Polym. Bull.

DOI 10.1007/s00289-016-1641-3

ORIGINAL PAPER

A comparison between polyethylene glycol (PEG)

and polypropylene glycol (PPG) treatment
on the properties of nano-titanium dioxide (TiO2) based
natural rubber (NR) nanocomposites

Kumarjyoti Roy1 • Swapan Kumar Mandal1 •

Md. Najib Alam1 • Subhas Chandra Debnath1

Received: 15 October 2015 / Revised: 6 February 2016 / Accepted: 8 March 2016

Ó Springer-Verlag Berlin Heidelberg 2016

Abstract The purpose of the present article is to modify the surface of nano-
titanium dioxide (TiO2) and to investigate the reinforcing effect of both unmodified
and surface-modified nano-titanium dioxide (TiO2) on the mechanical properties
and thermal stability of natural rubber (NR) nanocomposites. Surface of nano-TiO2
is modified by polyethylene glycol (PEG) and polypropylene glycol (PPG). The
effective surface modification of nano-TiO2 is evaluated by Fourier transform
infrared (FTIR) spectra and field emission scanning electron microscopy (FESEM).
The result notifies that the final properties of NR nanocomposites are dramatically
improved in the presence of surface-modified nano-TiO2 in comparison to
unmodified nano-TiO2. The excellent reinforcing capability of surface-modified
nano-TiO2 is due to its better hydrophobicity and uniform dispersion within the NR
matrix, as confirmed from morphological analysis. Furthermore, due to its small size
PEG is better surface modifier for nano-TiO2 than PPG.

Keywords Nanocomposites  Reinforcement  Mechanical properties 

Morphology  Thermal properties

Introduction

Among the various types of rubber, the unique mechanical properties of natural
rubber (NR) make them crucial and irreplaceable materials in dynamic properties
related applications like tire industry [1]. Several reasons like highly stereoregular
microstructure, the rotational freedom of the a-methylenic C–C bonds and high
elasticity are responsible for the exceptional mechanical properties of NR [1]. But,
the application of reinforcing filler is very common for the attainment of optimum

& Subhas Chandra Debnath

debnathsubhas@yahoo.com
1
Department of Chemistry, University of Kalyani, Nadia, Kalyani 741235, WB, India

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properties required in industrial field of rubber research [2]. For a long time, carbon
black and silica are the most commonly used fillers in manufactured rubber
products. However, due to large particle size, both the fillers have tendency to
agglomerate within the rubber matrix [3]. As a result, the reinforcing ability of both
the fillers is effectively reduced in rubber compounds [3]. On the other hand, large
specific surface area is responsible for the uniform dispersion of nano-fillers within
the rubber matrix [3]. Thus, the application of nano-fillers is an interesting way to
achieve appropriate mechanical and physical properties of rubber compounds [3].
In present decades, the civilization of rubber chemistry by the suitable application
of nanotechnology has received great attention for modern rubber researcher.
Several research papers have been reported in literature related to the reinforcement
of rubber composites using some common nano-fillers like carbon nano-tube [4–6],
nano-clay [7, 8], nano-calcium carbonate [9–12], etc. Now, homogeneous disper-
sion of nano-filler within the rubber matrix is the key factor in improving the
properties of rubber nanocomposites [13]. It was importantly stated that hydrophilic
nature of nano-filler creates definite problem on its uniform distribution within
hydrophobic rubber matrix [14, 15]. Thus, surface modification is undoubtedly the
vital step for the versatile use of nano-filler in rubber industry.
Recently, some researchers have reported the surface modification of nanoparticles
by the successful use of various surfactants [15–18]. It was described that surface
grafting of zinc oxide (ZnO) nanoparticles is possible using long hydrophobic chains
of polyethylene glycol (PEG) and polypropylene glycol (PPG) [15]. Ma et al. [16]
confirmed that cationic surfactant cetyltrimethylammonium bromide (CTAB) is very
effective in modifying the surface of silica nanoparticles. It was reported that the
grafting of surfactant on the surface of silica probably occurs by the reaction between
surface hydroxyl group of silica and CTAB [16]. In another work, Qu et al. [17] also
modified the surface of nanocrystalline anatase with CTAB. Thus, the use of surfactant
provides unique way for the surface modification of nanoparticles.
It has been stated by several researchers that nano-TiO2 is an environment friendly,
non-toxic additive and polymer nanocomposites containing nano-TiO2 are also
‘‘environmentally safe’’ [19, 20]. It is noted that study related to reinforcing effect of
titanium dioxide (TiO2) is very common for polymer composites [21]. But, till now the
utilization of surface-modified nano-TiO2 to improve mechanical, thermodynamic
and thermal properties of rubber nanocomposites is in the early stages. According to
authors’ best knowledge, vast study based on PEG- and PPG-modified nano-TiO2
reinforced NR nanocomposites has not been reported in the literature. Thus, it is very
interesting for rubber researchers to study the improvement in the properties of NR
composites in presence of both PEG- and PPG-modified nano-TiO2.

Experimental

Materials and physical measurements

Natural rubber (RMA-1X), zinc oxide (Merck, Germany), stearic acid (Loba
Chemie, India), sulfur (Loba Chemie, India), tetra benzyl thiuram disulfide

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(TBzTD) (Apollo tyre Ltd., India) and toluene (Merck) are used as received.
Polyethylene glycol (PEG, MW = 400) and polypropylene glycol (PPG,
MW = 2000) are also supplied by Merck (Germany) company. Nano-TiO2 is
prepared using the procedure given by Behnajady et al. [22].
Fourier transform infrared (FTIR) spectra of unmodified and surface-modified
nano-TiO2 are measured on a Perkin-Elmer L 120-000A spectrometer on KBr disks.
Field emission scanning electron microscopy (FESEM) study is done using
instrument JSM 6700F. The cure characteristics of the different samples are
determined using the Monsanto Rheometer R-100 at 3° arc for 160 °C. The
vulcanizates are cured under pressure at 160 °C for optimum cure time (t90) and
kept for 24 h at room temperature before measuring the mechanical properties like
modulus at 100 % (M100) elongation, tensile strength (T.S.) and elongation at break
(E.B.) according to ASTM D 412-51 T using dumbbell-shaped test pieces in an
Amsler (Sweden) tensile tester. Hardness (shore A) of the vulcanizates is calculated
by a Hirosima Hardness Tester as per ASTM D 1415-56T. Thermogravimetric
analysis (TGA) is carried out in order to study the thermal stability of NR
vulcanizates. TGA scans are performed using a TA instrument (Q 5000) under
nitrogen flow from 20 to 800 °C with a heating rate of 10 °C/min.

Surface modification of TiO2 nanoparticles

Surface of nano-TiO2 is modified by two different surfactants namely PEG and

PPG. In the first step, 25 g of nano-TiO2 is dispersed in 100 ml water by stirring for
30 min under ultrasonic agitation. In the next step, the solution of PEG is prepared
by dissolving 1.25 g PEG into 100 ml water. Then, the PEG solution is added to the
previously prepared nano-TiO2 suspension and the mixture is stirred for 24 h at
room temperature for proper surface capping of nano-TiO2 by PEG. The surface-
modified TiO2 nanoparticles are collected by centrifugation. The TiO2 nanoparticles
are washed with distilled water to remove excess PEG on the surface of nano-TiO2.
Finally, TiO2 nanoparticles are dried in a vacuum oven for 5–6 days. Same
procedure is followed to modify the surface of nano-TiO2 by PPG. The surface
modification of nano-zinc oxide (ZnO) by PEG and PPG was reported previously by
Taghvaei-Ganjali et al. [15].

Preparation of NR nanocomposites

NR is first masticated in a two-roll mixing mill. In the next step, ZnO and stearic
acid are added and again masticated. Subsequently, unmodified nano-TiO2 is added
to the rubber matrix and the mixing done for sufficient time. In the last step,
accelerator and sulfur are mixed to the rubber matrix and the mixing is done near
about for 10 min. Total concentration of the accelerator is fixed at 9 mmol/100 g of
rubber. The repetitive process is done to prepare NR nanocomposites containing
different amount of surface-modified nano-TiO2. Mixing composition of different
NR nanocomposites is shown in Table 1.

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Table 1 The formulation of studied vulcanizates in parts per hundred parts of rubber (phr)
Formulation Compound designation

NR- NR/0.5 NR/1 NR/1.5 NR/2 NR/1.5 NR/1.5

gum NTiO2 NTiO2 NTiO2 NTiO2 NTiO2/PEG NTiO2/PPG

NR 100 100 100 100 100 100 100

ZnO 5 5 5 5 5 5 5
Stearic acid 2 2 2 2 2 2 2
TBzTD 4.896 4.896 4.896 4.896 4.896 4.896 4.896
Sulfur 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Unmodified – 0.5 1 1.5 2 – –
nano-TiO2
PEG-treated – – – – – 1.5 –
nano-TiO2
PPG-treated – – – – – – 1.5
nano-TiO2

Results and discussion

Confirmation of surface modification of TiO2 nanoparticles

FTIR spectroscopy gives significant idea about surface capping of TiO2 nanoparticles.
Figure 1 denotes the FTIR spectra of both unmodified and surface-modified TiO2
nanoparticles. The peak around 2800 to 3000 cm-1 generally indicates the stretching
vibration of the C–H bond [15]. There is a significant peak at about 2917 cm-1 in the
FTIR spectra of PEG-modified nano-TiO2 (Fig. 1b) due to the C–H stretching
vibration in the PEG which is present on the surface of nano-TiO2. Similarly, in the
FTIR spectra of PPG-modified nano-TiO2 (Fig. 1c), the strong peak at about
2920 cm-1 is correlated to the C–H stretching vibration in the PPG. Again, the broad
peak between 3200 and 3600 cm-1 is the characteristic peak of surface hydroxyl
group [15]. Moreover, the strong peak of surface hydroxyl group is noticeably shifted
towards lower wave number region in the FTIR spectra of both PEG- and PPG-treated
nano-TiO2 in comparison to unmodified nano-TiO2. The shifting of surface hydroxyl
group towards lower wave number region clearly concludes the effective surface
modification of nano-TiO2 using PEG and PPG [15, 18].
FESEM analysis is utilized for further confirmation of the surface modification of
nano-TiO2 using PEG. Figure 2 displays the difference between the FESEM images of
unmodified and PEG-modified nano-TiO2. Figure 2a shows that unmodified TiO2
nanoparticles are not well distributed and aggregated. But Fig. 2b confirms that the
dispersion state of nano-TiO2 is successfully modified by surface treatment with PEG.

Mechanism of surface modification of TiO2 nanoparticles

It was reported that surface modification of nano-TiO2 with silane coupling agent
occurs by the reaction between active hydroxyl groups on the surface of TiO2
nanoparticles and alkoxy groups of silane compounds [23]. The probable schematic

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Fig. 1 a FTIR spectra of unmodified TiO2 nanoparticles. b FTIR spectra of PEG-modified TiO2
nanoparticles. c FTIR spectra of PPG-modified TiO2 nanoparticles

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Fig. 2 SEM images of

a unmodified, b PEG-modified
TiO2 nanoparticles

mechanisms for surface modification of TiO2 nanoparticles by PEG and PPG are
elucidated in Fig. 3. In this mechanism, the hydrogen bonds are formed between
surface hydroxyl groups of nano-TiO2 and the modifiers. Due to the formation of
these types of hydrogen bonds, the strong band of surface hydroxyl group is shifted
towards lower wave number region in surface-modified TiO2 nanoparticles in
comparison to unmodified nano-TiO2 [18].

Cure characteristics of NR nanocomposites

Table 2 summarizes the cure characteristics of NR nanocomposites in presence of

both unmodified and surface-modified nano-TiO2. The cure properties of NR
nanocomposites are elucidated in terms of maximum rheometric torque (R?),
optimum cure time (t90) and cure rate index (CRI).
R? generally defines the degree of crosslinking of rubber vulcanizates [24]. Cure
study shows that for NR nanocomposites the improvement in the value of R? is
very small in presence of unmodified nano-TiO2 in comparison to unfilled NR
vulcanizate. However, considerable enhancement in the value of R? occurs when
1.5 phr surface-modified nano-TiO2 is added to the NR matrix. This is due to

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Fig. 3 The probable schematic mechanisms for surface modification of TiO2 nanoparticles by PEG and
PPG

excellent interaction between NR matrix and surface-modified nano-TiO2. It is

noted that PEG-treated nano-TiO2 has much greater ability to interact with NR
matrix in comparison to PPG-treated nano-TiO2 and R? value shows a noticeable
increment by *26.56 % for NR/1.5 NTiO2/PEG in comparison to NR-gum.
Now, it was already established that filler plays a vital role in accelerating the
cure rate in the vulcanization of rubber [10]. Both unmodified and surface-modified
nano-TiO2 are able to reduce the value of optimum cure time (t90), i.e., to activate
the cure reaction during vulcanization of NR. The scorch time (t2) remains almost

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Table 2 Cure and mechanical properties of NR nanocomposites in presence of unmodified and surface-
modified nano-TiO2
Sample code Maximum Optimum Scorch Cure rate M100 T.S. E.B. Hardness
rheometric cure time, time, t2 index, (MPa) (MPa) (%) (shore A)
torque, R? t90 (min) (min) CRI = 100/
(dNm) (t90 - t2)
(min-1)

NR-gum 32 8.5 2.5 16.66 0.758 13.21 730 50

NR/0.5 NTiO2 32.5 8.25 2.5 17.39 0.789 13.79 725 51
NR/1 NTiO2 34 8 2.5 18.18 0.829 14.32 720 51
NR/1.5 NTiO2 35 7.75 2.75 20 0.853 14.77 720 52
NR/2 NTiO2 35 8 2.75 19.04 0.848 14.67 720 50
NR/1.5 40.5 7 2.75 23.52 1.006 16.21 660 54
NTiO2/PEG
NR/1.5 38 7 2.75 22.22 0.934 15.23 680 53
NTiO2/PPG

unchanged for different rubber vulcanizates. Figure 4 represents the variation of

cure rate index (CRI) of various NR nanocomposites. It is clearly notified that
unmodified nano-TiO2 enhances the value of CRI up to 1.5 phr loading level. Above
1.5 phr loading level, unmodified nano-TiO2 is not able to increase CRI value due to
its tendency of agglomeration [10]. It is noticeable that both PEG- and PPG-treated
nano-TiO2 are much more effective to activate cure process of NR nanocomposites
in comparison to unmodified TiO2 nanoparticles. The CRI value shows an
increment by 41.18 and 33.37 % for NR/1.5 NTiO2/PEG and NR/1.5 NTiO2/PPG,
respectively, in comparison to NR-gum.

Fig. 4 Variation of cure rate index of NR nanocomposites

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Mechanical properties of NR nanocomposites

The mechanical properties of NR nanocomposites containing both unmodified and

surface-modified nano-TiO2 are described in Table 2. The value of M100 increases
constantly as the amount of unmodified nano-TiO2 in NR matrix increases up to 1.5
phr loading level, as shown in Fig. 5. Above 1.5 phr loading level, the ability nano-
TiO2 to increase the value of M100 reduces due to its agglomeration [10]. Moreover,
unmodified nano-TiO2 causes very little enhancement in the value of M100 for NR
nanocomposites. But, it is clear from Fig. 5 that surface-modified nano-TiO2 leads
to remarkable improvement in the M100 value of NR nanocomposites. Thus, the
modulus value indicates the interfacial interaction between rubber matrix and nano-
TiO2 becomes much better after surface treatment of nano-TiO2 by PEG and PPG.
Out of two surface-modified nano-TiO2, PEG-treated nano-TiO2 causes greater
enhancement in the modulus value and the value of M100 shows a tremendous
increment by 32.72 % for NR/1.5 NTiO2/PEG in comparison to NR-gum. The
superior surface capping of nano-TiO2 by PEG may be due to the smaller size of
PEG in comparison to PPG [15].
Now, at the same loading level, surface-modified nano-TiO2 is found to be more
efficient to enhance the tensile strength of NR nanocomposites in comparison to
unmodified nano-TiO2 (Fig. 6). Actually, increase of hydrophobicity of nano-TiO2
after surface treatment by PEG and PPG is the key factor for producing better
compatibility between surface-modified nano-TiO2 and NR matrix. As a result,
surface-modified TiO2 nanoparticles are distributed much more homogeneously
within the NR matrix in comparison to unmodified nano-TiO2. The tensile strength
is observed to improve by 22.71 % for NR/1.5 NTiO2/PEG and by 15.29 % for NR/
1.5 NTiO2/PPG in comparison to NR-gum.
The value of elongation at break remains almost unaffected due to incorporation
of unmodified nano-TiO2 in NR matrix. However, surface-modified nano-TiO2

Fig. 5 Variation of modulus value at 100 % elongation (M100) of NR nanocomposites

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Fig. 6 Variation of tensile strength of NR nanocomposites

leads to the increase of crosslink density of NR vulcanizates [25, 26]. As a result,

there is a reduction in the elongation at break value of NR nanocomposites in
presence surface-modified nano-TiO2. On the other hand, surface-modified nano-
TiO2 is slightly more effective to increase the value of hardness in comparison to
unmodified nano-TiO2.

Morphology of NR nanocomposites

The phase morphology of NR nanocomposites is useful in determining the

dispersion level of TiO2 nanoparticles within the rubber matrix. Figure 7 illustrates
the SEM images of NR vulcanizates containing both unmodified and surface-
modified nano-TiO2 at 1.5 phr loading level. The black phase represents NR matrix
and white dot specifies agglomerated TiO2 nanoparticles in rubber matrix. Figure 7a
clearly indicates that unmodified TiO2 nanoparticles are not properly distributed
within the NR matrix and large amount of agglomeration is present. But, Fig. 7b, c
confirms the uniform dispersion of surface-modified TiO2 nanoparticles within the
NR matrix. This is due to the greater hydrophobicity of nano-TiO2 after surface
modification with PEG and PPG. Thus, the ability of the surface treated nano-TiO2
to enhance the mechanical properties of NR nanocomposites is far greater in
comparison to untreated nano-TiO2.

Variation of elastic Gibbs free energy (DG) and conformational entropy

(DS) of NR vulcanizates

Table 3 represents the variation of thermodynamic parameters DG and DS for NR

nanocomposites containing same amount (1.5 phr) of unmodified and modified
nano-TiO2. Actually, the discussion of thermodynamic parameters of NR
nanocomposites is utilized to study the dispersion of nano-TiO2 in NR matrix

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Fig. 7 SEM images of NR nanocomposites containing a unmodified, b PEG-modified and c PPG-

modified TiO2 nanoparticles

Table 3 Variation of thermodynamic and thermal properties of NR nanocomposites

Sample code DG (J/mol) DS 9 10-2 (J/mol) Ti (°C) Tmax (°C)

NR-gum -8.55 2.82 299 374

NR/1.5 NTiO2 -8.81 2.90 304 377
NR/1.5 NTiO2/PEG -9.18 3.03 320 381
NR/1.5 NTiO2/PPG -8.98 2.96 314 377

[11]. The elastic Gibbs free energy (DG) is determined with the help of Flory–
Huggins equation [27]:
 
DG ¼ RT ln ð1  Vr Þ þ Vr þ v Vr2 ;
where R is the universal gas constant, T is the absolute temperature; Vr is the
volume fraction of swollen rubber, v is the rubber solvent interaction parameter.
The volume fraction of a rubber network in the swollen phase Vr is calculated
from equilibrium swelling data using Flory–Rehner equation [28],
Vr ¼ ðW2 =d2 Þ=fðW1 =d1 Þ þ ðW2 =d2 Þg

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where W1 is the weight fraction of the solvent, d1 is the density of the solvent,
W2 is the weight fraction of the polymer in the swollen specimen and d2 is the
density of the polymer. For the natural rubber–toluene system, v = 0.3795 [29],
the molar volume of toluene Vs is 106.2 cm3/mol, and the density of toluene is
0.87 g/cm3.
Again, from the statistical theory of rubber elasticity, DS is connected to DG by
the following equation, DG = -TDS, here it is assumed that no change of internal
energy of rubber network occurs during stretching [30]. The data represented in
Table 3 indicate the conformational entropy (DS) of NR/1.5 NTiO2/PEG is higher
as compared to both NR/1.5 NTiO2/PPG and NR/1.5 NTiO2. The uniform
dispersion of PEG-treated nano-TiO2 within the rubber matrix is responsible for the
higher value of DS in NR/1.5 NTiO2/PEG than other two mixes [30]. The value of
DG indicates that NR/1.5 NTiO2/PEG has greater elastic behavior in comparison to
either NR/1.5 NTiO2/PPG or NR/1.5 NTiO2 as DG is closely linked to the elastic
behavior of the material [30]. The better elastic behavior of NR/1.5 NTiO2/PEG is
explained by considering maximum level of interaction between rubber matrix and
PEG-treated nano-TiO2 [30].

Thermal stability of NR nanocomposites

Figure 8a, b shows the thermogravimetric analysis (TGA) and differential

thermogravimetric analysis (DTA) curves of various NR nanocomposites. TGA
study indicates a huge shift of rapid degradation region towards higher temperature
due to addition of PEG-treated nano-TiO2 into the NR matrix in comparison to
untreated nano-TiO2. This fact clearly implies much greater thermal stability of NR/
1.5 NTiO2/PEG as compared to both NR/1.5 NTiO2 and NR-gum.
DTA study gives very important interpretation on the excellent thermal stability
of NR nanocomposites containing PEG-modified nano-TiO2. The onset decom-
position temperature (Ti) and the temperature at which the rate of decomposition
is maximum (Tmax) are determined from DTA curves and described in Table 3.
The Ti values of NR nanocomposites are recorded at 304, 320, 314 °C for 1.5 phr
loading of untreated, PEG-treated and PPG-treated nano-TiO2, respectively, while
Ti value of NR-gum is 299 °C. The Ti value obviously suggests that surface-
modified nano-TiO2 provides remarkably greater thermal stability into the NR
matrix than unmodified nano-TiO2. The uniform dispersion of surface-modified
nano-TiO2 within the rubber matrix restricts the thermal motion of rubber chain
within the network structure and thereby increases degree of vulcanization [31].
Also, uniform dispersion of surface-modified nano-TiO2 leads to the homogeneous
heat distribution throughout the rubber matrix [32]. These two facts are
responsible for the improved thermal stability of NR nanocomposites in
combination with surface-modified nano-TiO2. It is also noted that PEG-treated
nano-TiO2 delivers slightly greater thermal stability than PPG-treated nano-TiO2
in NR nanocomposites.

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Fig. 8 a TGA analysis of NR vulcanizates. b DTA analysis of NR vulcanizates

Conclusions

In summary, the present paper mainly reveals a comparison between NR

nanocomposites based on unmodified and surface-modified nano-TiO2. The surface
of nano-TiO2 is modified successfully by PEG and PPG. The surface modification
of nano-TiO2 may be occur via hydrogen bonding interaction between surface
hydroxyl group of nano-TiO2 and PEG or PPG. Due to the better hydrophobicity,

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the extent of dispersion of surface-modified nano-TiO2 within the non-polar rubber

matrix is far better as compared to unmodified nano-TiO2. Thus, the interfacial
interaction between surface-modified nano-TiO2 and rubber matrix is more
operative than unmodified nano-TiO2. As a result, surface-modified nano-TiO2
leads to the remarkable enhancement in the mechanical and thermal properties of
NR nanocomposites in comparison to unmodified nano-TiO2. Both, morphological
and thermodynamic studies confirm the improvement in the dispersion level of
nano-TiO2 in NR matrix due to surface modification.
Again, due to its small size, PEG is more efficient surface modifier than PPG for
TiO2 nanoparticles. This is clearly reflected in the resulting properties of nano-TiO2
filled NR nanocomposites. Thus, PEG nano-TiO2 will be the part of great interest
regarding its application as an effective property reinforcing material in rubber
industry.

Acknowledgments Authors thankfully acknowledge Department of Science and Technology, West

Bengal, India (Sanction No. 715(Sanc.)/ST/P/S&T/6G-1/2013 dated 12.11.2014) for financial support.
Mr. Kumarjyoti Roy sincerely thanks University of Kalyani for fellowship assistance.

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