Chemical Engineering Journal Advances 11 (2022) 100349

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Chemical Engineering Journal Advances

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Treatment of natural rubber with bio-based components: A green endeavor

to diminish the silica agglomeration for tyre tread application
Abhijit Bera a, Debabrata Ganguly a, Sanjoy Kumar Ghorai a, Jyoti Prakash Rath b,
S. Ramakrishnan b, Job Kuriakose b, S.K.P. Amarnath b, Santanu Chattopadhyay a, *
a
Rubber Technology Centre, Indian Institute of Technology Kharagpur, Kharagpur-721302, WB, India
b
Apollo Tyres Limited, Chennai-600018, Tamil Nadu, India

A R T I C L E I N F O A B S T R A C T

Keywords: Production of green tyres by replacing carbon black (CB) with silica in natural rubber (NR) has gathered
Natural Rubber attention in automotive industries in the recent past. Incorporating high dosages of silica in NR by solid-state
Silica mixing is a huge challenge. In green tyre technology, abrasion resistance index (ARI) is crucial alongside roll­
Mechanical Properties
ing resistance, wet grip, and heat build-up. In this study, two new non-silane coupling agents have been intro­
Surface Treatment
duced to replace bis(3-Triethoxysilylpropyl)disulfide (TESPD). Amidst them, chemical-A (sorbitol) as an
Blocking Agents
Green Tyre alternate coupling agent of TESPD effectively achieved most properties except ARI. Hence, the naturally
Sustainable composite obtainable sustainable and cost effective chemicals A and B (B-sorbic acid) are incorporated during mastication,
acting as blocking agents. Consequently, chemical-A as a blocking agent executed remarkable improvement in
crucial properties, including ARI. Furthermore, the optimization study of sorbitol is accomplished based on
curing time, FTIR, and XPS analysis. Subsequently, using similar quantity (0.5 phr) sorbitol in silica-CB filled NR
compound evidenced better performances as tyre tread compound.

1. Introduction modulus of NR vulcanizates is evidenced due to the presence of amino

Unwanted components in natural rubber are corroborated and
composed of lipids, carbohydrates, and proteins (~5 to 7% w/v).
Moreover, the natural rubber molecules contain ω and α terminals.
Therein, the α terminal ends attach to long (1000 – 3000 units) cis-1,4
isoprene chains, and the ω terminal consists of two units of trans 1,4
isoprene segments. The hydrogen bond between α terminal and phos­
pholipid makes a link between them. On the other side, ω terminal as­
sociates with protein with the help of hydrogen bonding as well [1, 2, 3,
4]. In the case of silica-silane incorporated NR compound, there is al­
ways a competition between silane and protein regarding the hydro­
phobation on the surface of silica [5, 6]. However, the functional groups
present in the protein of NR create a chemical interaction with hydroxyl
groups of silica filler. The higher quantity of proteins stave the reactivity
of silane, and it helps suppress the grafting on silica surface by silane
polycondensation [7, 8]. According to Marcey and Gregg unwanted
components present in NR are responsible for higher tear strength, high
modulus, and faster scorch time of NR compound [9]. At low concen­
trations, protein acts as a reinforcing filler and cure activator. The rise in
acids and hydrolyzed constituents. It is primarily owing to arginine and
alanine, the neutral and basic amino acids, respectively. The presence of
unwanted components in NR creates an essential role in maintaining the
physical as well as dynamic properties of the compound. Thus, it is not
easy to get rid of those components from NR. Therefore, rather than
using a DPNR, blocking or modifying the functional groups of unwanted
components present in NR could be a probable solution regarding this
issue.
Sorbitol is a sugar alcohol, also known as d-glucitol, originating from
glucose within aldose reductase’s catalytic function [10]. This low
molecular weight polyol has versatile applications such as sugar sub­
stitute, health care, cosmetics, food, personal care, plasticizer, nucle­
ating agent, and other industrial uses [11, 12, 13, 14, 15]. In a recent
research study, assorted quantities of maltose, sucrose, fructose, and
glucose were embodied into synthetic isoprene (IR), deproteinized NR
(DPNR), and fresh NR (FNR) to stabilize and diminish the viscosity of
NR. Consequently, the proteins present in FNR minimized the ability of
monosaccharides to decrease the Mooney viscosity through the inter­
ference of Millard reaction between the monosaccharides and the

* Corresponding Author: Santanu Chattopadhyay, Ph- + (91) 9434055304, Rubber Technology Centre, IIT Kharagpur, PIN-721302, West Bengal, India
E-mail address: santanuchat71@yahoo.com (S. Chattopadhyay).

https://doi.org/10.1016/j.ceja.2022.100349

Available online 23 June 2022

2666-8211/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
A. Bera et al. Chemical Engineering Journal Advances 11 (2022) 100349

proteins in FNR [16]. Table 1

Sorbic acid (SA or chemical-B) is a cheap, readily available, and NR Compound formulation
ecologically secure natural organic compound. Generally used as a Ingredients Quantity (Phr)
preservative agent and extensively in food products, pharmaceuticals, Sample designation
and cosmetics to some extent [17, 18]. Each molecule of sorbic acid S2T S2A10 S2B10 S2AB10
NR: TSR-10 100 100 100 100
consists of two conjugated double bonds and one carboxyl group. This
CB: N134 30 30 30 30
typical structure is believed to be used as an interfacial modifier of filler HD Silica 20 20 20 20
and rubbers. According to Grussel. K. F et al., incorporation of Coupling agent TESPD:10 % Chemical A: Chemical B: Chemical
chemical-B in CB/ EPDM masterbatch increased crosslinked density of silica filler 10 % of silica 10 % of silica A&B: 10 % of
which radically provided extraordinary improvement in mechanical filler filler silica filler
Blocking agent - - - -
properties [19]. Formation of in-situ zinc disorbate (ZDS) was observed
(During
in the case of natural rubber and silica or halloysite incorporated rubber mastication)
compound [20, 21, 22, 23]. Moreover, SA assisted as an intermediate ZnO 4 4 4 4
linker between SBR and HNTs (halloysite nanotubes) through hydrogen Stearic acid 3 3 3 3
6PPD 2 2 2 2
bonding or grafting copolymerization mechanism [20]. It is also used as
TMQ 1 1 1 1
an eco-friendly curing agent in the EPDM rubber system besides Ozone 1 1 1 1
improving the filler dispersion in the compound [24, 25]. protecting
In the current article, at a fixed phr of total filler loading of silica/ CB wax PE
(20/30), the effectiveness of new non-silane coupling agents sorbitol Soluble Sulfur 1.5 1.5 1.5 1.5
DPG (Diphenyl 2 % of silica 2 % of silica 2 % of silica 2 % of silica
and sorbic acid over TESPD are examined by exploring the mechanical
guanidine) loading loading loading loading
and dynamic properties of the respective vulcanizates. Secondly, the TBBS 1.5 1.5 1.5 1.5
utility of using the same non-silane coupling agents as a modifying or
S2 – 20 phr silica and 30 phr CB,
blocking agent of unwanted components present in natural rubber. Af­
T – TESPD,
terward, the optimization study of chemical-A is carried out by
A10 – Chemical A (Sorbitol) 10% of silica loading
following the optimization cure time, and FTIR analysis of the entire B10 – Chemical B (Sorbic acid) 10% of silica loading
carbon black loaded NR compounds. Finally, a similar quantity of AB10 - Chemical A and B (Sorbitol: Sorbic acid = 50:50) 10% of silica loading
chemical-A is incorporated in silica-CB filled NR composites to confirm
the effectiveness of optimized phr of sorbitol in NR vulcanizates.
Table 2
2. Materials and methods Sample designation
Sample Blocking agent Coupling agent Other
2.1. Materials (during mastication) ingredients
A10S2T Chemical A: 10 % of silica TESPD:10 % of silica Similar
filler filler
Most of the compounding materials were used as supplied by Apollo
B10S2T Chemical B: 10 % of silica TESPD:10 % of silica Similar
Tyres (R&D, Chennai). These are: natural rubber (NR) – Technically filler filler
specified rubber (TSR-10), highly dispersible silica (HD silica) [grade- AB10S2T Chemical A&B: 10 % of TESPD:10 % of silica Similar
160007/ N2SA-182.54 (m2/g) by], carbon black (CB)-134 (SAF- super silica filler filler
abrasive furnace black) [N2SA-138.42 m2/g], zinc oxide (ZnO), stearic A1S2T Chemical A: 0.5 phr TESPD:10 % of silica Similar
filler
acid, very effective antiozonant and antioxidant – N-(1,3-dimethylbu­ A2S2T Chemical A: 1 phr TESPD:10 % of silica Similar
tyl)-N-phenyl-p-phenylenediamine (6PPD), antidegradant – 2,2,4-Tri­ filler
methyl-1,2-Dihydroquinoline polymer (TMQ), ozone protecting wax
PE, curing accelerator – N-Tertiarybutyl-2-benzothiazole sulfenamide
(TBBS), DPG – Diphenyl guanidine and curative - soluble sulfur. Silane Kingdom) and cooled to room temperature.
coupling agent – Bis-(triethoxysilylpropyl) disulfide (TESPD) were
purchesed from local suppliers (analytical grade). Chemical-A and 2.2.3. Mixing condition
chemical-B are the new non-silane coupling agents and the modifying or Fig.1
blocking agents procured from Sutaria Chemicals, Mumbai. AB is the
50:50 mixture of both chemicals A and B. 2.3. Testing and characterization of samples

2.2. Compound preparations
2.2.1. Rubber formulation
In this work, the formulation of the natural rubber compound was
followed, as mentioned in Table 1.
Table 2
2.2.2. Mixing procedure
The complete mixing was carried out through three stages, depicted
below as per the sequence. The rotor used was a tangential type rotor,
and the fill factor was about 0.65. After the 3rd stage mixing in Banbury,
the compound was passed through a two-roll mill to achieve a sheet of 8
mm thickness and stored for 24 h at ambient temperature. The optimum
cure time of the composites was determined by Moving Die Rheometer
(MDR 2000 Alpha Technologies, U.S.A) at 160◦ C for 30 minutes. Ac­
cording to the optimum cure time (Tc90), the molding was operated at
160◦ C using a compression molding machine (Moore Press, United
The rheological properties of the composites were tested at 160◦ C for
30 minutes using an MDR (Alpha Technologies) to understand the cure
characteristics. Also, the Mooney viscosity and Mooney scorch of the
composites were tested at 135◦ C for 30 minutes using a Mooney
viscometer (Alpha Technologies).
The hardness of all the samples was measured by a durometer A and
IRHD combined model hardness tester (Gibitre Instrument, Italy) ac­
cording to the ASTM D 2240 test method. The results were reported as
an average of four observations. Tensile (dumbbell-shaped) and tear
(angular) specimens were punched out from the molded sheets using a
hollow die punch (CEAST, Italy). The tests were carried out in a uni­
versal testing machine (Zwick Roell Z010, Germany) at a 500 mm/
minute crosshead speed at 25 ± 2◦ C. Tensile and tear tests were carried
out according to the ASTM D 412-98 and ASTM D 624-99 methods,
respectively.
The abrasion samples were prepared using a three-piece, 16-cavity
mold at 160◦ C for 30 minutes. The testing was done by a 6012 DIN

2
A. Bera et al.
Fig. 1. 3 stage mixing flow chart of NR composites
abrasion tester (Zwick Gmbh & Co, Germany) following the testing
protocol of the ISO 4649 method. The abrasion resistance index (ARI)
expresses the abrasion loss for each sample.
The dynamic mechanical thermal analysis was conducted using
parallelepiped samples with dimensions of 25 mm x 10 mm x 2 mm
using a dynamic mechanical analyzer (DMA) (VA 4000, Metravib,
France) in the tension mode. Single point and complete temperature
sweeps were carried out for the composites to understand the dynamic
mechanical properties.
A simple three-piece, 16-cavity mold was utilized to make cylindrical
rubber specimens, having a diameter of 17.8 mm and height of 25 mm
according to ASTM D 623-93 for the Goodrich Flexometer tester. Sam­
ples were cured at 160◦ C for 30 minutes under the DavidBridge hy­
draulic press compression moulding machine. The samples were
preheated for 30 minutes and allowed to equilibrate at 50◦ C for another
25 minutes by getting hammered at 1800 rpm with each stroke length of
4.45 mm. The average of three samples has been reported here. The
error associated with measurements in HBU was found to be ± 0.2◦ C.
The rebound resilience test was performed in schob type rebound
pendulum apparatus (Zwick Roell 5109, Germany) following the ASTM
D 7121 – 05. A Nano indenter (TI-950) (Hysitron Inc., USA) was used to
carry out nanoindentation studies of the specimens. The nanoindenter
was subjected to 1000 nm constant depth into the material.
The XPS study of treated and un-treated NR sheet samples was
analyzed with a PHI 5000 VERSA PROBE III [ULAVC PHI (physical
electronics), USA, using a monochromatic Al X-ray source with focused
beam (< 10 μm to 300 μm) for rapid x-ray induced secondary electron
imaging (SXI). It has an 1800 hemispherical electron energy analyzer
supported with a 128 channel detector. Atomic Force Microscopy (AFM)
analysis was executed using Agilent 5500 (USA) instrument. A properly
cleaned moulded NR sheet samples were subjected to study the surface
roughness of the vulcanizates and delineated as the phase images. The
scanning of 5ⅹ5 μm area was done by a SiN4 (silicon nitride) tip via
tapping mode at a resonance frequency of 150 kHz and 42 N/m force
constant.
The pieces of rubber vulcanizate samples were ultra microtomed to
approximately 300 nm thickness in a liquid nitrogen atmosphere. The
microtomed pieces samples were collected on a copper grid and pro­
jected to an analytical transmission electron microscope. The TEM
visualization was carried out with the FEI Tecnai G2 20S-Twin trans­
mission electron microscope (Czech Republic) instrument at an
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Chemical Engineering Journal Advances 11 (2022) 100349
accelerating voltage of 120 kV.
Scanning electron microscopy analyses were executed in a Carl ZEISS
Supra 55VP system under an accelerating voltage of 5 kV. Fractography
studies of the samples were carried out after cryofracture. The fractured
surface was coated with a 14 Å thick layer of Au and subsequently
observed through the microscope using the secondary electron detector.
3. Results and discussion
3.1. Cure characteristics
Chemical-A embodied silica-CB filled NR compound experienced low
Tc90 than B and TESPD incorporated compounds as shown in Table 3
and Fig. S1. The hydrogen bonding between the functional groups pre­
sent in chemical-A, silica filler, and un-wanted components of natural
rubber helped accelerate the vulcanization process. The hydrogen
bonding between the functional groups present in chemical-A, and un-
wanted components of natural rubber basically hindered the interfer­
ence of NR functional groups in curing as well as the interaction of silica
with amine groups of protein. Thence, the accelerators present in system
could effectively accelerate the vulcanization process than the standard
compound (S2T) [26, 27, 28].
3.2. Mechanical and dynamic properties
The endeavor of using the chemical-A, B, and 50:50 mixture of both
chemicals as non-silane coupling agents instead of TESPD is carried out.
The output of that trial work is represented as a table form in Table 3.
Thereafter, the concept of implementing those chemicals as blocking
agents during the mastication of natural rubber and finally monitored
the ultimate results (Fig. 2 to 5) of the silane-modified silica and CB
filled NR composites. The addition of coupling agents A and AB in silica-
CB filled rubber showed an extensive contribution in improving tensile
strength and elongation at break than the compound of TESPD, except
the compound of B as shown in Fig. 2a.
Chemical-B exhibited an increment in modulus at both 100 % and
300 % extension compared with chemical-A, AB, and TESPD (Fig. 2b).
The higher modulus indicates the compound’s higher stiffness, which is
reflected in the case of tensile and elongation properties. Therefore, the
stiffer vulcanizates showed inferior tensile strength and low elongation
at break. That is because, as stiffness goes high of the filled vulcanizates,
A. Bera et al. Chemical Engineering Journal Advances 11 (2022) 100349

Table 3
Cure characteristics, mechanical and dynamic properties of silane and non-silane coupling agents incorporated CB-silica filled NR vulcanizates
Samples Tc90 Hardness M100 M200 M300 T.S EB Tear strength ARI Rebound (%) Tanδ @70 ᵒC
(min) (shore A) (MPa) (MPa) (MPa) (MPa) (%) (N/mm) (%)
S2A10 4.41 61.6 1.9 4.2 8.2 28.0 634.5 122.4 92.5 52.7 0.1371
S2B10 5.18 65.5 2.4 4.6 9.2 26.1 573.1 124.9 103.3 47.8 0.1831
S2AB10 4.83 64.4 1.7 3.6 7.0 28.3 659.2 120.2 112.6 52.8 0.1516
S2T 5.40 62.6 1.8 4.8 9.6 26.9 606.7 107.3 127.8 54.7 0.1322

Fig. 2. (a) Tensile strength and elongation at break, (b) Tear strength and reinforcement index properties, (c) Abrasion resistance index and heat build-up properties,
(d) 100 and 300 % modulus of silica-CB filled NR vulcanizates.

in all probability the elongation will be reduced. Therefore, it may not

reach to the desired tensile strength as well. The vice versa is observed in
the case of chemical A and AB compounds. That is due to a slightly lower
crosslink density of compound A10S2T and AB10S2T according to the
results of delta torque of MDR data. In case of S2A10 the chemical-A was
added along with silica filler as a non-silane coupling agent to replace
TESPD, has shown an inferior ARI property. The higher value of ARI
indicates the least abrasion loss due to a superior reinforcement of the
rubber vulcanizates [29]. Therefore, the higher value corresponding to
S2T proves a better dispersion and reinforcement in the presence of
TESPD than other compounds mentioned in Table 3. However, when the
same chemical-A was added during NR mastication as a blocking agent
of NR functional groups, in presence of TESPD the vulcanizate exhibited
a significant improvement in ARI as depicted in Fig. 2d. It is distinctly
clear from the morphological studies and Payne effect properties that
the early stage insertion of sorbitol in the elastomer has helped to pacify
the interference of NR’s functional groups during silanization reaction
and provide a better filler dispersion as well as lower filler-filler inter­
action into the system.
The measurement of rebound resilience of different rubber vulcani­ Fig. 3. Rebound resilience property of silica-CB filled NR vulcanizates.
zates is shown in Fig. 3. The higher value of rebound resilience indicates
an inferior rubber to filler bonding of the rubber vulcanizates [30]. The moderate rubber-filler interaction than other compounds alluded to in
presence of reinforcing filler creates friction between filler and rubber, Table 3. As the delta torque obtained from curing data (Fig. S2), signifies
along with the displacement of polymer chains from the filler surface. the trend of crosslink density of the vulcanizates. Therefore, the ten­
Thus, the dissipation of energy through filler-rubber friction conveys the dency of crosslink density of various vulcanizates can be predicted
term hysteresis [30, 31]. Hence, S2T, S2A10, and S2AB10 indicate a easily. A10S2T and AB10S2T evidenced better filler-rubber interaction

4
A. Bera et al.
although both of them interestingly recorded almost similar rebound
resilience property like, S2T. This is attributed to the enhancement in
crosslink density besides better rubber–filler interaction and silica
dispersion of both two vulcanizates [32, 33, 34, 35].
In Fig. 4, the results of nano-indentation are depicted as load vs.
displacement curve and hardness of NR vulcanizates. The loading - un-
loading and nano-indentation effect can be studied by measuring the
hardness and reduced modulus. According to Fig. 4a, a high hysteresis
loss is evidenced for the sample B10S2T than the other 3 samples. This is
due to more filler-filler interaction and lower elastomer-filler interaction
of the sorbic acid-treated NR vulcanizates. Moreover, the presence of
sorbic acid into the NR compound enhanced the optimum cure time due
to its acidic nature. Therefore, the number of mono-sulfide linkages over
di or poly-sulfide linkages is predicted to be more than the other com­
pounds. Thus, the sorbic acid-treated vulcanizate exhibited maximum
hardness followed by a 50:50 mixture of sorbitol and sorbic acid, then
sorbitol, and the minimum is for the un-treated regular compound [36,
37].
Tan δ at 70◦ C acquaint regarding the hysteresis of the tyre tread. This
fundamental property is known as tyres’ rolling resistance (RR). Lower
the value of it proves the improvement of RR of the tyre tread. Hence,
the NR vulcanizates S2A10 and S2T monitored (Table 3) incomparable
lower tan δ values are evidence of a superior rolling resistance apart
from other compounds as shown in Fig. 5a [38]. Moreover, S2T in
Fig. 5a evinced a lower Tan δ at 70◦ C, and the difference between S2T
and A10S2T is less than 6%. The heat build-up (HBU) properties of the
rubber compounds A10S2T and S2T are almost similar. But, the HBU
values of compounds B10S2T and AB10S2T expressed an extreme
elevation of heat in comparison to S2T and A10S2T. However, a poor
filler-rubber interaction could be the probable reason in case of high
heat build-up property, as indicated by the Payne effect in Fig. 5b. The
same leads to further poor bonding of rubber chains with filler particles
during dynamic tests [39].
3.3. Optimization study of chemical-A
As the quantity of chemical-A was not optimized, 10% of silica was
chosen to get a confirmation study. In this optimization study, the
chemical-A was varied from 0 to 2 phr in 50 phr carbon black loaded NR
compound. The presence of silica filler could distract the properties of
the optimization study; therefore, filler loading was entirely based on
carbon black.
Following Table S1, the optimization study was carried out mainly
by following the compounds’ optimization cure time (Tc90). The
interaction between hydroxyl groups of chemical-A and functional
Fig. 4. Nano-indentation study: (a) load vs. displacement graph and (b) hardness of various NR vulcanizates.
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Chemical Engineering Journal Advances 11 (2022) 100349
groups present in NR makes a hydrogen bond between chemical A and
the backbone of NR. Because of that, the amine groups present in NR
could not participate in the curing reaction. In the case of further
addition (A3 and A4), the number of inter and intramolecular hydrogen
bonding was higher. The higher number of hydrogen bonding helped
accomplish the curing a bit faster. Consequently, as the A1 and A2 both
showed higher values of Tc90, both 0.5 and 1 phr were considered for
optimizing the quantity of chemical-A as a blocking agent.
The XPS analysis was used to re-confirm the blocking of amine
groups present in proteins of NR by hydroxyl groups of sorbitol.
Importantly, two N1s peaks are monitored in the spectra of untreated
and treated natural rubber samples and designated as ~398 eV – N-H/ C-
N, ~400.5 – amide N [40]. The intensity of un-treated NR N1s spectra is
higher than the treated NR sample [41]. The 2nd peak of N1s spectra of
un-treated NR (Fig. 6a) at 400.5 eV is for the nitrogen groups of amide
present in proteins. The addition of sorbitol into it exhibited a clear shift
towards higher binding energy, proving the hydrogen bonding during
the interaction of amine groups of protein and –OH groups of sorbitol
[42, 43]. The similar evidence were observed from FTIR studies as
shown in supplementary information (Fig. S4).
3.4. Implementation of the optimized quantity of chemical-A in silica-CB
filled NR compounds
The reinforcement index (RI = M300/M100) of all vulcanizates is
illustrated in Fig. 8b. As expected, the 0.5 phr (A1S2T) exhibits a higher
reinforcement index followed by A2S2T and S2T, correspondingly.
Fig. 7
The higher RI value of rubber vulcanizates connotates higher rubber-
filler interaction and crosslink density. The stiffness of the vulcanizates
monitored the same trend according to modulus. Nevertheless, all the
vulcanizates showed indistinguishable values of hardness.
Figs. 8a and 8b displayed tensile and tear strength, respectively. The
plot indicates that incorporating 0.5 phr of chemical-A distinctly
enhanced the tensile and tear strength of the vulcanizate than 0 and 1
phr. Moreover, Fig. 8a evidenced the utmost strain at the break of S2T
compared to the other two vulcanizates. It is owing to the fact that the
modified NR compound accommodates more hydrogen bond, which
provides more stiffness and comparatively less elongation at break than
that of the un-modified NR compound.
The ARI of the modified and un-modified NR vulcanizates is depicted
in Fig. 8c. The addition of a blocking agent in NR proved a significant
improvement of abrasion resistance of the rubber vulcanizates. The
interaction between the functional groups of blocking agent, silica filler,
and coupling agent enhanced the percentage of filler-rubber interaction,
A. Bera et al.
Fig. 5. (a) Tan δ @70◦ C and E’ of silica-CB filled NR vulcanizates (b) Payne effect of individual NR vulcanizates.
Fig. 6. XPS plots of a) un-treated natural rubber and b) treated natural rubber
which might be the probable reason behind a better dispersion of filler.
This interaction can be explicated for the improvement of ARI over the
un-modified NR vulcanizate.
The performances of tyre firmly rely on the properties of rubber.
Viscoelasticity of rubber compounds is liable for cyclic deformation,
which includes remarkable heat generation and extensive temperature
ascent in all tyre parts [44]. Temperature increment influences the
viscoelastic as well as mechanical properties of rubber compounds. In
addition, temperature enhancement can lead to a blowout of tyres or
diminish fatigue life and material aging. Furthermore, power loss of
tyres, energy dissipation, and high rolling resistance bring out the
emission of plenty of carbon and high energy consumption. The heat
build-up property of silica-NR vulcanizates shown in Fig. 8d is decres­
cent with chemical-A loading. This attributes to the supporting contri­
bution of the blocking agent in silica-NR masterbatch, which enhances
the rubber-filler interaction and facilitates the filler dispersion within
the rubber matrix. Low-temperature heat build-up of silica-filled NR
vulcanizates indicates higher crosslink density along with low
compression set values [45]. As shown in Fig. 8d, the dynamic
compression set is an essential factor that signifies the elasticity of
rubber vulcanizates. Fundamentally, an efficient elastic rubber can
restrain its actual shape after the withdrawal of applying external stress
[46]. Consequently, sample A1S2T is the best elastic rubber vulcanizate
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Chemical Engineering Journal Advances 11 (2022) 100349
in nature as it exhibited the lowest compression set value. In other
words, sample S2T displayed a maximal compression set compared with
other samples.
Cyclic extension and contraction indicate the loss of energy (hys­
teresis or hysteretic loss), which designates rubber samples’ viscoelastic
behavior. Rolling resistance (RR) (Fig. 9a) of a tyre tread can be corre­
lated with the hysteresis loss of the compound. A higher hysteresis loss
value signifies higher RR of a tyre tread and higher fuel consumption
[47].
Moreover, according to D. M. Park et al., the heat build-up of any
filled rubber compound is proportional to the hysteresis loss [48]. Thus,
the higher heat build-up of the samples can be predicted for broad
hysteresis loss. Hence, the difference between the 10th and 1st hysteresis
loop area is measured for each sample and shown in Fig. 8a. More the
difference indicates poor elasticity of the sample that implies the higher
rolling resistance and higher heat build-up. The difference between the
Eʹ (storage modulus) higher and lower strains designate the (ΔEʹ) Payne
effect. The higher degrees of filler-filler interaction indicates the higher
delta storage modulus value. The samples A1S2T and A2S2T exhibited a
lower Payne effect (Fig. 9b) due to the presence of both blocking agent
and coupling agent (TESPD), which attributed to an improved
filler-rubber interaction to the sample, irrespective of only blocking
agent or coupling agent.
A. Bera et al. Chemical Engineering Journal Advances 11 (2022) 100349

Fig. 7. (a) Tensile strength and elongation at break, (b) Tear strength and reinforcement index, (c) ARI and rebound resilience, (d) Heat build-up and dynamic
compression set properties of rubber vulcanizates.

Fig. 8. Hysteresis loops and the difference between the 1st and 10th loop area of the samples.

3.5. Morphology analysis
The surface roughness of the NR vulcanizates assures the filler
dispersion in the NR matrix. In Fig. 11a, the broad particles of silica filler
distinctly confirm the agglomeration of silica filler. That is attributed to
unwanted substances’ intervention subsisting in NR obliterating the
silanization reaction. Surprisingly, Fig. 10b of A10S2T affirms a clear
dispersion of silica filler compared with other vulcanizates.
The TEM analysis of NR vulcanizates provides a clear image of filler
dispersion in the NR system, as shown in Fig. 11. The light grey and
black portions of the TEM images are rubber and silica particles,
respectively. TEM micrographs of Fig. 11b exhibit a homogeneous
dispersion of fillers within the rubber matrix. Whereas a large number of
agglomeration is visible in the case of other rubber compounds indicates
the inappropriate dispersion of filler within the rubber matrix.
Surface electron microscopy (SEM) of cryo fractured NR vulcanizates
is depicted in Fig. 12. The small spherical shape with white color spots
represents silica particles within the NR rubber matrix. The same trend
of dispersion morphology is observed in SEM as visible in TEM images
except for the composite AB10S2T. Agglomerated silica particles are
visible in the case of untreated NR composite (S2T) and sorbic acid-
treated NR composite (B10S2T). The sorbitol treated NR vulcanizate

7
A. Bera et al. Chemical Engineering Journal Advances 11 (2022) 100349

Fig. 9. (a) Full temperature sweep of DMA study, (a1) close view of DMA curves at high temperature region (b) Payne effect of the NR vulcanizates at room
temperature.

Fig. 10. AFM images of NR vulcanizates: (a) un-treated NR (b) Sorbitol treated NR (c) Sorbic acid-treated NR and (d) 50:50 mixture of sorbitol and sorbic acid-
treated NR

8
A. Bera et al. Chemical Engineering Journal Advances 11 (2022) 100349

Fig. 11. Comparison of TEM images for silica-CB filled various treated NR vulcanizates: (a, a’) Un-treated NR (b) Sorbitol treated NR (c) Sorbic acid-treated NR and
(d) 50:50 mixture of sorbitol and sorbic acid-treated NR. (a-d in 100 nm and a’-d’ in 200 nm scale)

9
A. Bera et al.
Fig. 12. Scanning electron microscope images of NR vulcanizates: a) Un-treated NR b) Sorbitol treated NR c) Sorbic acid-treated NR and d) 50:50 mixture of sorbitol
and sorbic acid-treated NR
exhibited a minimal quantity of silica aggregates and fascinating me­
chanical and dynamic properties. Henceforth, the FESEM analysis re­
assures and manifests the better dispersion of filler in NR compound in
the presence of sorbitol. The tiny rounded spots (vacuoles) are noticed
and marked by red circles in Fig. 12d, probably due to the generation of
CO2 inside the rubber composite during the interaction between sorbitol
and sorbic acid. Owing to that reason, the compound AB10S2T has
performed very poorly in the case of both dynamic and mechanical
properties [49]. The better silica dispersion in optimized blocking agent
embedded NR compound is also evidenced in Fig. S5.
4. Conclusions
Introducing the new non-silane coupling agents in silica-filled nat­
ural rubber compound showed better results for tensile strength,
modulus, elongation at break, and rebound resilience at the expense of
little abrasion resistance index to TESPD incorporated NR compound.
The idea of incorporating a non-silane coupling agent as a blocking
agent in the mastication stage worked perfectly for chemical-A, in
particular amongst the NR rubber compounds. Along with all the other
properties, the three fundamental properties, i.e., abrasion resistance
index (ARI), heat build-up (HBU), and rolling resistance (Tan δ @ 70◦ C),
displayed a significant improvement by the use of chemical-A over
TESPD. The optimization study of chemical-A as a blocking agent is
executed via the average values of optimization cure time and FTIR
analysis. The FTIR peak shifts towards the lower signified the hydrogen
bonding and blocking of the functional groups of proteins and phos­
pholipids of the NR backbone. Optimization study, including optimizing
the rubber vulcanizates’ cure time, assisted in choosing A1 (0.5 phr) and
A2 (1 phr) for further study of the NR vulcanizates. Eventually, the same
optimized quantity of sorbitol was employed in silica-CB filled NR
composite. Based on the detailed mechanical and dynamic property
analysis, 0.5 phr of sorbitol is chosen for its best performance in the NR
compound as a blocking agent, which would be a promising ingredient
in formulating NR-based tyre tread compounds in automotive industries.
10
Chemical Engineering Journal Advances 11 (2022) 100349
Funding Information
The authors are grateful to the Ministry of Human Resource Devel­
opment, Govt. of India, Apollo Tyres Global R&D Chennai, and Indian
Institute of Technology Kharagpur for financial support.
CRediT authorship contribution statement
Abhijit Bera: Conceptualization, Writing – original draft, Writing –
review & editing. Debabrata Ganguly: Writing – review & editing,
Methodology. Sanjoy Kumar Ghorai: Writing – review & editing,
Methodology. Jyoti Prakash Rath: Project administration. S. Ram­
akrishnan: Project administration. Job Kuriakose: Project adminis­
tration. S.K.P. Amarnath: Writing – review & editing. Santanu
Chattopadhyay: Supervision.
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
Authors would like to acknowledge the Indian Institute of Technol­
ogy Kharagpur and Apollo Tyres Pvt. Ltd, Chennai for their financial
support and all kinds of facilities. The authors are also thankful to the
Central Research Facility of IIT Kharagpur for carrying out the different
characterization of the samples. The author also likes to thank Mr.
Rajesh De, Junior Technician/Junior Laboratory Assistant, Rubber
Technology Centre, IIT Kharagpur. For microscopic studies, the authors
also express their heartfelt gratitude to Mr. Praveen S., Defence Research
and Development Organisation (NMRL), Pune.
A. Bera et al.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ceja.2022.100349.
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