coated OPA filled natural
rubber composites, the fractured surface showed more
holes and the fractured zone tended to be smooth (as
shown in Fig. 4a). This observation explains why the tensile
strength of LENR-coated OPA filled natural rubber com-
posites was higher than that of the non-coated OPA ones.
These micrographs support the tensile properties obtained,
which offer higher retention of tensile strength and elon-
gation at break for LENR-coated OPA filled natural rubber
composites, due to efficient stress transfer when an
external force was applied to it. Therefore, LENR-coated
OPA filled natural rubber composites require more energy
to fracture.
3.3. Thermogravimetric analysis
Fig. 7 presents the TGA and DTG curves of non-coated
OPA and LENR-coated OPA filled natural rubber compos-
ites. The detailed variation of 5% weight loss (T5%), 10%
weight loss (T10%), 50% weight loss (T50%), temperature at
maximum weight loss rate (TmaxI) and char residue (%) are
summarized in Table 3. According to Fig. 7, the gum natural
rubber composites showed the highest weight loss of all
OPA filled natural rubber composites along the TGA curves.
This was mainly attributed to the OPA itself, which con-
tained inorganic constituents that are able to withstand
very high temperatures without weight change. As re-
ported earlier [13], the main mineral constituents in OPA
are quartz (silica) and calcite (calcium carbonate). In
conjunction with the findings reported by Lee [14], the use
of silica brought an improvement to the heat resistance for
most rubber matrixes (such as natural rubber, styrene
butadiene rubber, nitrile butadiene rubber, chloroprene
rubber, and etc.) Therefore, the thermal stability of natural
rubber composites was enhanced when the OPA loading
was increased.
In the case of LENR-coated OPA filled natural rubber
composites, there was more weight loss than for the cor-
responding natural rubber composites filled with non-
coated OPA (as depicted in Fig. 7). The results shown in
Table 3 also indicate that the temperatures at 5%, 10%, 50%
weight loss, even the temperature at maximum weight
loss, of LENR-coated OPA filled natural rubber composites,
were lower than those of non-coated OPA materials. This
lowering of thermal stability corresponded mainly to the

Fig. 6. SEM images of (a) 7.0 phr non-coated OPA, and (b) 7.0 phr LENR-coated OPA filled natural rubber composites after thermal ageing at 100
C for two days.
 Z.X. Ooi et al. / Polymer Testing 37 (2014) 156e162 161

Fig. 8. Thermal stability of the gum NR, non-coated OPA, and LENR-coated
OPA filled natural rubber composites at 7 phr, ranging from 95
C to 130
C.

filler and matrix would contribute to higher thermal sta-

Fig. 7. Thermal stability of the non-coated OPA and LENR-coated OPA filled
natural rubber composites.
bility by hindering the diffusion of volatile decomposition
products. However, this phenomenon was only applicable
before the decomposition of the LENR coating layer. Once
the decomposition of natural rubber, as well as the LENR
had started, the LENR-coated OPA filled natural rubber
composites became less thermally stable; as the diffusion
rate of the volatile decomposition increased.

decomposition of the LENR coating layer, which was 4. Conclusions

derived from an organic substance. As previously
mentioned, the ratio of organic phase volume to inorganic Based on the ageing tests, it can be concluded that the
filler increased when LENR-coated OPA was added. addition of LENR-coated OPA could provide better ageing
Furthermore, the thermal decomposition of organic sub- resistance to natural rubber composites by showing higher
stance was mainly in the range 200
C to 500
C [15], whilst retention of tensile strength and elongation at break values
the inorganic substances are very stable in that tempera- than that of non-coated OPA ones. This was further proved
ture range. This explanation was proven by the percentage by the fractured surface of non-coated OPA and LENR-
of char residue (as summarized in Table 3), where the char coated OPA filled natural rubber composites. However,
residue for LENR-coated OPA filled natural rubber com- the FT-IR spectra of LENR-coated OPA filled natural rubber
posites showed a lower percentage than that of the non- composites did not show any significant difference over
coated ones. non-coated OPA ones. TGA showed that the LENR-coated
However, for the temperature range 95
C to 130
C, the OPA filled natural rubber composites possessed a higher
LENR-coated OPA filled natural rubber composites exhibi- thermal stability than non-coated OPA filled natural rubber
ted higher thermal stability, where the weight loss within composites. However, this phenomenon was only appli-
this temperature range was less than that of non-coated cable up to the temperature where the organic phase
OPA filled natural rubber composites (as shown in Fig. 8). started to decompose.
This interesting finding means the higher thermal stability
possessed by the LENR-coated OPA filled natural rubber
composites was due to better interfacial adhesion between Acknowledgement
OPA and the LENR coating layer. Abdolmohammadi et al.
[16] also reported that better adhesion between reinforced This work was financially supported by the Ministry of
Science, Technology and Innovation, Malaysia (MOSTI)
science fund (Project no. 305/PBAHAN/6013380) and
MyPhD (Z.X. Ooi).
Table 3
Thermal stability data derived from TGA and DTG curves for non-coated
OPA and LENR-coated OPA filled natural rubber composites. References
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