Kinetic of Thermal Degradation and Thermal Stability of

Natural Rubber Filled With Titanium Dioxide Nanoparticles

Nabil Hayeemasae ,1* Hanafi Ismail,2 Suradet Matchawet,3 Abdulhakim Masa4

1
Department of Rubber Technology and Polymer Science, Faculty of Science and Technology, Prince of
Songkla University, Pattani Campus, Pattani, 94000, Thailand

2
School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia,
Penang, Malaysia

3
Department of Rubber and Polymer Technology, Faculty of Science and Technology, Rajamangala University of
Technology Srivijaya, Nakhon Si Thammarat, 80110, Thailand

4
Sino-Thai International Rubber College, Prince of Songkla University, Hat Yai, Songkhla, 90110, Thailand

This article deals with the kinetic of thermal degradation
and thermal stability of natural rubber (NR) filled with
titanium dioxide (TiO2) nanoparticles. Incorporation of
TiO2 nanoparticles was done through a latex mixing
method. This is to ensure the homogeneity of TiO2 nano-
particles throughout the NR matrix. Adding TiO2 nano-
particles results in shifting the decomposition
temperature and char residue irrespective of the load-
ings of TiO2 nanoparticles. This is confirmed by the cal-
culated kinetic parameters of the composites, indicating
that higher energy is required to decompose the NR
chains. Based on this analysis, a schematic model for
thermal stability of TiO2 nanoparticles filled NR compos-
ites is proposed. POLYM. COMPOS., 2018. © 2018 Society of
Plastics Engineers
INTRODUCTION
Rubber materials are commonly subjected to oxidation
during their service life. The rate of oxidation depends on
rubber types, processing methods and design formulations
[1]. Thermogravimetric analysis (TGA) has been proven as
successful technique to determine the thermal stability of
polymers [2,3]. The respective outputs are frequently used
to study the kinetic of thermal degradation and its mecha-
nism. Mathew et al. [4] studied the thermal degradation of
natural rubber/polystyrene interpenetrating network and
evaluated the kinetic of thermal degradation using the
method of Coats and Redfern [5]. Zhang et al. [6] deduced
the kinetics of the thermal degradation of silicone rubber/
Correspondence to: N. Hayeemasae; e-mail: nabil.h@psu.ac.th
DOI 10.1002/pc.25163
Published online in Wiley Online Library (wileyonlinelibrary.com).
© 2018 Society of Plastics Engineers
carbon black composites. The kinetics of degradation were
further evaluated by the method of Freeman-Carroll [7].
Both studies have shown that the activation energy corre-
lates to the thermal stability of the rubbers.
Several methods of mixing and functionalization have
been reported to improve the thermal stability of rubber.
Addition of inorganic nanomaterials to a rubber is one of
the methods that strongly influences the thermal stability of
the rubbers [8]. As for example, Hayeemasae et al. [9]
studied the effect of ZnO nanoparticles on the thermal per-
formance of natural rubber/recycled ethylene propylene
diene rubber blends. It was observed that incorporation of
ZnO nanoparticles increased the activation energy irrespec-
tive of the loadings of ZnO nanoparticles, suggesting that
the thermal stability is influenced greatly by incorporation
of ZnO nanoparticles.
Titanium dioxide (TiO2) is one of inorganic nanomater-
ials that attract great interest due to the breadth of its cur-
rent and potential applications. The use of TiO2
nanoparticles has received much interest due to its nontoxi-
city, chemical stability, and high effectiveness [10–12].
TiO2 nanoparticles do not possess any active hydroxyl
groups on their surface unlike silica particles that have
available surface hydroxyl groups. This could provide a
less tendency to form aggregate which leads to a better dis-
persion of the TiO2 accompanied with strong interfacial
adhesion between matrix and filler in the polymer compos-
ites [13].
Seentrakoon et al. [14] prepared natural rubber/TiO2
nanoparticles composites with different contents of TiO2
nanoparticles. The addition of TiO2 nanoparticles into NR
improved not only the mechanical properties, but also the
resistance to UV irradiation. More importantly, the

POLYMER COMPOSITES—2018
obtained NR/TiO2 nanoparticles composites exhibited
strong antibacterial property. Comparison study of TiO2
and silica nanoparticles was also reported by Meera
et al. [15], the mechanical properties of the composite con-
taining silica nanoparticles had given better results whereas
the stress relaxation behavior of natural rubber reinforced
with TiO2 and silica nanoparticles was found to be qualita-
tively similar in both systems.
This has shown that TiO2 attract a lot of attention because
of its scientific and commercial importance. It is commonly
used in the rubber industry as an inorganic additive for many
years. Although a number of efforts focused on an under-
standing of the effect of the nanofillers on the performance
of an elastomeric matrix [11,15], there is a lack of detailed
study on the thermal stability of natural rubber incorporated
with TiO2 nanoparticles. There are already a certain number
of reports about the effect of TiO2 nanoparticles on the anti-
aging properties of polymer materials such as polyurethane
[16], epoxy [17], and acrylic coatings [18]. The ever-
increasing need for thermally stable NR composites is creat-
ing a demand for more information on the pyrolysis kinetics.
The aim of this study was to investigate the effect of
TiO2 nanoparticles on the thermal stability of natural rub-
ber. Thermal behavior of the composites is studied through
the kinetic of thermal degradation. This enables monitoring
of thermal stability quantitatively, giving detailed informa-
tion of degradation process. This study will lead to the sci-
entific understanding on how TiO2 nanoparticles could
influence the thermal stability of the NR and extend to be
source of useful information for preparing the NR/TiO2
nanoparticles based heat-shielding materials.
To date, no research on its kinetics of thermal degrada-
tion has been found. Finally, this study also proposes a
new route of dispersing TiO2 nanoparticles and a schematic
model representing the relationship between thermal stabil-
ity and corresponding interfacial adhesion of TiO2 nanopar-
ticles and NR.
EXPERIMENTAL
Materials
The compounding formulation used in this study is listed
Table 1. Low ammonia type Centrifuged Natural rubber
latex (LA-TZ), bentonite clay and Disodium 2,20 -methylene-
bis-naphthalene sulfonate (Tamol) were supplied by Zarm
Scientific (M) Sdn. Bhd., Penang, Malaysia. TiO2 nanoparti-
cles were purchased from Sigma-Aldrich Co., LLC., USA.,
with the size ranging from 15–40 nm (transmission electron
microscope [TEM]), 4.26 g/ml in density, Brunauer–
Emmett–Teller (BET) surface area of 35–65 m2/g, and
>99.5% purity based on an analysis of trace materials [19].
Other compounding ingredients, such as zinc oxide, stearic
acid, N-cyclohexyl-benzothiazyl-sulphenamide (CBS), N-
2-Propyl-N0 -phenylenediamine (IPPD), and sulfur were pur-
chased from Bayer (M) Ltd.
2 POLYMER COMPOSITES—2018
TABLE 1. Compounding formulations used in this study.
Ingredients Amount (phr)
Natural Rubber 100
ZnO 5
Stearic acid 2
CBS 0.5
IPPD 2
Sulfur 2.5
TiO2 nanoparticles 0, 2, 4, 6, and 8
Preparation of the Composites
Figure 1 shows the diagram for the preparation of TiO2
nanoparticles filled NR composites and the starting mate-
rials used for compounding are listed in Table 1. The mix-
ing was performed in a latex stage. The aqueous dispersion
of TiO2 nanoparticles was prepared by using a mechanical
ball mill. The compositions of 40 parts (w/w) of TiO2
nanoparticles, 2 parts (w/w) bentonite clay as a colloidal
stabilizer, 1 parts (w/w) of Disodium 2,20 -methylene-bis-
naphthalene sulfonate (Tamol) as a dispersing agent and
57 parts (w/w) of distilled water as the medium, were
added to the jar of the ball mill. Then, the whole mixture
was kept on the ball milling machine for 24 h at the rota-
tion speed of 10 rpm. Later, the dispersion form of TiO2
nanoparticles was stored in an amber glass bottle to prevent
from self-photooxidation process.
The compounding preparation was done by mixing the
centrifuged NRL with the aqueous dispersion of TiO2
nanoparticles. The mixture was agitated mechanically for
8 h in order to ensure the homogeneity. Subsequently, this
colloidal mixture was poured into a tray and dried in hot
air oven at 100 C for 8 h (C1 compound) prior to com-
pound with other additives (C2 compound) on the labora-
tory size two-roll mill (Model XK-160). The compounds
were finally compression-molded using a stainless steel
mold at 150 C with a pressure of 10 MPa using a labora-
tory hot-press based on the respective curing times.
Curing Characteristics
The curing characteristics of the NR composites were
obtained by using a Monsanto Moving Die Rheometer
(MDR 2000), which was used to determine torques, scorch
time (ts2) and curing time (tc90) according to ASTM:
D2084-11. Samples of the respective composites were
tested at 150 C.
Morphological Studies
The examination of TiO2 nanoparticles particles was
carried out using transmission electron microscope (TEM)
model Philips CM12 and the images were analyzed using
Docu version 3.2 image analysis. The dispersion of TiO2
nanoparticles throughout the NR matrix was carried out by
using scanning electron microscopes (SEM) model Zeiss
DOI 10.1002/pc
 FIG. 1. Schematic representation of the preparation of TiO2 nanoparticles filled NR composites.

Supra-35VP. The fractured pieces were coated with a layer rod or elongated shapes and are far smaller than other com-
of gold/palladium to eliminate electrostatic charge buildup mercial fillers such as silica, calcium carbonate and so
during examination. forth, indicating that high compatibility and thermal stabil-
ity can be attained by incorporating TiO2 nanoparticles.
The dispersion of TiO2 nanoparticles inside the NR
Thermogravimetric Analysis matrix can be visibly seen in Fig. 3. TiO2 nanoparticles
Thermogravimetric analysis (TGA) of TiO2 nanoparti- were dispersed homogenously in the rubber matrix, indicat-
cles filled NR composites was carried out with a Perkin- ing that using the new route for preparing the composites
Elmer Pyris 6 TGA analyzer. The sample was scanned results in better dispersion. The homogeneity of the com-
from 30 to 600 C at the N2 air flow of 30 ml/min with posites is significantly improved; especially with loading
heating rate of 20 C /min. up to 6 phr. Well-dispersed TiO2 nanoparticles are respon-
sible for the improved thermal stability which will be dis-
cussed in later session. Varghese and Karger-Kocsis [20]
Activation Energy of Degradation Process have found similar finding, better dispersion of filler was
made possible through the latex compounding. In addition
The activation energies of degradation for the NR com-
to that, Abraham et al. [21] has shown from their SEM
posites were determined by applying the Coats-Redfern’s
method as follows [5].
     
− logð1 − αÞ AR 1 − 2RT E
log ¼ log × −
T2 βE E 2:303RT
ð1Þ

Here α is the fractional mass loss at time t, T is the

absolute temperature, A is the pre-exponential factor, R is
the universal gas constant, β is the heating rate, and E is
the activation energy. A plot of log[−log(1−α)/T2] as a
function of 1/T gives a straight line with the slope equal to
E/2.303R and the y-intercept log[(AR)/(βE)(1−2RT/E)].

RESULTS AND DISCUSSION

Morphology
Figure 2 shows the TEM image of TiO2 nanoparticles FIG. 2. TEM micrograph of raw TiO2 nanoparticles at 35 k×
particles. It was visibly seen that TiO2 nanoparticles are in magnifications.

DOI 10.1002/pc POLYMER COMPOSITES—2018 3

 FIG. 3. SEM micrographs of TiO2 nanoparticles filled NR composites at 0 (100× magnifications), 2, 6, and
8 phr (35,000× magnifications) of TiO2 nanoparticles.

images that the homogenous dispersion of filler was clearly motion of macromolecules and tends to reduce resistance
from the latex mixing method. They suggested that the dis- to flow [23]. Similar observations were also made for tor-
tribution level of the filler within the matrix could be major que difference (MH–ML), which is a measure of the differ-
reasons for this enhancement of thermal properties. ence between the stiffness or shear modulus of a fully
vulcanized and non-vulcanized test specimen taken at the
lower point of the vulcanizing curve. The is simply attrib-
Curing Characteristics uted to the high stiffness observed when additing TiO2
The curing characteristics of TiO2 nanoparticles filled nanoparticles
NR composites are tabulated in Table 2. The addition of
TiO2 nanoparticles resulted in delayed scorch (ts2) and cur-
Thermogravimetric Analysis
ing times (tc90). Increased loadings of TiO2 nanoparticles
result in a shorter curing process than gum vulcanizate. TGA measures the amount and rate of the mass transi-
The ts2 and tc90 are the measures of premature vulcaniza- tion of a sample as a function of temperature in a certain
tion and the optimum vulcanization process of the compos- atmosphere. Such analysis is used primarily to determine
ites [22]. In general, a slower cure rate is obtained when the thermal stability and compositional properties of mate-
fillers have a high surface area [9]. This causes retardation rials. The thermal decomposition behavior and derivative
of the accelerator activity, which slows down the sulfur weight thermograms of TiO2 nanoparticles filled natural
vulcanizing reaction, leading to increased ts2 and tc90. rubber composites are shown in Figs. 4 and 5. The decom-
Maximum torque (MH) is a measurement of the stiffness or position temperatures at various weight loss stages and char
shear modulus of completely vulcanised test specimens at residue are also listed in Table 3. Two regions of degrada-
the curing temperature. MH increased consistently with the tion were subsequently observed. The initial minor weight
increase of TiO2 nanoparticles. Increments of MH corre- loss at around 180–200 C was associated to the presence
lated to increasing loadings of TiO2 nanoparticles which of volatile matter such as stearic acid and absorbed water at
were due to the TiO2 itself. It highly restricts molecular around 300 C [24]. The major stage in the degradation of
the composites started at about 330 C and was completed
TABLE 2. Curing characteristics of TiO2 nanoparticles filled NR at around 450 C. This is attributed to the degradation of
composites. NR segment. The degradation of the NR segment is sensi-
tive to the presence of the oxidized structure as well as the
Amount of TiO2 MH MH–ML ts2 tc90
nanoparticles (phr) (dN.m) (dN.m) (min) (min)
depletion of sulfidic cross-link in NR [25].
It is interesting to note that the decomposition tempera-
0 phr 6.21 6.17 3.31 9.02 ture at 10, 50, and 70% weight loss of NR composites was
2 phr 6.53 6.42 2.83 8.46 greatly influenced by the presence of TiO2 nanoparticles. It
4 phr 6.55 6.43 3.01 8.47
was found that the decomposition temperature clearly dif-
6 phr 6.62 6.49 3.05 8.73
8 phr 6.56 6.39 3.06 8.76 fered from the earlier stages of decomposition. Introducing
TiO2 nanoparticles into the NR composites greatly affected

4 POLYMER COMPOSITES—2018 DOI 10.1002/pc


FIG. 4. TG curves and corresponding char residue of TiO2 nanoparticles
filled NR composites.
Based on these results, a schematic illustration repre-
senting thermal stability and corresponding interfacial
adhesion of TiO2 nanoparticles filled NR composites is
proposed in Fig. 6. In this model, TiO2 nanoparticles are
dispersed in the crosslinked NR composite, and the NR
matrix is strongly interacting with the TiO2 nanoparticles
in the areas where they are in contact. Upon thermal condi-
tion, the rod or elongated shape of TiO2 nanoparticles is
adsorbed along the molecular chains, providing more con-
tacted area to the NR molecular chains. Consequently, the
NR chains are less decomposed, the thermal stability of the
NR increases due to the collaborative interfacial adhesion
of NR with dispersed TiO2 nanoparticles. As a result, more
heat is required to deplete the molecular chains, leading to
a significant increase in the thermal stability. This is very
good agreement to Keblinski et al. [26], who proposed the
possible mechanisms for enhancing the thermal conductiv-
ity and suggested that the size effect, the clustering of
nanoparticles and the surface adsorption could be major
reasons for this enhancement of thermal properties.
Furthermore, the char residue of all composites was
influenced by introducing of TiO2 nanoparticles. This is
simply due to the fact that the amount of filler was varied;
thus keeping the char residue mostly changed. According
to Chakraborty et al. [27], the amount of char is very much
dependent on the type and amount of filler. The difference
in filler amount mainly concerns the char formation.

Activation Energy of Degradation Process. Since

thermal stability is related to both to the initial temperature
and to the rate of degradation of polymers, the determina-
tion of kinetic parameters associated with the degradation
process is an interesting topic. Thermal analysis can also
be used for the durability assessment and lifetime predic-
FIG. 5. DTG curves and the temperature at maximum weight loss of
TiO2 nanoparticles filled NR composites.
tion of a product. Such study is very important for
improvement of a product’s service performance [28]. The
TABLE 3. Temperatures at various weight loss of TiO2 nanoparticles
different stages of degradation can be conveniently identi-
filled NR composites. fied from different slopes. Coats–Redfern plots, for the NR
composites with and without the presence of TiO2 nanopar-
Temp. @ Temp. @ Temp. @ ticles, are presented in Fig. 7 and the activation energies
Amount of TiO2 10% weight 50% weight 70% weight obtained by this approach are shown in Fig. 8. From the
nanoparticles (phr) loss ( C) loss ( C) loss ( C)
DTG curves, only single stage of degradation was observed
0 phr 348.3 401.2 415.5 for the NR composites, which can be attributed to the deg-
2 phr 350.2 402.8 418.2 radation of NR composites.
6 phr 355.0 403.8 421.3 The degradation of unfilled NR (330–450 C) involved
8 phr 359.3 405.3 424.6 activation energy of 89.57 kJ/mol, the activation energies
are towards higher value when the TiO2 nanoparticles are
used for NR. It is found to be at 101.25, 102.45, and
their thermal stability. The decomposition temperature of 109.10 kJ/mol for 2, 4, and 8 phr of TiO2 nanoparticles,
the composites showed further improvement at the decom- respectively. Activation energy indicates the energy
position temperatures above 50% of weight loss. TiO2 required to decompose the molecular network. Here, it was
nanoparticles do not possess any active hydroxyl groups on found that the presence of TiO2 nanoparticles gave higher
their surface unlike silica particles that have available sur- activation energy than the unfilled NR had, suggesting that
face hydroxyl groups. This could provide a less tendency highly dispersed TiO2 nanoparticles were achieved in the
to form aggregate which leads to a better dispersion of the blends. Another probable reason might be due to the TiO2
TiO2 accompanied with strong interfacial adhesion between nanoparticles itself, which contains thermally stable inor-
matrix and filler in the rubber. ganic substance. It was postulated that such substances

DOI 10.1002/pc POLYMER COMPOSITES—2018 5

 FIG. 6. Schematic representation of thermal behavior of TiO2 nanoparticles filled NR composites.
FIG. 7. Coat-Redfern’s plots of TiO2 nanoparticles filled NR
composites.
were able to increase the resistance to bond cleavage or
depletion at the degradation temperature. Higher activation
energy with TiO2 nanoparticles clearly indicates improved
thermal stability of the NR composites; irrespective of the
TiO2 nanoparticles content in the NR composites.
CONCLUSIONS
The following conclusion can be presented:
1. Rod or elongated shape of TiO2 nanoparticles is clearly seen in
TEM image, indicating that high contact area and thermal sta-
bility can be attained by incorporating TiO2 nanoparticles.
6 POLYMER COMPOSITES—2018
FIG. 8. Activation energies of degradation process of TiO2 nanoparticles
filled NR composites.
2. The thermal decomposition temperature of the rubber has shifted
to a higher temperature when TiO2 nanoparticles are used
3. The thermal stability of TiO2 nanoparticles filled NR compos-
ites is confirmed by the calculated kinetic parameters where
higher energy is shown upon the inclusion of TiO2 nanoparti-
cles in NR, indicating that more heat is needed to decompose
the sample.
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