Received: 5 May 2020 Revised: 31 August 2020 Accepted: 10 September 2020

DOI: 10.1002/pen.25541

RESEARCH ARTICLE

Improved dispersion and physico-mechanical properties of

rubber/silica composites through new silane grafting

Saikat Das1 | Santanu Chattopadhyay1 | Sawar Dhanania2 |

Anil K. Bhowmick1,3

1
Rubber Technology Centre, Indian
Institute of Technology Kharagpur,
Kharagpur, West Bengal, India
2
Mutual Technologies Pvt. Ltd., Kolkata,
West Bengal, India
3
Department of Chemical and
Biomolecular Engineering, The University
of Houston, Houston, Texas
Correspondence
Anil K. Bhowmick, Rubber Technology
Centre, Indian Institute of Technology
Kharagpur, Kharagpur 721302, West
Bengal, India.
Email: anilbhowmick@gmail.com
Funding information
Ministry of Human Resource
Development, Grant/Award Number:
UAY/IITKGP006/HPN
Abstract
3-Octanoylthio-1-propyltriethoxysilane (a new silane) grafted styrene butadiene
rubber/ silica composites were prepared in the present work, where grafting
weight percentage of the base rubber (0%, 2%, 4%, and 6%) and filler content of
the composites (0, 5, 15, 35, and 50 phr) were varied to investigate dispersion of
the filler in the rubber. A detailed quantitative study of morphology-physical
property relationship of the composites using dispersion degree parameter was
carried out. Pronounced improvement of dispersion was observed with increas-
ing grafting weight percentage of the base rubber. A mechanism of polymer to
filler interaction was shown by Fourier transform infrared spectroscopy. The dis-
persion rate constant from the torque-time curve increased with the grafting per-
centage. Bound rubber content and Payne effect measurement indicated
improved rubber-filler interaction for the grafted rubber compound. A relation
between low strain modulus of the composites and grafting percentage was pro-
posed. The nanoindentation studies gave further insight into the results. Other
physico-mechanical properties at different grafting weight percentages at partic-
ular filler loading (50 phr) and at different filler loadings at a particular grafting
weight percentage (4%) were evaluated. The improved mechanical and dynamic
mechanical properties with increasing grafting weight percentage are an indica-
tion that this methodology could be used in green tire application.

KEYWORDS
composites, dispersion, morphology, rubber, silica

1 | INTRODUCTION
Organic-inorganic nanohybrids are investigated nowadays
for their extraordinary surface and bulk properties. The
inorganic compounds are usually layered clays or
nanosilicas or other materials with a wide range of shapes.
The properties of these nanocomposites depend on the
dimension, shape of the nanofillers, and interfacial bonding
of the base materials with the fillers.[1] Filler-polymer inter-
action has become most important with the introduction of
the green tire technology using silica in passenger car tire
tread applications. The functionality of the polymer chain
plays an important role in the case of polymer-filler interac-
tion to increase the dispersion of silica besides controlling
the silanization process. The main research objective of
researchers in this field is to design functionalized elasto-
mer, especially in the case of solution styrene butadiene
rubber (S-SBR) and to reduce the hydrophobic characteris-
tics of the hydrocarbon polymers to make the hydrophilic
silica more compatible and dispersible in SBR, thus

Polym Eng Sci. 2020;60:3115–3134. wileyonlinelibrary.com/journal/pen © 2020 Society of Plastics Engineers 3115
3116
providing better silica dispersion and polymer -filler interac-
tion.[2-7] The surface hydroxyl groups on silica make it
hydrophilic. Because of the lack of hydrophobicity, the infe-
rior interaction between silica and SBR causes poor
mechanical properties over their carbon black counterpart.
This is an active area of research over the last few years.
The efficiency of a vehicle can improve by increasing the sil-
ica content in the tire tread compound. If the silica does not
mix well, it can deteriorate the properties and processing of
a tire tread to a large extent.[8] Meanwhile, silica with new
structure and surface area is available for tire composition.
Their interaction with polymer is little understood. A new
hexagon-linking model of silica aggregation in a tread for-
mulation was proposed and studied using transmission,
scanning, and analytical electron microscopy by li et al.[9]
Interfacial interaction and performance of silica/epoxy
group functionalized styrene-butadiene rubber without any
coupling agent were studied by Qiao et al.[10] The contribu-
tion of silica-rubber interaction on the viscoelastic behavior
of modified SBR was studied by Qu et al.[11] The influence
of nanofillers on the mechanical properties of poly-
acrylicester polymer was studied by Bhowmick et al. in this
laboratory.[12] Effects of polymer-filler interaction of epoxi-
dized natural rubber/silica composite on solvent swelling
and dynamic mechanical properties were also studied by
Bhowmick et al.[13] Effect of silica loading and coupling
agent on wear and fatigue properties of a tread compound
was studied by Bhowmick et al.[14-16] One of the ways to
enhance interaction between silica and rubber is to use a
coupling agent, mainly silanes. Several types of silanes have
been developed and each one, added externally, has been
evaluated.[17] In our laboratory we have been examining
the effects where some of the newly developed silanes are
directly grafted onto a tire polymer.[18] Morphology and dis-
tribution of modified silica through atomic force microscopy
(AFM) on the ethylene-octene copolymer rubber silica com-
posites was also studied in this laboratory.[19] Filler-filler
and polymer-filler interaction in ethylene-octene copolymer
rubber silica composites was investigated in this laboratory
where silica was treated with triethoxyvinyl silane.[20] Natu-
ral rubber/silica nanocomposites were developed, and its
morphology and dynamic mechanical properties were
investigated by Chen et al.[21] The influence of organically
modified nanoclay-carbon black hybrid filler on the curing
behavior of natural rubber composites was explored by the
other researchers.[22] Natural rubber/siliceous earth filler
composites were prepared by the mechanical and latex
mixing process where cure characteristics and mechanical
properties of the composite were investigated.[23] In our
work, we have attempted to improve the dispersion of silica
filler in a tire formulation by grafting of a novel
3-Octanoylthio-1-propyltriethoxysilane (NXT silane) onto
SBR.[24] We have further prepared grafted SBR/silica
DAS ET AL.
composites with varying grafting weight percentage and
filler loading. In the present work, we have focused on the
quantification of nano-silica (ULTRASIL 7000GR) disper-
sion in 3-Octanoylthio-1-propyltriethoxysilane grafted sty-
rene butadiene base rubber by scanning electron
microscopy (SEM) and AFM. The dispersion of silica has
been quantified directly for a new silane grafted rubber/sil-
ica composite using dispersion degree parameter. The inter-
action between silica and pendent propyltriethoxy silane
moiety has been proved by Fourier transform infrared spec-
troscopy (FTIR). Silica dispersion with increasing grafting
weight percentage has been also shown. Correlation
between degree of dispersion and mechanical properties
has been established where improvement of physico-
mechanical properties due to the good dispersion of silica
and strong rubber-silica interaction has been studied.
Mechanical, dynamic mechanical and other properties with
increasing grafting weight percentage and filler dispersion
have been investigated here with special reference to the
morphology of the composites. A relation between low
strain modulus of the composites and grafting weight per-
centage has been developed. The nanoindentation method
to understand dispersion was used for the first time. The
properties of the composites have been found to be better
than the previously reported silane grafted or silane added
rubber/silica composites.
2 | EXPERIMENTAL
2.1 | Raw materials
Polymer: (SBR 1502, styrene content-23.5%,
Mw = 522 558 g mole−1, Tg = −54
C, Mooney viscosity,
ML1 + 4 at 100
C = 51) was bought from Kumho Petro-
chemicals, South Korea.
Filler: HD silica (ULTRASIL 7000GR) with specific
surface area(CTAB) of 160 m2/g (6.5 pH) was bought
from Evonik Degussa India Pvt. Ltd., Mumbai.
Silane: NXT (3-Octanoylthio-1-propyl triethoxysilane)
silane (Mw = 365.0 g/mol) was procured from
Momentive, Bangalore, India.
Free radical generator: mercaptobenzothiazole (MBT)
was procured from Sigma-Aldrich, Germany.
2.2 | Modification of SBR
Reactive modification of SBR was carried out in an inter-
nal mixer (Haake Rheomix) by using 3-Octanoylthio-
1-propyl triethoxysilane and MBT. The proof of successful
grafting of propyltriethoxysilane onto the SBR backbone
by reactive grafting process was discussed in our earlier
DAS ET AL. 3117

communication.[24] We prepared a range of modified rub- T A B L E 2 Mixing procedure for compounds preparation
bers and characterized these elaborately in this paper. (internal mixer)

Cumulative
Mixing procedure time (min)
2.3 | Preparation of silane grafted SBR/ 1. Internal mixer
silica compounds
Silane grafted SBR mastication 2

SBR/ silica compounds were prepared, where the amount
of grafting of the base rubber and the contents of the
filler were varied. The formulation of various composi-
tions is given in Table 1. The preparation of these com-
pounds was done in an internal mixer.
A Haake Rheocord having a capacity of 85 cm3 and
the fill factor of 0.7 was used to carry out the mixing and
evaluate the mixing properties of silane grafted SBR with
highly dispersible silica. A volume of 85 cm3 of each for-
mulation was introduced in a Haake internal mixer and
the mixing was done for 18 minutes at 60 rpm at 130
C.
The torque corresponding to the shear resistance devel-
oped during the mixing was recorded with time for each
formulation.
The mixing procedure of all the formulations in an
internal mixer and two-roll mill is given in Table 2,
where first half of mixing was performed in a Haake
Rheocord for 19 minutes. At first silane grafted SBR was
mixed for 2 minutes to reduce the viscosity of the rubber
matrix. Then 50% of silica was added for 2 minutes and
kept 2 minutes for mixing. After that, another half of sil-
ica, carbon black and TDAE oil were added carefully for
2 minutes to disperse in the mix properly. It was kept for
3 minutes to mix all the fillers properly with the silane
grafted SBR. Then, ZnO, stearic acid and 6PPD were
Addition of 50% of silica 4
Addition of remaining silica, Carbon 5
black, and TDAE oil
Addition of ZnO, stearic acid and 6PPD 8
2. Two roll mill
Mixing of curatives and sheeting out 2
added subsequently for 2 minutes and kept 6 minutes for
mixing. After 19 minutes of mixing in an internal mixer,
the samples were cooled at room temperature and rub-
ber/silica compound was taken in a two-roll mill to mix
with the curatives for 2 minutes and sheeted out.
2.4 | Characterization techniques
NXT-g-SBR/silica vulcanizate sample for morphology
and dispersion study was prepared by a compression
molding technique to obtain a cryosection of about 2 mm
thickness at 150
C. A Field Emission Scanning Electron
Microscope (FESEM) of ZEISS (Germany) at an accelera-
tion voltage of 20 kV was used for the cryofractured sam-
ple. To avoid the damage of the sample at the time of

TABLE 1 Mixing formulations of different NXT-g-SBR/silica compounds with different grafting percentage

Ingredients Parts per hundred parts of rubber (phr)

Varying grafting weight percentage (50 phr filler) Varying filler content (4 wt.% grafting)

B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8

SBR 1502 100 0 0 0
NXT-g-SBR (0%) 100(2%) 100(4%) 100(6%) 100 100 100 100
NXT silane 0 0 0 0 0 0 0 0
HD silica 50 50 50 50 0 15 25 35
N330 3 3 3 3 3 3 3 3
TDAE 10 10 10 10 10 10 10 10
ZnO 3 3 3 3 3 3 3 3
6PPD 1 1 1 1 1 1 1 1
Stearic acid 2 2 2 2 2 2 2 2
DPG 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
CBS 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6
Sulfur 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7
3118
electron discharge, a sputter coating of gold was applied
on to the sample.
Dispersion of silica in NXT-g-SBR /silica composites
was also done with the help of Atomic Force Microscopy
(AFM, Make-Park System NX10, South Korea) study
using tapping mode. The sample for the testing was pre-
pared by cleaning the surface of a square-shaped sample
by acetone at room temperature and followed by drying
in a vacuum drier. The tip radius was 10 nm. The force
constant of the tip was 10.769 N/m, and resonance fre-
quency was 330 kHz.
Fourier-transform infrared (FTIR) spectra of Attenu-
ated total reflection mode (A Perkin Elmer spectrum Two
IR spectrometer of 4 cm−1 resolution), USA was used to
acquire the IR spectra of the samples within a range of
400 cm−1 to 4000 cm−1 using a ZnSe prism. An average
of five scans was done for each sample.
Bound rubber content of the uncured rubber com-
pound without any curative was measured by putting a
small amount of compound (0.5 g) into a filter paper in
toluene. It was kept for 72 hours, and the toluene was
changed after every 24 hours. The sample was then
removed from toluene and kept at 50
C for 24 hours to
constant weight. Bound rubber content was measured by
the following equation,
m −ms
Bound rubber content ð%Þ = × 100: ð1Þ
mr
Where m is the weight of the total compound after tak-
ing out from the solvent, ms is the weight of the silica pre-
sent in the sample, and mr is the total weight of the rubber.
Calculation of the Payne effect was done by the Strain
sweep measurements in RPA 2000, where strain was var-
ied from 0.56% to 100%, 0.5 Hz frequency at 100
C. Payne
effect was calculated from the difference in storage shear
modulus at 0.56% and 100% strain.[25]
The swelling studies of the rubber vulcanizates were
carried out. The vulcanized sample was kept in toluene
at ambient conditions (27
C) for 3 days. Vr, which is the
volume fraction of SBR in the swollen gel, was calculated
using Equation (2).


Ds − F f Aw ρr− 1
Vr =
 ð2Þ
Ds −F f Aw ρr− 1 + As ρr− 1
Where,
Aw = Weight of the swollen test specimen.
Ds = De-swollen weight of the test specimen.
Ff = Weight fraction of insoluble components.
As = Weight of absorbed solvent corrected for swell-
ing increment.
DAS ET AL.
ρr = Density of rubber.
ρs = Density of the solvent.
The apparent cross-link density of silica-reinforced
NXT-g-SBR vulcanizates was calculated according to
Flory-Rehner equation (Equation 3) using the value
of Vr.[26]
 
  ρr 1=3 Vr
− lnð1 −Vr Þ + Vr + xV2r = × Vs Vr − : ð3Þ
Mc 2
Where,
x = Flory-Huggins polymer-solvent interaction
parameter.
ρr = Density of rubber.
Mc = Molecular weight between cross-links.
Vs = Molar volume of the solvent.
For each sample, three experiments were performed.
The mean was found to be ±0.05% for the cross-link den-
sity measurement. Here, the value of x was taken as 0.390
for SBR-toluene system.[27] Vr represents the volume frac-
tion of rubber in swollen gel. ρr represents the density of
the rubber.
Mechanical properties of the NXT-g-SBR/silica com-
posites were studied by using Zwick UTM, Model - Z010
(Zwick GmbH and Co., Germany) at a 500 mm/min
cross-head speed at 25
C. Dumb-bell shaped specimens
were punched out from a 2 mm thick molded sheet
according to ASTM D 412-98 and the average of three
tests was reported here.
Low strain modulus (Emod) of rubber/silica compos-
ites, which is the ratio of σ/ϵ (where σ and ϵ are stress
and strain respectively of the composites), was calculated
from the slope of the stress-strain curve in the low defor-
mation range (below 50% elongation). In this range,
stress-strain plot is linear.
The tear strength of the vulcanized rubber sheet was
measured, by using a Zwick Roell Z101 after cutting a
crescent-shaped specimen of 2 mm thickness, at a cross-
head speed of 500 mm/min following the ASTM D624.
Dynamic mechanical analysis data was reported
by analyzing the specimen in Anton Paar (Modular
Compact Rheometer 102). A sample (35 mm ×
7 mm × 2 mm) was cut from the vulcanized rubber
sheet. The sample specimen was analyzed in torsion
mode and the temperature range was from −80 to 100
C
with 10 Hz frequency, at a heating rate of 5
C/min and
0.01% strain.
Nanoindentation studies of the specimens were done
in a Nano indenter (TI-950) (Hysitron Inc., USA). The
nanoindenter was subjected to 1500 nm constant depth
into the material.
The hardness of all the composites was calculated by
the following equation,
DAS ET AL.
Pmax
H= : ð4Þ
Aðhc Þ
Where Pmax is the maximum force calculated from
the plot and A(hC) projected contact area (AP) between
the indenter and the specimen. The projected contact
area of the indenter of known geometry can be calculated
by the use of contact depth (hC) and probe area function
(A) with the equation as follows[28]:
Ap = Aðhc Þ = 24:5ðhc Þ:
For an ideal Berkovich probe, the value of area func-
tion was taken as 24.5. Now, the contact depth (hc) can
be calculated by maximum depth (hmax), maximum load,
stiffness, and indenter geometry constant (ε) as
pmax p + 3:9201 × 10 − 6 ðx =sÞ4 :
hc = hmax −ϵ = hmax – 0:75 max :
s s
Where the geometric constant of Berkovich indenter
was taken as 0.75. The stiffness (S) was calculated from
the slope of the initial portion of the unloading curve that
is, S = dP/dh.
The reduced modulus of the of the composites was
calculated from the following equation,
pffiffiffi
1 π S
Er = pffiffiffiffiffiffiffiffiffiffiffiffiffiffi :
β 2 AP ðhc Þ
Where Er is thee reduced modulus, β is the geometrical
constant, and S is indicating the stiffness of the contact.
2.5 | Filler flocculation rate (FFR)
measurement
The filler flocculation rate (FFR) of the uncured
SBR/silica compounds was studied by RPA at 100
C tem-
perature, a strain of 0.56%, and a test time of 70 to
140 second. The storage shear modulus was recorded at
different measurement times.
The silica filler flocculation rate was calculated using
the following equation,

 ΔG00:56
FFR MPa:Sec − 1 = : ð8Þ
Δt
Where FFR is the filler flocculation rate, ΔG00:56 is the
difference in storage shear modulus at 0.56% strain
between G00:56 ðt Þ and G00:56i , where G00:56 ðt Þ is the storage
modulus at test time t, and G00:56i is the initial storage
3119
modulus at ti. Δt is the difference in final time and initial
time. The initial time for the measurement was 70 second.
3 | RESULTS A ND DISCUSSION
3.1 | SEM studies
A clear picture of dispersion of nanosilica in NXT grafted
SBR/silica matrix was given by SEM. The dispersion
ð5Þ degree of nanosilica was quantified by dispersion degree
parameter, dispersion index (DI).[26,29] DI is formulated
as, following the earlier papers:
DI = 1:1539 × 10 − 2 + 7:5933 × 10 − 2 ðx =sÞ
+ 6:6838 × 10 − 4 ðx =sÞ2 −1:9169 × 10 − 4 ðx =sÞ3
ð9Þ
ð6Þ
Where s stands for SD.
Mean and SD have been calculated from the inter-
particle distance by using these expressions
X Xi
x = : ð10Þ
iN
and
ð7Þ sP
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
x Þ2
i ðx i −
s= respectively: ð11Þ
ðN −1Þ
DI is defined as the free path distance (interparticle
distance) distribution between the nanoparticles, which
lies in the range of 0.9 x to 1.1 x . x is the mean spacing
between the nanofillers. Higher the value of dispersion
degree parameter, better will be the dispersion. The dis-
persion will be very high if the value of DI is high. Inter-
particle distance distribution follows a Gaussian
distribution model, as shown in Figure 1.
Figure 1A-D shows the SEM image of the different
SBR/silica composites with varying grafting weight percent-
age at 4 phr of silica loading and Figure 1E displays the
image for 50 phr of silica loading and 4% grafting. To quan-
tify the state of dispersion of these composites the grey
images obtained from the SEM were processed using Image
J software.[26[ Contrast of the SEM image was increased by
this software to measure the interparticle distance properly.
The interparticle distance was determined by using a line
tool randomly from the center of a particle to another parti-
cle, as shown in Figure 2. Several measurements (N ≥ 200)
of the interparticle distance were done and histogram from
those data was constructed. The value of x /s was calculated
3120
using a lognormal fit imposed on the histogram. Table 3
shows that average interparticle distance increased with
increasing grafting weight percentage at 4 phr of silica
loading as more number of propyltriethoxysilane moie-
ties would be available to react with the hydroxyl groups
on the silica surface.
Figure 1A'-D' shows the histogram of interparticle dis-
tance data of different composites. As shown in this
Figure 1, the mean interparticle distance of the compos-
ites shifted towards right and increased with grafting
DAS ET AL.
F I G U R E 1 SEM image and respective distribution
of SBR/silica composites (4 phr of silica loading) at 0%
grafting (A and A'), 2% grafting (B and B'), 4% grafting
(C and C'), 6% grafting (D and D') and 50 phr silica
loading at 4% grafting (E and E')
weight percentage but decreased at higher amount of sil-
ica loading (50 phr) as compared to the low amount of
grafting (4%). These two cases should be treated sepa-
rately. The latter case might be due to the fact that more
number of silica failed to react with the 3-Octanoylthio-
1-propyltriethoxysilane moiety, available in the SBR
matrix, increasing the probability of aggregation and as a
result reducing the interparticle distance and DI. As
shown in Table 3, DI of the composites increased with
grafting weight percentage at 4 phr silica loading and
DAS ET AL.
F I G U R E 2 Measurement of interparticle distance through
image J software (0% grafting and 4 phr of silica loading) [Color
figure can be viewed at wileyonlinelibrary.com]
decreased with filler loading at a constant level of
grafting (4%). The silica was dispersed uniformly in
3-Octanoylthio-1-propyltriethoxysilane grafted SBR
matrix.
As shown in Figure 1, the median of the gaussian dis-
tribution of the interparticle distance of silica particle
(4 phr) was shifted towards the right at a higher value.
The mean interparticle distance in the B-1, B-2, B-3, and
B-4 samples was 153, 274, 455, and 630 nm respectively.
With the help of calculated interparticle distance and the
SD, as shown in Table 3, we have calculated the DI. The
value of the DI is the direct measure of the silica disper-
sion in the NXT-g-SBR/silica composites, which
increased with increasing grafting weight percentage.
Higher value of DI means less number of filler aggregate
present in a particular surface area of the rubber/silica
composites at a constant loading of filler.
3.2 | AFM studies
Three-dimensional topographical analysis of silica aggre-
gates on the surface of the composites and morphological
analysis of their dispersion state was carried out using
TABLE 3 Mean, SD and dispersion degree parameter of different composites
B-1 (0%)
B-2 (2%)
4 phr silica
Mean (x ), nm 153.28 274.92
SD (S) 78.32 126.25
x /s 1.95 2.17
DI (%) 16.15 17.84
3121
AFM. Images were analyzed and acquired with XEI data
processing and analysis software using tapping mode.
The particle heights were measured using this software
to analyze a wide range of particle size parameters for
each composite cluster, and measurement statistics for
the set.[30]
The sequence of 10 μm2 scan range images is shown
in Figure 3. Table 4 shows how the particle number den-
sity decreases with level of grafting. The median of the
particle height distribution in Figure 3 shifted towards left
(low particle height), indicating the reduction of silica
aggregate size, and consequently increasing dispersion of
silica. In Figure 3E' median of particle height distribution
shifted towards right at high particle height which repre-
sents the increasing filler-filler interaction with the filler
loading. As shown in Figure 3, silica nanoparticles are
found in clustered form in various regions of the molded
surface of the pristine SBR/silica vulcanizates, leaving
out the areas without any silica. Compared to the silane
grafted SBR composites, a significantly greater aggrega-
tion of the particles can be observed on the composites
with 0% grafting. Number of detected particle per clusters
decreased with increasing grafting weight percentage
because of higher rubber-filler interaction than the
filler-filler interaction. High rubber filler interaction
results in good silica dispersion in 3-Octanoylthio-
1-propyltriethoxysilane grafted SBR. With increasing filler
loading, number of detected particles per cluster increased
as the filler-filler interaction increased. The brighter
regions in the height image represent the stiffer regions
and the softer domains are less bright.
The images have clearly shown the changes occurring
in the composite surface structure with increasing
grafting weight percentage. The number of particles per
cluster decreased and the particle height decreased as the
grafting wt.% increased. This was because aggregates size
was reduced with the increasing degree of dispersion as
shown by SEM in Table 4.
Additional surface analysis to quantify the surface
morphology of the composites was investigated by mean
roughness, Ra, measurements.[1] The height image of
SBR/silica composites for scan areas of 10μm2 and 40μm2
B-3 (4%) B-4 (6%)
B-3 (4%)-50 phr of silica
455.80 630.00 250.47
188.47 143.73 110.33
2.41 4.38 2.27
19.69 34.50 18.52
3122
containing 0, 2, 4, 6 wt% of grafting at 4 phr of silica
loading and 4% grafting at 50 phr of silica loading is
shown in Figure 4. The cross-section of the height-
profiles was taken along the red lines; for all the height-
profiles, the Y-axis was adjusted to 120 nm for 10 μm2
and 160 nm for 40 μm2 to make the height profiles com-
parable. Ra increased strongly with the increasing
grafting wt. % and was 12.87 nm and 24.76 nm for
10 μm2 and 40 μm2 scan areas respectively at 6 wt%
DAS ET AL.
F I G U R E 3 AFM image and respective particle height
distribution of SBR/silica composites (4 phr of silica
loading) at 0% grafting A and A', 2% grafting B and B', 4%
grafting (C and C'), 6% grafting (D and D') and 50 phr
silica loading at 4% grafting (E and E') [Color figure can be
viewed at wileyonlinelibrary.com]
grafting. For 50 phr of silica loading Ra value is
17.82 nm and 29.24 nm for 10 μm2 and 40 μm2 scan
areas respectively at 6 wt% grafting (Table 4). The trend
is the same as observed at the lower loading. The
increasing value of composite surface roughness with
grafting weight % means increasing number of individ-
ual filler particles on the composite surface that is, the
lower number of aggregates/agglomerates and high
mean surface roughness at high amount of silane
DAS ET AL. 3123

TABLE 4 Particle/cluster, particle height, and mean roughness of NXT-g-SBR vulcanizates

Mean roughness, Ra (nm) Particle height (nm)

Sample (4 phr silica) No. of detected particle/clusters 10 μm2 40 μm2 Mean SD

B-1A (0% grafting) 138 6.24 15.62 29.41 6.44
B-2A (2% grafting) 127 8.43 21.56 23.41 5.47
B-3A (4% grafting) 117 9.71 22.94 22.60 7.28
B-4A (6% grafting) 116 12.87 24.76 22.58 6.24
Sample (50 phr silica)
B-1 (0% grafting) 293 9.65 19.15 58.84 3.71
B-2 (2% grafting) 285 12.32 24.70 55.37 3.06
B-3 (4% grafting) 278 15.95 27.46 45.45 5.32
B-4 (6% grafting) 271 17.82 29.24 33.35 2.21

grafted composite. For Figure 4E, E' (composite with
50 phr of silica), Ra is higher than the other low phr sil-
ica composites. This is because instead of the filler-filler
aggregation of the high phr silica containing rubber/sil-
ica composites more number of silica particles in a par-
ticular surface area is available.
3.3 | ATR-FTIR analysis
Figure 5A shows the FTIR spectra of pristine SBR,
SBR/silica composites where the silane was added sepa-
rately and NXT-g-SBR/silica composite at 4% grafting
level and 4 phr of silica loading. FTIR spectrum of NXT-
g-SBR/silica composites shows the characteristic peaks,
where the peaks at 2844 and 2918 cm−1 are for asym-
metric CH stretching, the peak at 1080 cm−1 is attrib-
uted to the asymmetric vibration of Si-O-C or Si-O-Si
bond, the Si-O-Si skeletal stretching is found at
798 cm−1 and 459 cm−1 peak is attributed to Si-O-Si
bending vibration. The peaks at 2973, 2927, and
2856 cm−1 are attributed to -CH2 stretching vibrations
of 3-Octanoylthio-1-propyltriethoxysilane (NXT silane).
The peak at 1693 cm−1 is due to the C=O stretching
vibration of the silane. The peaks at 1106 and 1075 cm−1
correspond to the alkoxy C-O stretching peak of the “Si-
O-CH2CH3” group of silane. The peak at 1100 cm−1
attributed to Si-O-Si bond, which was newly formed due
to the interaction of silane coupling agent with silica,
merged with the peak at 1080 cm−1 and broadened
it. The peak intensity at 1080 cm−1 increased and broad-
ened after grafting of silane with the SBR in NXT-g-
SBR/silica composite. The intensity of the peaks in the
FTIR spectra reveals better interaction of silica with the
NXT grafted SBR than the system having external addi-
tion of silane. Filler-filler interaction of silica was
reduced after grafting of propyltriethoxysilane moiety of
NXT silane onto SBR chain.
Figure 5B depicts the FTIR spectrum of NXT-g-SBR/
silica composites with varying grafting percentage. It can
be seen that with increasing grafting percentage, the peak
intensity and peak area at 1080 and 459 cm−1 are increas-
ing, which are indication of increasing rubber-filler inter-
action. A possible bonding mechanism between silica
and grafted silane on the SBR backbone is shown in
Figure 6. The silanol groups present on the silica surface
can form hydrogen bonding between the silica particles
and help in aggregation of the particles. These aggregated
silica particle can form agglomerates after mixing. This
reformation of silica particle aggregates is called agglom-
erate which increases with the heat treatment at the time
of mixing or molding.[31,32] As shown in Figure 6, silica
particles would form Si-O-Si bonds with the grafted
alkoxysilane moiety by the process of hydrolysis and con-
densation and the degree of dispersion is also increased
by this process.[33,34]
3.4 | Torque time curve of NXT-g-SBR/
silica compounding in an internal mixer
(Haake Rheocord)
In Figure 7, the mixing torque vs time are shown for the
NXT grafted rubber- silica composites where the later stage
of the mixing displays the clear difference. The mixing tor-
que value after adding the ingredients can be considered as
a measure of the viscosity of the mix.[35] The torque during
the final stage of mixing at high temperature decreased with
increasing grafting weight percentage due to increased rub-
ber filler interaction, as shown in Figure 7A.
The compound viscosity decreased due to the
shielding of the hydrophilic surface of the silica with the
3124
F I G U R E 4 AFM height image and height profile (cross-
section) image of SBR/silica composites at 0% grafting A, and A', 2%
grafting B, and B', 4% grafting C, and C', 6% grafting D, and D' and
50 phr silica loading at 4% grafting E and E' [Color figure can be
viewed at wileyonlinelibrary.com]
alkoxy groups of the propyltriethoxysilane moiety grafted
on the SBR polymer backbone and consequently a lower
mixer torque had resulted. The lower mixing torque also
yielded lower viscous dissipation and in turn, lower heat
generation.[36]
DAS ET AL.
After the addition of the last ingredient, the plot of
mixing torque vs mixing time shows an exponential drop,
to some limiting value P∞. These data can be fitted by the
following Equation.[37,38]
pt − p∞
ln = −K:t: ð12Þ
p0 −p∞
Where p0, pt, and p∞ represent the torque values just
after the addition of the last ingredient at 12 minutes,
the torque at time t and the limiting torque after long
mixing. The total change in torque (p0 − p∞) can be rep-
resented as a measure of the initial volume of occluded
rubber and (pt − p∞), is proportional to the volume of
occluded rubber at the time't'. The constant 'K' repre-
sents the rate at which the filler is dispersed. The pro-
cess obeys the first-order kinetics as seen from the above
equation.
The efficiency of mixing of the filler in rubber was
evaluated from the rheograms using Equation 12. The
slope values indicate that with increasing grafting
weight percentage (Group-1), efficiency of mixing silica
in SBR has increased considerably (Table 5). With
increasing filler loading (Group-2) slope (-K) decreased
initially, indicating the decreasing mixing efficiency at a
constant level of grafting (4%). The final torque value
was also increased with the filler loading in group-2.
The mixing efficiency, as given by the slope (-K), is
given in Table 5.
3.5 | Bound rubber content and Payne
effect measurement of rubber/silica
compound
Bound rubber content of SBR/silica compounds
increased with the amount of grafting. As shown in
Figure 8A, the value of bound rubber content was 53%
for the NXT-g-SBR/silica compound (when the grafting
level was 6%) and the same for the pristine SBR/silica
compound was 42% with 0% grafting. The bound rubber
content obtained is attributed to the chemical bond
attached to the siloxane and silanol group attached to the
silica surface. NXT-g-SBR/silica composite was most
effective to form chemical bonds with the silica surface
than the pristine SBR/silica composite, and the interac-
tion was increased with increasing amount of grafting.
The direct indication of the strength of the filler-
filler networks is the difference between storage shear
modulus at 0.56% and 100% strain (Payne effect).
Figure 8B represents the Payne effect plot of different
SBR/silica composites. Pristine SBR/silica composite
showed maximum value of delta G' and NXT silane
DAS ET AL. 3125

F I G U R E 5 FTIR analysis of rubber/ silica vulcanizates to show the interaction between silica with the NXT-g-SBR [Color figure can be
viewed at wileyonlinelibrary.com]

F I G U R E 6 Interaction model of NXT-g-

SBR polymer chain with the silanol group of
silica surface [Color figure can be viewed at
wileyonlinelibrary.com]
3126 DAS ET AL.

F I G U R E 7 Mixing torque vs time curve of different rubber silica composites with A, varying grafting weight percentage and B, varying
filler loading [Color figure can be viewed at wileyonlinelibrary.com]

TABLE 5 Filler mixing studies (Haake Rheocord)

Mixing parameters

Temp Temp Final mixing Mixing Torque Slope

Groups Sample (Initial)
C (Final)
C torque (Nm) (Nm. min.) (-K)
Group- B-1(0% 100 149 32.3 545 −0.133
1 grafting)
B-2(2% 100 126 23.5 539 −0.083
grafting)
B-3(4% 100 159 18.6 418 −0.074
grafting)
B-4(6% 100 147 17.5 385 −0.079
grafting)
Group- B-5 (0 phr 100 132 11.7 243 −0.068
2 filler)
B-6(15 phr 100 142 15.2 311 −0.052
filler)
B-7(25 phr 100 145 17.3 351 −0.062
filler)
B-8(35 phr 100 146 19.2 395 −0.070
filler)

grafted SBR/silica composite showed minimum value of
delta G'. The reduction of the delta G' is due to the
improved dispersion of the silica particle in the modified
rubber composite, reduced filler flocculation and
improved rubber-filler interaction. Pristine SBR/silica
composites where the same amount of silane added sep-
arately at the time of mixing showed higher value of
delta G' than the grafted composite, which indicates bet-
ter dispersion of filler and better rubber-filler interac-
tion than the latter.
3.6 | Filler Flocculation rate
measurement of rubber/silica compounds
Figure 8C shows the plot of filler flocculation rate vs
bound rubber content of SBR/silica compounds. The plot
shows maximum filler flocculation rate (0.0145 MPa.
Sec−1) for pristine SBR/silica compound where no silane
was added externally at the time of mixing. The value of
FFR decreased with increasing bound rubber content.
Tendency for filler flocculation reduced as the higher
DAS ET AL.
F I G U R E 8 A, plot of bound rubber content with Dispersion Index (DI), B, plot of Payne effect measurements of different SBR/silica
compounds, and C, plot of filler flocculation rate vs bound rubber content of different rubber silica compounds [Color figure can be viewed
at wileyonlinelibrary.com]
amount of bound rubber leads to a lower filler-filler inter-
action.[39] The value of flocculation rate decreased when
silane was added separately. The lowest value
(0.0026 MPa. Sec−1) was obtained when 100% NXT-g-
SBR with 9.5% grafting level was used as a base rubber
for the compound. This is because of the decreased filler-
filler interaction and increased rubber-filler interaction
after grafting base rubber with the silane.
3.7 | Cure characteristics of rubber/silica
composites
Table 6 shows that the effect of grafting weight percent-
age and silica loading on the cure properties of vulca-
nized NXT grafted SBR silica composites. The data were
calculated from Figure 9, plotting torque against time. As
shown in the table, optimum cure time decreased as well
3127
as the cure rate index increased with increasing grafting
weight percentage at the same phr of filler loading. This
is because with increasing amount of grafting more pen-
dent propyltriethoxysilane groups are available to react
with the surface silanol groups of silica. Thus, less num-
ber of “OH” groups on silica surface is available which is
acidic and could react with the basic accelerators. More
number of accelerators are available to take part in the
curing reaction. Optimum cure time and torque differ-
ences increased with increasing filler content because
silanol groups present on the silica surface are acidic
which can easily interact with the basic accelerator.[40]
On increasing filler loading, the cure rate increased ini-
tially, whereas the optimum cure time was enhanced
because of the filler effect and excess silanol groups.
As shown in Table 6, scorch time decreased with
increasing grafting weight percentage at constant filler
loading and increased with increasing filler loading at a
3128 DAS ET AL.

TABLE 6 Curing parameters of different rubber/silica composites

Opt. Cure time

Groups Sample Cure rate index (min−1) MH (N.m) ML (N.m) Scorch time, Ts2(min) (TC90) in minutes
Group-1 B-1 10.70 8.43 1.84 10.23 19.5
B-2 15.64 5.16 1.08 8.64 15.0
B-3 23.36 6.73 1.31 8.20 12.4
B-4 23.46 8.14 0.96 7.96 12.2
Group-2 B-5 7.52 3.86 0.63 6.18 11.0
B-6 22.67 5.41 0.74 6.77 11.1
B-7 23.44 6.82 0.85 6.78 11.7
B-8 23.97 6.15 1.08 7.34 19.4

F I G U R E 9 Plot of cure curve of rubber/silica composite A, with varying grafting weight percentage at 50 phr of silica loading, and B,
with varying silica loading [Color figure can be viewed at wileyonlinelibrary.com]

constant percentage of grafting. This is because, with a
higher amount of grafting, more propyltriethoxy silane
moieties are available to react with the silica surface,
which leads to decreased curatives adsorption on silica
surface as a result of lower hydrophilicity on the silica
surface. The opposite thing is happening in the case of
increasing filler loading where more hydrophobic silica
would be available to react with the curatives.
3.8 | Swelling studies
Figure 10A,B shows the plot of apparent cross-link den-
sity of different vulcanizates with varying grafting weight
percentage (Group-1) and filler loading. As shown in
Table 7, apparent cross-link density of the vulcanizates
increased with increasing grafting weight percentage and
filler loading. The effect of cross-link density was
reflected on its vulcanizate properties. With the
increasing amount of grafting, more number of
alkoxysilane site will be present to react with the silica
surface as well as more number of grafted propyltriethoxy
silane moiety from two or more polymer chain can react
with each other forming Si-O-Si bonds, thus producing
additional interaction to increase the cross-link density.
With increasing filler loading, more number of filler sites
was available to interact with the silane, which increased
polymer-filler interaction. For the composites where pris-
tine SBR was used (Group-3) as base rubber cross-link
density increased with the filler loading but the incre-
ment was less than silane grafted SBR/silica composites
(Group-2). There is less improvement of cross-link den-
sity for the silane grafted and non-grafted vulcanizates
with 0 phr of silica. After adding silica, the difference
between the cross-link densities is prominent between
Group-2 and Group-3 curve which indicates the better
rubber-filler interaction and good dispersion of silica in
silane grafted SBR matrix. The extent of rubber-filler
DAS ET AL. 3129

F I G U R E 1 0 Plot of apparent cross-link density of different rubber silica vulcanizates with A, varying grafting weight percentage,
and B, varying filler loading (0% and 4% grafting) [Color figure can be viewed at wileyonlinelibrary.com]

TABLE 7 Comparison of cross-link density of various NXT-g-SBR/silica composites at different grafting weight percentage and filler
loading

Groups Sample Vr Apparent cross-link density × 10−4 (mol/cm3)

Group-1 (50 phr of silica) B-1 (0% grafting) 0.245 6.20 ± 0.06
B-2 (2% grafting) 0.276 8.15 ± 0.12
B-3 (4% grafting) 0.271 8.40 ± 0.05
B-4 (6% grafting) 0.294 10.28 ± 0.08
Group-2 (4% grafting) B-5 (0 phr silica) 0.188 3.13 ± 0.01
B-6 (15 phr silica) 0.216 4.45 ± 0.05
B-7 (25 phr silica) 0.247 6.36 ± 0.02
B-8 (35 phr silica) 0.265 7.70 ± 0.06
Group-3 (0% grafting) B-9 (0 phr silica) 0.180 2.81 ± 0.03
B-10 (15 phr silica) 0.204 3.86 ± 0.06
B-11 (25 phr silica) 0.216 4.44 ± 0.03
B-12 (35 phr silica) 0.239 5.83 ± 0.05

interaction is also influenced by the filler aggregation in
the rubber matrix at higher concentrations. Some effect
of increasing cross-link density is reflected on the various
physico-mechanical properties of the nanocomposites in
the subsequent sections
With increasing silane grafting, chemical interaction
through propyltriethoxy silane moiety between the rub-
ber and silica surface increased (Figure 6). There is a
chance of the grafted silane moiety to react between
themselves and act as an additional interaction between
the two phases and increase the cross-link density. How-
ever, there is a very small difference in cross-link density
between only grafted and non-grafted rubber composites
without any silica loading, as mentioned above. In
Figure 10B, we can see that after the interaction of the
grafted silane with silica filler, the cross-link density of
the composites was much more improved.
3.9 | Tensile strength, modulus and tear
strength measurement
Figure S1 (S for supporting information) shows the
stress-strain plot of NXT-g-SBR silica composites by vary-
ing grafting weight percentage and filler loading. The eth-
oxy groups attached on one side of the NXT silane
chemically react with the hydroxyl groups on the silica
surface at the mixing stage via hydrolysis mechanism as
3130
shown above in Figure 6. The mechanical property of the
vulcanizates increases due to the formation of a stable
silica-silane-rubber network. With the increasing amount
of grafting, tensile strength and modulus increased and
elongation at break decreased.
The improvement of the tensile strength and the low
strain modulus (Emod) in the silica reinforced NXT-g-SBR
vulcanizates, is due to the higher degree of dispersion with
increasing grafting weight percentage as well as better
rubber-silica interaction leading to the reinforcement. This
would help in better stress transfer. At the same time, the
higher cross-linking density of NXT-g-SBR vulcanizates
due to good dispersion increases the rubber molecular
chain rigidity and consequently there is a decrease in the
elongation at break. In order to prove this, tensile strength,
low strain modulus and elongation at break are plotted
against DI in Figure 11A. It is clearly demonstrated that as
the dispersion is improved, the tensile strength and modu-
lus are enhanced at 50 phr filler loading, but the elonga-
tion at break reduced gradually.
F I G U R E 1 1 Plot of A, tensile strength, Emod, and elongation at break vs dispersion index of rubber/silica composites with varying
grafting weight percentage, B, linear fit of increasing Emod with grafting weight percentage, and C, plot of tear strength with dispersion index
(DI) [Color figure can be viewed at wileyonlinelibrary.com]
DAS ET AL.
From the plot in Figure 11B, we can formulate rela-
tionship between the modulus and grafting level of NXT-
g-SBR/silica composites at 50 phr of silica loading
(Figure 11B) as shown in Equation 13.
From linear fit of Figure 11B, we can derive the fol-
lowing equation,
E mod = 1:923 + 0:169 × %grafting: ð13Þ
Where,
Emod = Modulus of the NXT-g-SBR silica composites
at 50 phr of silica loading.
% grafting = Weight percentage grafting of the base
rubber grafted with NXT silane.
Figure 11C shows the effect of DI on tear strength. The
tear strength increased with the increasing DI due to the
increasing rubber-filler interaction. The value of tear
strength is lower for SBR/silica composite with 0% grafting
due to the silica nanoparticles agglomeration, which reduces
the role of nano silica in reinforcing rubber composites.[41]
DAS ET AL. 3131

3.10 | Dynamic mechanical property
measurement
Dynamic mechanical analysis of all the composites has
been done to assess the effect of grafting wt% and filler
loading on the viscoelastic properties. It was reported that
loss tangent (tan δ) at 50
C to 80
C is an indirect measure
of the rolling resistance, and the lower the value of tan δ
at this high temperature, the better will be the rolling
resistance.[42-44]
The tan δ value of silica reinforced NXT-g-SBR vulca-
nizates is shown in Figure 12. NXT-g-SBR/silica vulcani-
zates show better rolling resistance property than the
pristine SBR/silica vulcanizates. The value of tan δ at
50 to 80
C, which is an indirect measure of rolling resis-
tance, improves with the increasing amount of grafting.

FIGURE 12 Temperature dependence plot of tan δ (−80 to 80
C) of silica reinforced NXT-g-SBR vulcanizates with A, varying grafting
wt.-% and B, varying silica loading (phr), C, Storage modulus (E') vs temperature plot of silica reinforced NXT-g-SBR vulcanizates with
varying grafting wt%, D, plot of tan δ and storage modulus vs dispersion index (DI), and E, Storage modulus (E') vs temperature plot of silica
reinforced NXT-g-SBR vulcanizates with varying silica loading (phr) [Color figure can be viewed at wileyonlinelibrary.com]
3132
Tan δ peak height also decreased with the increasing
amount of grafting as the segmental mobility of the SBR
polymer chain was reduced as a result of improved inter-
action with silica after grafting.
From Figure 12B, it can be seen clearly that the
rolling resistance of the composites are improved with
increasing filler content. This can be attributed to the
strong SBR-silica interaction and good dispersion of sil-
ica. The tan δ peak value decreases with increasing filler
loading due to the hindering segmental motions of poly-
mer chains resulting from the incorporation of nano-
silica, interaction of SBR with silica, and the increasing
cross-link density. There is no improvement of wet grip
property (tan δ at 0 to 10
C) with the increasing amount
of grafting in NXT-g-SBR/silica composites. This may be
due to the increasing cross-link density of the composites
with grafting percentage, which increases the storage
modulus.
Figure 12C shows the storage modulus (E') vs temper-
ature plot of different silica reinforced NXT-g-SBR vulca-
nizates which can be considered as a direct measure of
the filler reinforcement of the composite after increasing
amount of grafting in the nonpolar rubber matrix which
depends on the state of filler dispersion, and rubber-filler
interaction.
In this experiment, storage modulus at the rubbery
region was increased with an increasing amount of
grafting of the composites as shown in Figure 12C. This
is because of the increasing cross-link density due to the
increasing rubber-filler interaction as discussed in the
earlier section. With increasing degree of dispersion of
silica, rubber-silica interaction was improved. The tan δ
and storage modulus values in the region of 50 to 80
C
from Figure 12A and Figure 12C respectively are plotted
against DI in Figure 12D. The value of tan δ at higher
temperature decreased with the increasing DI of the silica
in the grafted rubber matrix as the grafting weight per-
centage increased. It can be notable that the value of stor-
age modulus increased with increasing DI and the
improvement is very significant for B-4 (6% grafting). The
same trend was found when amount of filler was varied.
Figure 12E depicts the increasing storage modulus with
increasing filler loading in the rubbery region. With the
increasing amount of filer loading reinforcement of the
NXT-g-SBR matrix was increased because of the increas-
ing the silica reinforcement.
3.11 | Nanoindentation studies
Nano indenter is an important tool to measure various
low strain mechanical properties such as hardness (H),
and reduced modulus (Er). At a fixed displacement of
DAS ET AL.
1500 nm, the load vs displacement curve of all the com-
posites was studied. Rubbers are very sensitive to loading
and unloading. The effect of nanoindentation and this
loading - unloading can be characterized by the measure
of reduced modulus (Er) and hardness. Figure S2a,b
shows the nanoindentation plot of load vs displacement
curve with varying grafting weight percentage and filler
loading. Compared with the three polymer composites,
the softer polymeric surface (B-1 with 0% grafting at
50 phr of silica) requires lower normal force to induce a
constant indenter penetration. More hysteresis loss can
be seen for pristine rubber/silica vulcanizate as the resid-
ual displacement of the loading -unloading curve after
withdrawal of the nano indenter at 0% grafting (the value
in B-1 in Figure S2a was maximum than the other three
curves). This is due to the less rubber- filler interaction of
the composite and reaggregation of filler.
The hardness and the reduced modulus (Er) of the
composites increased gradually with an increasing
amount of grafting and the amount of silica loading, as
shown in Figure S3a,b. The percentage improvement of
hardness was 21%, 56%, and 96% with increasing grafting
percentage over the pristine composite. With increasing
filler loading the improvement of hardness was 55%, 68%,
108%, and 189%. This increment of the hardness and the
reduced modulus (Er) value is an indication of the good
rubber-silica interaction after grafting. With increasing
filler loading the available functional group on the silica
surface increased to react with pendent ethoxysilane
groups. These increased amounts of covalent bond and
polar-polar interaction, in turn, increase the hardness of
the composite.
4 | CONCLUSIONS
This present study mainly focused on the dispersion of
nanosilica in 3-Octanoylthio-1-propyltriethoxysilane
grafted SBR and its effect on the properties of the
uncured and cured rubbers. The dispersion degree of
nanosilica was quantified by Dispersion degree parame-
ter DI. SEM studies show an improved degree of disper-
sion of silica with increasing grafting weight percentage.
The number of detected particle per clusters and the par-
ticle height decreased with the increasing degree of dis-
persion as shown by AFM. This indicated less number of
individual particles per cluster present with an increasing
amount of grafting. Interaction of NXT-g-SBR with silica
was shown by FTIR. A schematic of the interaction was
shown. Dispersion efficiency from the torque-time curve
displayed an increasing trend with the increasing amount
of grafting and decreased with the filler loading. Torque-
time curve from the internal mixer gave the dispersion
DAS ET AL.
rate, which improved with increasing grafting weight
percentage of the base rubber. Bound rubber content,
filler flocculation rate, and Payne effect measurement
indicated improved rubber-filler interaction of the com-
pound after grafting with the silane. Pristine SBR/silica
composite showed much higher value of delta G' than
that of NXT silane grafted SBR/silica composite. Filler
flocculation rate decreased with increasing bound rubber
content. Physico-mechanical properties of the composites
had shown constant improvement with improved
grafting percentage and filler loading. Tensile strength at
50 phr of silica loading was better than the other compos-
ite materials previously reported. Tear strength of the
composites gradually improved with the improved disper-
sion of silica. Better rolling resistance property of the vul-
canizates was found with the increasing amount of
grafting. The mechanical and dynamic mechanical prop-
erties were shown as a function of DI. The
nanoindentation studies gave further insight into the
results. This concept can be used in the tire industry, as
improved physico-mechanical properties could be
achieved by improved dispersibility of silica filler by
directly grafting the silane onto the rubber.
A C K N O WL E D G M E N T S
The authors are thankful to Indian Institute of Technol-
ogy Kharagpur (affiliated institute) for extending help
and cooperation to give us the research facility. They are
also grateful to MHRD, New Delhi; DHI, New Delhi and
Mutual Technologies Pvt. Ltd., Kolkata for providing a
research grant (UAY-HPN-IIT KGP-006) to Professor
Anil K. Bhowmick.
CONFLICT OF INTEREST
The authors declare no potential conflict of interest.
ORCID
Saikat Das https://orcid.org/0000-0002-0064-0310
Anil K. Bhowmick https://orcid.org/0000-0002-8229-
5353
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DAS ET AL.
SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Das S, Chattopadhyay S,
Dhanania S, Bhowmick AK. Improved dispersion
and physico-mechanical properties of rubber/silica
composites through new silane grafting. Polym Eng
Sci. 2020;60:3115–3134. https://doi.org/10.1002/
pen.25541