Resources, Conservation & Recycling 154 (2020) 104629

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Resources, Conservation & Recycling

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Full length article

Cradle-to-cradle approach to waste tyres and development of silica based T

green tyre composites
Joyeeta Ghosha, Sakrit Haitb, Soumyajit Ghoraia, Dipankar Mondalc, Sven Wießnerb, Amit Dasb,*,
Debapriya Dea,*
a
Chemistry Department, MCKV Institute of Engineering, Liluah, Howrah, 711204, India
b
Department of Polymer Science & Technology, University of Calcutta, Kolkata, 700009, India
c
Leibniz-Institut für Polymerforschung Dresden e.V., D-01069, Dresden, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: This work is about simultaneous devulcanization and chemical functionalisation of waste styrene butadiene
Green tyre rubber vulcanizate (SBR) using thermo-mechanical treatment and sulphide based multifunctional devulcanizing
Rubber recycling agent. The as-grown compounds are reinforced with nano-silica and re-vulcanized to prepare rubber composites.
Silica rubber composites The curing and processing characteristics, and mechanical performance are further compared with those of
Dynamic mechanical performance
conventional silica based green tire formulations. The extent and quality of devulcanized rubber are monitored
through the measurement of sol content, inherent viscosity of sol fraction, cross-link density and degree of
devulcanization as a function of cross-link density. By our method based on restoring the curing and other
processing parameters, the revulcanized composites offer ∼11 MPa tensile strength, ∼26 MPa tear strength
together with elongation at break value as much as 450 %. Such values are comparable with those of the
composites consisting of the associated fresh components of the systems. Surprisingly, the higher storage
modulus and lower tanδ of SBR-devulcanized SBR-silica composite as compared with standard counterpart
sample (SBR-silica composite) confirms magnificent dynamic mechanical performance of the composites. This
work may pave a new route for reuse of waste tyre in tyre production.

1. Introduction environmental and economical aspect wherein the lowest level is the
energy recover through burning of waste rubber (Machin et al., 2017),
Decreasing source and rising price of crude oil become a serious but it generates huge amount of CO2 and particulate matters re-
alarm for availability of feedstock to the production of synthetic rubber. sponsible for global environmental damage. The second level is back-to-
Among different synthetic rubbers large amount (∼74 %) of styrene feed stock which is popularly known as pyrolysis of waste rubber (Wang
butadiene rubber (SBR) are used in tyre industry for its low rolling et al., 2019). This technology involves pyrolysis of the rubber products
resistance due to reduced fuel consumption results in less CO2 emission. to generate gas, oil, chemicals and pyrolytic carbon black which can be
Apart from tyre industry, SBR is also used in other applications such as used as reinforcing filler for rubber. But it is quite clear that one cannot
conveyor belts, industrial hoses, different moulded and extruded rubber expect to recover hydrocarbon monomers or even oligomers from
goods, footwear and other consumer goods etc. A few grades of SBR are complex rubber structures. The next level is the material recycling; it
also used in the cable industry. As a fallout, every year approximately transforms used rubber into products which is inferior to the fresh
800 millions (∼ 10 million tons) of scrap tyres are being produced material. Finally, the most efficient rubber waste management route or
across the globe (Asaro et al., 2018). Both the developed and the de- the highest level of the hierarchical ladder is to transform used rubber
veloping countries are paying great attention to the disposal of these goods into products having comparable properties with that of the
huge amounts of discarded tyres. These materials cannot return to the virgin rubber products.
natural environment through biological degradation, hydrolyzation or As regards technological aspects devulcanization/reclaiming pro-
decomposition like plants or animals due to the cross-linked structure of cess includes mechanical, thermal, chemical, thermomechanical, me-
rubbers and the presence of stabilizers and other additives. Fig. 1 in- chanochemical, ultrasound, microwave, biotechnological processes etc.
dicates the most efficient waste management hierarchy under (Adhikari et al., 2000; Bockstal et al., 2019; Molanorouzi and Mohaved,

⁎
Corresponding authors.
E-mail addresses: das@ipfdd.de (A. Das), d.de@mckvie.edu.in (D. De).

https://doi.org/10.1016/j.resconrec.2019.104629
Received 23 July 2019; Received in revised form 29 October 2019; Accepted 2 December 2019
0921-3449/ © 2019 Elsevier B.V. All rights reserved.
J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

use of coupling agent. Mechanochemically devulcanized natural rubber

(Ghorai et al., 2016) and styrene butadiene rubber (Ghosh et al., 2017)
was prepared from waste natural rubber and styrene butadiene rubber
vulcanizate in an open-roll mixing mill at around ambient temperature
using bis(3-triethoxysilyl propyl) tetrasulfide (TESPT) to optimize the
processing parameters such as devulcanization time and concentration
of devulcanizing agent. Measurement of extent of devulcanization such
as sol fraction, inherent viscosity of sol rubber, cross-link density and
Mooney viscosity as well as revulcanization characteristics like me-
chanical properties and thermal behavior of devulcanized rubber
clearly indicated that the optimum concentration of TESPT was 6 mL/
100 g of rubber and the corresponding time of devulcanization was 40
min. Mechanochemical devulcanization of rubber vulcanizate was
found to be an efficient method compared to chemical devulcanization
Fig. 1. Waste management hierarchy. process only, as reported in other studies (Diaz et al., 2018; Formela
and Cysewska, 2014; Warner, 1994). However, the efficiency of me-
2016; Ghorai et al., 2019; de Sousa et al., 2019). In thermomechanical chanochemical devulcanization process could be significantly enhanced
devulcanization process, waste rubber is devulcanized with external by proper choice of devulcanizing agent.
thermal energy and mechanical forces which lead to the random scis- In present day tremendous efforts have been given not only in waste
sion of the crosslink bond and the polymer chain (Tao et al., 2013). disposal problem but also in different schemes for protecting the en-
However, in mechanochemical devulcanization process, scrap waste vironment. The tyre industry is also facing the same challenge for im-
rubber is devulcanized with mechanical forces in presence of chemical proving the energy efficiency in the automobile industry to reduce CO2
devulcanizing agent (De and De, 2011; Shi et al., 2014). Numerous emissions. In order to achieve energy savings from tyres, reduction of
disulfides are reported as devulcanizing agent for the production of rolling resistance is very important, which can be achieved by using
devulcanized rubber that includes several inorganic compounds silica instead of carbon black in tyre compound. Silica/rubber compo-
(Adhikari et al., 2000). Mechanochemical devulcanization of ground sites show low rolling resistance without deterioration of wet skid re-
rubber tyre (GRT) was performed by a multifunctional devulcanizing sistance (Job, 2014). Further it shows its potential in the manufacturing
agent, tetramethyl thiuram disulfide (TMTD) by the authors (De et al., of ‘green tyres’ with high fuel efficiency, low green house gases emis-
2006). The developed devulcanized rubber could be revulcanized sion and high driving safety (Wang et al., 2016; Marimin et al., 2018).
without addition of extra TMTD. Devulcanization of natural rubber Moreover, the interfacial modification between rubber matrix and silica
industry waste was carried out in a twin screw extruder at 80° and 100 particles is essential to facilitate the rubber reinforcement as required
°C with a specifically designed screw profile for rubber recovery for manufacturing high performance rubber/silica nanocomposites
(Seghar et al., 2019). It was found that due to self heating of rubber, the (Zou et al., 2016) as well as different types of rubber goods such as
temperature of the samples increased to ∼145 °C and ∼155 °C re- conveyor belt, flooring and moulding, belting and treads for off-the-
spectively. The results also revealed that the increase in the input road equipments (agriculture, construction etc.). But silica has some
temperature did not promote devulcanization rather it induced polymer inherent limitations as reinforcing filler in styrene butadiene rubber
degradation. Chemo-thermomechanical devulcanization of waste (SBR) compound due to poor dispersion of silica in the rubber matrix.
rubber powder was carried out using thiobisphenol, 4, 4/-dithiobis(2, 6- The large surface area and high surface energy of SiO2 nanoparticles
di-t-butylphenol) in an internal mixer at 180° and 200 °C (Zhang et al., facilitate the aggregate or agglomerate formation, restrain the disper-
2018). The results from this study suggested that higher temperature sion of silica in the rubber matrix. Moreover, hydroxyl groups (−OH)
and devulcanizing agent (thiobisphenol) concentration decreased the present on the surface of silica, result poor compatibility with the most
cross-link density and Mooney viscosity of devulcanized rubber and hydrophobic rubber matrix (Yatsuyanagi et al., 2001; Gui et al., 2016).
increased the sol content of devulcanized rubber. Chemical devulcani- In green tire application, silica/SBR nanocomposites are found to be
zation of sulfur-vulcanized natural rubber was studied using benzoyl the most important material system having superior mechanical prop-
peroxide as a devulcanizing agent in presence xylene as solvent erties and lower rolling resistance due to the presence of silica nano-
(Sabzekar et al., 2015). Influence of important reclaiming parameters particles. Zou et al. (Zou et al., 2016) synthesized a multifunctional
like reaction time, reaction temperature and concentration of de- rare-earth complex, dithio-aminomethyl-lysine samarium and in-
vulcanizing agent as a function of sol fraction, cross-link density and corporated the complex in silica/SBR composite which catalyzed and
Mooney viscosity of devulcanized rubber and mechanical properties of accelerated the vulcanization process, facilitated the dispersion of silica
revulcanized reclaim specified at that lower devulcanization time and into the rubber matrix, enhanced interfacial adhesion between rubber
lower concentrations of the devulcanizing agent, selective scission of and silica. The interfacial interaction between silica and SBR was im-
sulfur cross-links were observed. Longer reaction time led to lower proved by using epoxy group functionalized SBR with different epoxy
cross-link density resulting in significant decrease in tensile strength group content (Qiao et al., 2017). The developed epoxy group func-
and elongation at break. Both unfilled and precipitated silica filled si- tionalized silica/SBR nanocomposites were characterized by low rolling
licon rubbers can be devulcanized by means of the ultrasonic extruder resistance, high wet skid resistance and excellent mechanical proper-
(Shim and Isayev, 2001). Measure of cross-link density and gel fraction ties. Lin et al. (Lin et al., 2016) developed silica/reduced graphene
indicated that higher degree of devulcanization was achieved at higher oxide (SiO2@rGO) hybrid filler by an electrical assembly and in-
amplitude and at low flow rate of material. However, less devulcani- corporated into SBR to prepare the composite. The hybrid filler-SBR
zation of filled rubber was achieved since a certain level of ultrasonic composite shows better interfacial interaction than those of the SBR/
energy was consumed to break physical cross-links between poly- SiO2 and SBR/rGO composites. Lei et al. (Lei et al., 2010) synthesized 1-
dimethylsiloxane (PDMS) and fillers. Generally, bis(3-triethoxysilyl methylimidazolium methacrylate (MimMa) and used as interfacial
propyl) tetrasulfide (TESPT) is used as a coupling agent during silica modifier of SBR for the dispersion of silica filler in the composite. The
filler dispersion in a virgin non polar rubber compound. For the first results indicated that the small addition of MimMa improved silica
time we use TESPT as a devulcanizing agent. The devulcanized rubber dispersion and mechanical performance of the composite. The in-
assists the silica dispersion in non-polar rubber compound without any creased mechanical loss under dynamic load showed a promising uti-
lization as a damping material. Antioxidant, 2-mercaptobenzimidazole

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Scheme 1. Process flow chart for devulcanized SBR preparation.

modified silica (SiO2-s-MB) exhibited better dispersion in SBR in com- by SEM analysis and dynamic mechanical behavior.
parison to that of the silane modified silica-SBR composites (Zhong Precisely, the paper reports the devulcanization of styrene buta-
et al., 2015a, 2015b). The higher mechanical properties of SBR/SiO2-s- diene rubber (SBR) vulcanizate by a novel devulcanizing agent, bis(3-
MB composite indicate that the modified hydrophobic silica surface can triethoxysilyl propyl) tetrasulfide and its subsequent application as an
adsorb more rubber chains on its surface and enhance the possibility of interfacial modifier in fresh SBR-devulcanized SBR-SiO2 vulcanizate.
physical entanglement near the silica surface which ultimately in-
creases the interfacial interaction between SBR and SiO2-s-MB. Zhong 2. Experimental
et al. (Zhong et al., 2015a, 2015b) studied the mechanical behavior of
vulcanization accelerator, ethylenethiourea (ETU) modified SiO2-SBR 2.1. Materials
composites. ETU was chemically attached on the surface of the silane
modified silica in order to form ETU modified silica (silica-s-ETU) DeVulcSBR is prepared from ground SBR (GSBR) vulcanizate by bis
which could uniformly disperse in SBR matrix and remarkably im- (3-triethoxysilyl propyl) tetrasulfide (TESPT), a multifunctional dis-
proved the mechanical properties of the composite than that of SBR- ulfide reclaiming agent, reported earlier (Ghosh et al., 2017). Styrene
silane modified silica composites. In order to improve the rubber-filler butadiene rubber (SBR-1502) (Synthetics and Chemicals Ltd., India),
interaction a two-step modification was employed to modify the silica bis(3-triethoxysilyl propyl) tetrasulfide (TESPT) as devulcanizing agent,
surface (Li et al., 2013). In this process initially hydrolysis of bis(3- zinc oxide (S.D. Fine Chem., India), stearic acid (LobaChemie, India),
triethoxysilyl propyl) tetrasulfide (TESPT) leads to the formation of sulfur (S.D. Fine Chem., India), N-cyclohexyl-benzothiazyl-sulphena-
silanol (Si−OH) group which subsequently reacts with the hydroxyl mide (CBS) and toluene (S.D. Fine Chem., India) were used as received
group on the silica surface to form TESPT grafted silica nanoparticles. without further purification. The silica used was Ultrasil VN-3, whose
Chen et al. (Chen et al., 2017) developed sulfur monochloride modified specific surface area is about 200 m2/g.
silica (silica-s-S2Cl2) nanoparticles by the reaction between chloric
atom and silanol hydroxyl group of the silica surface. The so-grown 2.2. Preparation of vulcanized and aged SBR and devulcanized SBR
devulcanizing agent, silica-s-S2Cl2 can be uniformly dispersed in SBR
matrix and cured the rubber compound without sulfur as cross-linking For the preparation of devulcanized SBR compounding of SBR (100
agent. Moreover, the morphological and interfacial studies indicated Phr) was carried out with various additives like ZnO: 5 phr, stearic acid:
that the dispersion and interfacial interaction respectively, were su- 2 phr, CBS: 1.2 phr and sulfur: 1.8 phr in an open roll mixing mill. The
perior for SBR/silica-s-S2Cl2 composites compared to those of the SBR/ compounded rubber was vulcanized at 150 °C for optimum cure time
sulfur and SBR/TESPT composites. 7.5 min determined through Elastograph 67.12 (Goettfert, Germany).
In this article, mechano-chemical devulcanization of waste SBR The vulcanized SBR were then aged at 100 ± 2 °C for 96 h as per ASTM
vulcanizate and its subsequent application in fresh rubber-silica com- D865-11 and then it was ground to prepare ground SBR (GSBR). The
posite were studied. The rubber devulcanization was performed in an particle size of GSBR vulcanizates was less than 1 mm. The physical
open-roll mixing mill at 70 °C by using bis(3-triethoxysilyl propyl) characteristics such as sol content, density, cross-link density and mo-
tetrasulfide. The extent of devulcanization was monitored through sol lecular weight between cross-links of GSBR were measured to be 4 %,
content, inherent viscosity of sol rubber, cross-link density and degree 0.975 g/cm3, 1.106 × 10−3 mol/cm3 and 0.904 × 103 cm3/mol re-
of devulcanization. Then the so-grown devulcanized rubber is used as spectively. From thermogravimetry study, the SBR content, char re-
an interfacial modifier in the fresh rubber-silica composite together sidue and oil present in the sample were found to be 92.8 %, 6.2 % and
with partial replacement of fresh rubber. Finally the performance of 1 % respectively.
devulcanized SBR was compared with that of the control SBR-silica One hundred grams of GSBR was thoroughly mixed with devulca-
composite both in presence and absence of silane coupling agent nizing agent, TESPT (6 per hundred parts of rubber). The mixture was
through the measurement of curing characteristics, mechanical prop- subsequently soaked in TESPT for 24 h prior to devulcanization and
erties, reinforcing efficiency by equilibrium swelling, morphology study then transferred to an open two-roll mill followed by compounding at a

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Table 1
Compound formulation of SBR/DeVulcSBR/SiO2 blend system.
Materials (Phr) Sample Code

Silica-10 Silica-20 Silica-30 Silica-40 Silica-30 (control) Silica-30 (control-TESPT)

SBR (SBR-1502) 70 70 70 70 100 100

DeVulcSBR 30 30 30 30 – –
Silica (Ultrasil VN3) 10 20 30 40 30 30
Bis(3-triethoxysilyl propyl) tetrasulfide (TESPT) – – – – – 1.5

Compound formulations: Zinc oxide: 5 phr; Stearic acid: 2 phr; Sulphur: 1.8 phr and CBS: 1.2 phr added in all the formulations.

friction ratio of 1:1.25 for 40 min at around ambient temperature (∼ Vr 0 f ⎤

= 1 − m⎡
65–70 °C). The flow diagram for the production of devulcanized SBR Vrf ⎢ 1 − f⎥ (1)
⎣ ⎦
(DeVulcSBR) is presented in Scheme 1. It is observed that with in-
creasing devulcanization time band formation occurs in the roll and the whereVr0 is the volume fraction of the gum rubber vulcanizates,
powder material is converted to homogeneous viscoelastic material. f the volume fraction of filler found from the ratio of volume of filler
The physical properties of DeVulcSBR such as sol content, inherent and the total volume of the recipe and m is the rubber-filler interaction
viscosity (ηinh ) of sol rubber, crosslink density and degree of devulca-
nization are determined to be 24.5 %, 0.188 g/dL, 0.968 × 10−3 mol/
parameter which was determined from the slope of the line when ( )
Vr0
Vrf

cm3, and 12.5 % respectively. ( ) f

is plotted against 1 − f . Vrf , the volume fraction of rubber network in
swollen phase is evaluated from the equation of Ellis and Welding (Ellis
and Welding, 1964). The degree of reinforcement was determined from
2.3. Preparation of SBR/DeVulcSBR/SiO2 composites the Cunneen and Russell equation (Cunneen and Russell, 1970) as
follows in Eq. (2):
Rubber compounds used in this study are presented in Table 1. Vr 0
Fresh SBR is mixed with DeVulcSBR in fixed 70:30 wt% ratio along with = ae−z + b
Vrf (2)
compounding ingredients in a laboratory size two-roll mill (Mill size:
6′ ′ × 13′ ′) for 25 min. In all the formulations the compounding in- where Vr0 and Vrf are the same as defined earlier, z the weight fraction of
gredients such as zinc oxide, stearic acid, sulfur and accelerator is filler, and a and b are constants.
added in fixed amount on the basis of 100 g of fresh rubber irrespective Tensile and tear strengths of the composites are measured by
of the proportion of DeVulcSBR, as the author already reported (De Universal Tensile Machine (DigiUTM-2000 V) as per ASTM D 412 and
et al., 2000) that the additives in devulcanized rubber originated from ASTM D 624 respectively. The abrasion resistance of the composites
parent compound were inactive. Based on the amount of silica content was measured using DIN abrasion tester following ASTM D 5963.The
the formulations are designated as silica-10, silica-20 etc. In order to dynamic mechanical behavior such as storage modulus (E′) and loss
optimize the silica content in SBR/DeVulcSBR composite, the silica tangent ( tan δ) of SBR/DeVulcSBR/SiO2 composites were measured an
content was varied from 10 to 40 phr and subsequent evaluation of the Eplexor 2000 N (Gabo Qualimeter, Ahlden, Germany) at a frequency of
performance of the composites indicate that the 30 phr silica loaded 10 Hz. The rectangular test sample of 33 mm long, 10 mm wide and 2
composite shows superior performance than that of the 10, 20 and 40 mm thick sample was tested in the temperature range from -100 to 100
phr silica loaded composites. To see the suitability of DeVulcSBR as °C with a heating rate of 10 °C/min. The samples were analyzed in the
interfacial modifier for silica the properties of SBR/SiO2-DeVulcSBR tension mode with 1 % static pre-strain and 0.5 % oscillating dynamic
composite compared with that of the SBR/silica and SBR/SiO2-TESPT strain. The measurements were performed with a heating rate of 2 K/
composite. In Table 1 the formulation containing fresh SBR and silica min under liquid nitrogen flow. Thermal behavior of the composites
(30 phr) is designated as silica-30(control) and the formulation con- was measured using a thermogravimetry analyzer (TGA) (Model:
taining fresh SBR, Silica (30 phr) and TESPT is designated as silica- Netzsch, Germany STA 449C) in nitrogen atmosphere at heating rate 10
30(control-TESPT) composite. °C/min. The values presented were based on residual contents at 600
The curing behaviors of the different SBR/SiO2-DeVulcSBR, silica- °C.
30(control) and silica-30(control-TESPT) compounds were studied by
Elastograph 67.12 (Göttfert, Germany) as per ASTM D 1646 at 150 °C.
3. Results and discussion
The samples were then cured in a compression molding machine at 150
°C and 5000 psi pressure for the respective optimum cure time
3.1. Curing characteristics of SBR composites
(t = t 90) got from the rheographs.
The cure behavior of the compounded SBR/SiO2-DeVulcSBR, silica-
30(control-TESPT) and silica-30(control) is presented in Fig. 2a. From
2.4. Characterization
the figure it is evident that SBR/SiO2-DeVulcSBR showed plateau
modulus but both silica-30(control) and silica-30(control-TESPT)
The dispersion behavior of different SBR/SiO2-DeVulcSBR, silica-
showed marching modulus. The plateau nature, characteristics of for-
30(control) and silica-30(control-TESPT) composites were studied by
mulations based on DeVulcSBR, is retained at temperature 150 °C for 60
scanning electron microscopy (SEM) analysis of the tensile fractured
min which indicates the superior thermal aging behavior of the cured
surface of the samples by Zeiss EVO-MA10 at 0° tilt angle after coating
rubber samples. Therefore, the plateau modulus of SBR/SiO2-De-
the surface of the sample with sputtered gold. The Fourier transform
VulcSBR compound is the desired outcome as the curing being complete
infrared (FTIR) spectra of the composites was recorded in the ATR
and the formation of stable network (Andrew, 1999; Alan, 2001) in
mode by 64 scans at 4 cm−1 resolution using Bruker, GmbH (Model:
absence of degradation. This may be due to the presence of active
ALPHA), FTIR spectrophotometer. The rubber filler interaction was also
crosslinking sites in the devulcanized rubber, which is characteristic of
measured from equilibrium swelling experiment using the Kraus
devulcanize rubber (Makarov and Drozdovski, 1991). The rheographs
equation (Kraus, 1963) given in Eq. (1):
of silica-30(control-TESPT) and silica-30(control) compounds showed

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 2. Effect of silica loading on (a) curing characteristics; (b) cure rate (t 90 − t10) ; (c) extent of cure (MH − ML ) and (d) plots of (MH − MT ) vs time of different silica
rubber compounds.

marching modulus which specifies that these compounds also have heat 30(control-TESPT) composite with same silica loading (30 phr). The
and reversion resistance property. relatively higher scorch time (t10) and optimum cure time (t90) of silica-
Since the cure properties differed from the loading and surface 30(control-TESPT) composite may be due to the stronger interfacial
property of silica (Mathew et al., 2004) therefore, the cure properties adhesion between SiO2-TESPT and SBR, resulting in limited mobility of
such as scorch time (t10) and optimum cure time (t90) of the SBR SBR chains, which in turn retards the vulcanization (Raza et al., 2011).
compounds are presented in Table 2. From the table it can be observed The vulcanization rate of the composites measured through the differ-
that for SBR/SiO2-DeVulcSBR composites both the scorch time (t10) and ence between t90 and t10 i.e. (t90 – t10), indicates that in SBR/SiO2-
optimum cure time (t90) decreases with silica loading which indicates DeVulcSBR composite with increasing silica content, (t90 – t10) de-
that vulcanization accelerators are not adsorbed on the silica surface creases which signifies increasing trend of vulcanization rate with silica
due to chemical interaction of silica particles with DeVulcSBR but the loading. From Fig. 2b, the (t90 – t10) of silica-30(control) and silica-
respective values are much higher for silica-30(control) composite due 30(control-TESPT) compound are much higher than that of the SBR/
to adsorption of accelerators on the silica surface. Since the perfor- SiO2-DeVulcSBR compound when compared at 30 phr silica loading
mance evaluation of SBR/SiO2-DeVulcSBR composite indicates that which proves that vulcanization accelerators are not adsorbed on the
superior properties are obtained for 30 phr silica loaded composite silica surface rather they accelerate the cross-linking reaction. The
therefore, it is compared with that of the silica-30(control) and silica- difference between maximum torque (MH) and minimum torque (ML )

Table 2
Curing characteristics of SBR/DeVulcSBR/SiO2 blend system.
CuringCharacteristics Formulation Number

Silica-10 Silica-20 Silica-30 Silica-40 Silica-30 (control) Silica-30 (Control-TESPT)

Optimum cure time (t90, min) 14.62 10.69 9.97 8.98 43.93 39.19
t10, min 3.38 3.24 2.71 2.78 16.54 14.42
t90 – t10 (min) 11.24 7.45 7.26 6.20 27.39 24.77
Extent of cure (MH-ML) (Nm) 1.01 1.10 1.15 1.25 0.82 1.06
Cure rate index (min−1) 12.53 11.82 10.69 14.64 3.22 3.49
Cure rate constant, K × 10−3 (min-1) 69.4 96.3 81.5 157.4 63.25 81.9

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

values, represented as MH − ML (Fig. 2c) is a qualitative measure of the Table 3

cross-link density in the samples and is usually known as extent of cure. ηr , Mr and L values of the rubber compounds.
It is observed from the figure that in SBR/SiO2-DeVulcSBR sample the Sample code ηr Mr L
extent cure increases with silica loading whereas the respective value is
lowest for silica-30(control) and moderate for silica-30(control-TESPT) Silica-10 1.4338 1.1769 0.2569
sample. This is an indication of stronger interfacial interaction among Silica-20 1.7187 1.4108 0.3079
Silica-30 1.9316 1.5896 0.3420
SiO2, SBR and DeVulcSBR.
Silica-40 2.8203 1.7091 1.1112
The kinetics of cure reaction of SBR/SiO2-DeVulcSBR compound Silica-30(control) 1.8606 1.1187 0.7419
was evaluated from cure data (Mathew et al., 2003). The kinetic Silica-30(control-TESPT) 1.5057 1.3338 0.1719
equation of a first order chemical reaction was presented in Eq. (3):
ln (a − x ) = −kt + ln a (3)
respective values are much higher than that of the others indicating the
wherea is the initial concentration of the reactant, x is the concentra- presence of more silica agglomerates in the rubber composite.
tion of the product at any time t and k is the constant called velocity
constant for first order reaction. In the cross-linking reaction of the 3.2. Rubber-filler interaction
rubber compounds, the torque developed during cross-linking is the
measure of the cross-link formation. The torque developed is propor- 3.2.1. FTIR analysis
tional to the modulus of rubber. Therefore, (a − x ) and a can be re- In the mechanochemical devulcanization of vulcanized SBR by
presented as follows: TESPT in an open-roll mixing mill, temperature develops due to me-
(a − x ) = MH − MT (4) chanical shearing forces and as a result, homolytic scission of SeS
bonds (bond energy 22.8 Kcal/mol) of TESPT takes place leading to the
a = MH − ML (5) formation of the fragmented disulfide free radicals. Simultaneously, the
where, MH , MN and ML represents the maximum rheometric torque, cleavage of both polymer chain and cross-link bonds of vulcanized SBR
minimum rheometric torque and rheometric torque at any time t re- takes place. Since the free radicals are very much reactive due to the
spectively. By substituting these values in Eq. (3) we get presence of unpaired electrons, therefore, the fragmented disulfide free
radicals are readily combine with both the broken polymer chain and
ln (MH − MT ) = −kt + ln (MH − ML) (6) cross-link radicals, resulting in chain capping. The chemical interaction
The plots of ln (MH − MT ) vs t of rubber compounds are shown in between fragmented TESPT and granulated SBR was confirmed by
Fig. 2d. The linearity of the plots of all the compounds including SBR/ sulphur analysis and FTIR study. Here the DeVulcSBR sample was ex-
SiO2(30) and SBR/SiO2(30)-TESPT follows first order kinetics. The cure tracted initially for 48 h in acetone for removal of unreacted substances.
reaction rate constant (k ) was evaluated for different rubber compounds Then the sulphur analysis was carried out which indicated that sulphur
from the slope of the curve and presented in Table 2. From the table it is content increased from 2.47 % in GSBR to 2.75 % in DeVulcSBR (Ghosh
evident that in case of SBR/SiO2-DeVulcSBR compound with increasing et al., 2017). The FTIR spectrum of TESPT and DeVulcSBR are pre-
silica loading k value increases. The k value of SBR/DeVulcSBR/SiO2 sented in Fig. 3a. The characteristic peaks of TESPT appeared at 1165
compound with 30 phr silica loading is almost comparable with that of cm−1 (Si – O cage like stretching mode), 1071 and 955 cm−1 (Si – O
the silica-30(control-TESPT) compound whereas the k value of silica- stretching) and 1242 cm−1 (symmetric Si-C-H bending). In DeVulcSBR
30(control) compound is much lower compared to that of the other absorption peak at 1165 cm-1 for Si-O cage like stretching mode, 1078
compounds which indicates cure deactivation. Since the huge amount and 965 cm−1 for Si-O stretching and 1242 cm−1 for symmetric Si-C-H
of hydroxyl groups (−OH) present on the silica surfaces are responsible bending, indicating the chemical attachment of fragmented TESPT in
for agglomerate formation therefore maximum and minimum torque DeVulcSBR.
obtained from rheometric data can be used to study the dispersibility of The silica reinforcement mechanism of DeVulcSBR in the re-
silica filler in the rubber matrix because according to Lee (Lee, 1979) vulcanizates is shown in Scheme 2. Here, the fragmented TESPT (de-
the filler particles in the vulcanized and unvulcanized state indicates vulcanizing agent) attached with the broken polymer chain and cross-
the different amount of agglomerate formation. Lee coined a term L link bond in DeVulcSBR containing pendant ethoxy (−OC2H5) end
which is given by group, will form bond with the hydroxyl (−OH) group present in the
silica surface to form Si-O-Si linkages. To see the chemical interaction
L = ηr − Mr (7) between DeVulcSBR and silica the FTIR spectrum of SiO2, SBR/SiO2-
where ηr and Mr are the relative viscosity and relative modulus, which DeVulcSBR and SBR/SiO2-TESPT are presented in Fig. 3b. The broad
may be presented as follows: peak at 3446 cm−1 corresponds to −OH stretching of Si −OH and
another peak at 1105 cm−1 was attributed to Si – O – Si stretching in
Mf min
ηr = silica. But, no peak for −OH stretching is appeared either in SBR/SiO2-
Mg min (8) DeVulcSBR or SBR/SiO2-TESPT vulcanizate whereas, the characteristic
Mf max peak at 1070 cm−1 for SBR/SiO2-DeVulcSBR and 1078 cm−1 for SBR/
Mr = SiO2-TESPT vulcanizate, due to Si-O-Si stretching clearly specifies the
Mg max (9)
silica reinforcement in the vulcanizate due to chemical interaction be-
whereMf andMg represents the rheometric torque of filled and gum tween the hydroxyl group present in the silica surface and the pendent
compound respectively. For efficient dispersion ethoxy group (−OC2H5) of the DeVulcSBR to form Si-O-Si linkages. The
success of DeVulcSBR as an interfacial modifier in SBR/SiO2-De-
ηr = Mr (10)
VulcSBR composite is due to silanization of the silica. The silanization
Therefore, the value of L will give an idea about filler dispersion. reaction is divided into primary and secondary silanization as shown in
From Table 3 it is seen that both ηr and Mr increases with silica loading Scheme 2. The primary silanization reaction can proceed through two
in SBR/SiO2-DeVulcSBR compound and ηr values are higher than Mr pathways, either by direct condensation between the silanol groups of
values which indicates the presence of silica agglomerates. Even for the silica surface and one alkoxy group of fragmented TESPT which is
silica-30(control-TESPT) compound containing conventional silane attached with DeVulcSBR or by hydrolysis of the pendant alkoxy groups
coupling agent, shows higher ηr value than Mr . In case of 40 phr silica of the DeVulcSBR to form reactive hydroxyl groups prior to the con-
loaded SBR/DeVulcSBR composite and silica-30(control) composite the densation reaction (Görl et al., 1997). Both the reactions release ethanol

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 3. (a) FTIR spectra of TESPT and DeVulcSBR; (b) FTIR spectra of SiO2, SBR/DeVulcSBR/SiO2 and SBR/SiO2/TESPT.

silica loading in Fig. 4a. From the figure it is seen that in the different
silica loaded composites as solvent penetration decreases with silica
loading consequently volume fraction increases which specifies less free
space in the composite due to maximum rubber-filler interaction. Fur-
thermore, when the volume fraction is evaluated at a particular con-
centration of silica loading (30 phr), it is found that the lowest solvent
uptake as well as the highest volume fraction is observed for silica-30
composite followed by silica-30(control-TESPT) and silica-30(control)
composite. Fig. 4b shows the plot of ( ) against ( ) of SBR/SiO -
Vr 0
Vrf
f
1−f 2

DeVulcSBR composite according to Kraus equation (Kraus, 1963). The

nature of the plot gives a straight line and the negative slope of the line
indicates the polymer-filler interaction (Paul et al., 2009). Cunneen –
Russell equation was also used to further evaluate the interfacial in-
teraction between filler and rubber, which is presented in the Eq. (2)
(Cunneen and Russell, 1970). The plot of ( ) against e
Vr 0
Vrf
−z of SBR/SiO2-
DeVulcSBR composite presented in Fig. 4c gives a straight line with
positive slope having high a and low b value specifies rubber-filler in-
V
teraction and Vr 0 〈1 indicates reinforcement in the composite. Extent of
rf
reinforcement was determined from the Lorentz Park equation (Lorenz
and Parks, 1961) derived from Cunneen – Russell equation (Cunneen
Scheme 2. The schematic presentation of SiO2/SBR/DeVulcSBR vulcanizate and Russell, 1970).
with covalent bonding interface in absence of silane coupling agent.
Qf
= ae−z + b
(C2H5OH) as by-product. The secondary reaction frequently occurs Qg (11)
between adjacent pendant TESPT fragments of the DeVulcSBR, also
Where Q is the amount of solvent imbibed per unit weight of the rubber,
releasing ethanol. Besides, both the SBR/SiO2(30)-DeVulcSBR and SBR/
f and g refer to filled and gum vulcanizates.
SiO2(30)-TESPT composites show− CH−out of plane bending of trans
butadiene unit at 961 cm−1, 1, 2-vinyl group of butadiene at 909 cm−1, Qf Vro (1 − Vrf ) Vro
− CH− out of plane deformation and ring deformation of mono- = =
Qg Vrf (1 − Vr 0 ) Vrf (12)
substituted benzene due to butadiene part at 755 cm−1 and − CH− out
of plane deformation and ring deformation of monosubstituted benzene Vr 0
As from Cunneen and Russell Eq. (2), i.e., Vrf
= ae−z + b
only at 699 cm−1.
The Qg values at variable filler loading in SBR/SiO2-DeVulcSBR
Qf

composites as well as the slica-30(control) and slica-30(control-TESPT)

3.2.2. Equilibrium swellingexperiment composites having particular filler loading (30 phr) are shown in
The equilibrium swelling experiment of the composites was studied Table 4. The higher Qf Qg values, the lower will be the extent of inter-
to get an idea about the rubber-filler interfacial interaction. The volume action between filler and rubber. It is evident from the table that in case
fraction (Vrf ) of the rubber in the swollen composite is presented with of SBR/SiO2-DeVulcSBR composites Qf Qg decreases with filler loading

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 4. (a) Effect of silica content on volume fraction (Vr f ) ; (b) Variation of Vr 0/ Vrf with f /1 − f (Kraus Plot); (c) Variation of Vr 0/ Vrf with e−z (Cunneen and Russel Plot)
and variation of Qf / Qg with e−z .

Table 4 is calculated from the following expression:

Q
Vrf , Vr 0 , f and crosslink density values of the rubber composites.
Vrf Qg (Ms − Md )
Swellingindex(ΔM %) = × 100
Sample code Vrf Vr 0 Qf Cross-link Swelling Mi (13)
Vrf index
Qg density× 10−3 (mol/
cm3)
where Ms , Md andMi represent the swollen weight, dried weight and
initial weight of the composites. The penetration of solvent in the
Silica-10 0.243 0.926 0.865 1.185 234.96 composite mainly depends on the presence of void space inside the
Silica-20 0.258 0.873 0.769 1.217 213.69 composite. Decreasing number of void spaces inside the composite with
Silica-30 0.267 0.842 0.709 1.251 197.89
Silica-40 0.275 0.818 0.662 1.281 184.68
filler loading in SBR/SiO2-DeVulcSBR composite decreases the solvent
Silica-30(control) 0.167 1.345 1.306 1.051 361.38 uptake. The swelling index values of different composites are shown in
Silica-30(control- 0.215 1.044 0.961 1.177 261.17 Table 4. Slica-40 composite containing 40 phr silica shows minimum
TESPT) swelling index as a result higher reinforcing efficiency by silica whereas
the higher swelling index as well lower crosslink density of silica-
30(control) composite indicates the presence of silica agglomerates in
which indicates superior rubber-filler interaction. The lowest Qf Qg value
the vulcanizate.
is observed for 40 phr silica loaded silica-40 composite. This confirms
that maximum interaction between filler and rubber occurs in presence
of DeVulcSBR having 40 phr silica loading. A plot of Qf Qg against e−z 3.3. Mechanical properties
gives a straight line with positive slope as shown in Fig. 4c which
confirms the above findings. The reinforcing effect of the filler can be The stress-strain behavior of SBR/SiO2-DeVulcSBRs, silica-30(con-
supported by the cross-link density measurement. Table 4 shows the trol-TESPT) and silica-30(control) composites are shown in Fig. 5a and
cross-link density values in different composites. 40 phr silica loaded the respective values are summarized in Table 5. Comparing with the
silica-40 composite shows maximum cross-link density indicating stress-strain curve of silica-30, silica-30(control-TESPT) and silica-
maximum interaction between filler and rubber. Moreover, in case of 30(control) composites, the tensile modulus and ultimate tensile
SBR/SiO2-DeVulcSBR composites as the filler loading increases the strength silica-30 composite are improved significantly than that of the
cross-link density values are also found to increase. The swelling index silica-30(control) composite, which indicates stronger rubber-filler in-
which is a measure of the resistance to swelling of the rubber composite teraction in the composite. Although the respective values are almost
comparable with silica-30(control-TESPT) composite. SBR/SiO2-

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 5. (a) Stress-strain behavior of different silica-rubber vulcanizates; (b) abrasion loss with silica loading in the vulcanizate.

DeVulcSBR composites showed a remarkable increase in modulus and higher than that of the silica-30(control-TESPT) composite. The highest
strength of the composite with increase in silica loading. The tensile abrasion loss is seen for silica-30(control) composite due to poor in-
strength of the SBR/SiO2-DeVulcSBR composites increase with silica terfacial interaction. The study reveals that the silica-30(control-
loading which indicates enhanced rubber filler interaction between TESPT) composite has highest abrasion resistance property followed by
hydroxyl (−OH ) group of silica and the pendent ethoxy (–OEt ) func- silica-30 composite and silica-30(control) composite.
tional group of DeVulcSBR. Although the increment of tensile strength
with silica loading is much higher upto 30 phr silica loading but for
further increase in silica loading the increment of tensile strength is 3.4. Thermogravimetryanalysis
marginal. The elongation at break also increases till 30 phr silica
loading which indicates better reinforcement, but with further increase In case of rubber vulcanizates, the stability depends on environ-
in silica loading the vulcanizates become stiff due to agglomeration of ment, as degradation is primarily dependent on thermal or thermo-
silica particles resulting in diminution both in reinforcement and oxidative degradation, or both. The structure of the main chain, the
elongation at break. The poor tensile strength of slica-30(control) energy of main chain bonds, the nature of cross-links, and the presence
composite is mainly due to the non-uniform dispersion of silica filler of extra network affect the thermal stability of rubber vulcanizates. In
into the SBR matrix and the presence of silica agglomerates in the order to get the informations about the nature and extent of degrada-
composite due to hydrogen bonding in addition to Van der Waals forces tion of the material thermogravimetry and differential thermo-
and other physical interactions of the silanol groups present on the si- gravimetry analysis was carried out. Fig. 6 shows the thermogravi-
lica surface which inhibit stress transmission and reduce the tensile metric (TG and DTG) curves for SBR/SiO2-DeVulcSBRs, silica-
strength of the composite. However, the mechanical performance of 30(control-TESPT) and silica-30(control) composites. The decomposi-
slica-30(control-TESPT) is superior compared to that of the others, tion temperature at various weight loss, the temperature at maximum
because the conventional coupling agent, TESPT facilitate the silica weight loss, the rate of change of weight at Tmax and char residue are
dispersion in the SBR matrix and simultaneously enhance the interfacial presented in Table 6. It is to note that the peak temperatures of different
interaction through chemical bond formation. The tear strength of composites are more or less consistent except the Silica-10 which could
DeVulcSBR containing composite also increases with silica loading and be attributed to different specific heat capacity. However, it is an open
the maximum value is achieved at 40 phr silica loading. Also the question requires in-depth study. In SBR/SiO2-DeVulcSBR composite,
highest value of tear strength is obtained for silica-30(control-TESPT) the temperature at 50 % weight loss and the maximum degradation
composite but the tear strength of silica-30(control) composite is much temperature increases up to 30 phr silica loading, due to interfacial
inferior compared to that of the other composites due poor dis- interaction between DeVulcSBR and SiO2, although the temperature at
persibility of silica into SBR matrix. 70 % weight loss continuously increases with silica loading. The in-
The improved interfacial interaction and homogeneous dispersion crease in char residue of the composite is due to the presence of in-
of silica filler in SBR matrix either in presence of DeVulcSBR or TESPT creasing proportion of silica in the composite. The rate of change of
are further confirmed by the study of the abrasion resistance of the weight at Tmax decreases with silica loading which also supports the
composites. The abrasion loss of the composites presented in Fig. 5b rubber-filler interaction in the DeVulcSBR containing composite. After
clearly specifies that abrasion loss decreases with silica loading and the repeated experiment we found that the thermal decomposition of silica-
lowest value is obtained for 30 phr loading and the value is slightly 30(control) and silica-30(control-TESPT) composite is almost compar-
able. The comparable thermal behavior of both the composites can be

Table 5
Mechanical properties of the composites.
Sample Code 50 % Modulus (MPa) 100 % Modulus (MPa) Tensile Strength (MPa) Elongation at Break (%) Tear Strength (MPa)

Silica-10 1.07 ± 0.2 1.57 ± 0.1 3.42 ± 0.6 263 ± 8 10.33 ± 0.6
Silica-20 1.35 ± 0.3 1.97 ± 0.2 4.94 ± 0.7 289 ± 9 14.61 ± 0.7
Silica-30 1.45 ± 0.2 2.35 ± 0.2 10.34 ± 0.5 451 ± 7 22.68 ± 0.5
Silica-40 1.85 ± 0.1 2.78 ± 0.1 11.79 ± 0.6 426 ± 9 25.57 ± 0.8
Silica-30(control) 1.17 ± 0.3 1.63 ± 0.2 4.34 ± 0.7 336 ± 10 12.14 ± 0.9
Silica-30(control-TESPT) 1.02 ± 0.2 1.28 ± 0.2 9.98 ± 0.8 998 ± 11 26.03 ± 0.8

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

particles. When the strain goes beyond a critical value, the majority of
the modulus is attributed to the rubber itself. When the volume fraction
of filler increases, filler-filler interaction increases and causes a filler
network to form. This network causes reinforcement mechanisms dif-
ferent from those of simple hydrodynamics. In DeVulcSBR containing
vulcanizate the increasing trend of room temperature storage modulus
with silica loading is mainly due to strong interfacial interaction be-
tween the silanol groups on the silica surface and the pendent ethoxy
group present in the DeVulcSBR. Moreover, the room temperature
storage modulus value of TESPT (conventional silica coupling agent)
containing vulcanizate is almost comparable (Table 7) with that of the
DeVulcSBR containing composite having same silica loading.
The temperature dependence of loss modulus curves (Fig. 7b) shows
a maximum, whose intensity increases with silica loading, which in-
dicates with increasing silica loading, energy dissipation will be more.
Increasing proportion of filler loading results in a percolated network of
filler particles which can influence relaxation of the composite in dif-
ferent scale (Sridhar et al., 2009). From the figure it is seen the loss
modulus value during transition stage of silica-30 composite (474.3
Fig. 6. Thermogravimetry analysis and their respective differential thermo- MPa) is less than that of the silica-30(control-TESPT) composite (483.1
grams of different silica rubber vulcanizates.
MPa). The energy loss of the silica filled rubber composite, hence the
loss modulus during dynamic strain is largely controlled by the
Table 6 breakdown and reformation of the filler network (Wang, 1998). Since
Decomposition temperature at various weight losses of the composites. the optimum silica loading is 30 phr for SBR/DeVulcSBR composite,
Sample Code Degradation Tmax (oC) The rate of % Residue therefore, its loss modulus value is compared with that of the silica-
temperature (oC) change of 30(control-TESPT) composite having same proportion of silica content
weight at Tmax and the result specifies that the lower loss modulus of silica filled SBR/
T-50% T-70% (%/min) DeVulcSBR composite indicates higher filler-rubber interaction rather
Silica-10 451.0 468.7 447.8 11.3 16.0
than filler-filler interaction. The maximum loss modulus of silica-
Silica-20 454.8 476.5 463.2 9.6 20.8 30(control-TESPT) composite may be due to the fact that here the
Silica-30 461.7 486.2 465.5 9.2 26.4 ethoxy (−OEt ) functional group of TESPT is completely exhausted by
Silica-40 460.5 539.0 464.5 8.7 29.2 the chemical interaction with the hydroxyl (−OH ) group on the silica
Silica-30(control) 460.3 482.6 467.7 9.4 24.6
surface and the remaining silica fillers in the composite are involved in
Silica-30(control- 460.5 482.8 464.3 9.5 24.7
TESPT) aggregate or agglomerate formation due to strong filler-filler interac-
tion which ultimately increases loss modulus for reformation and
breaking of agglomerated silica network under dynamic strain.
explained in a different way. In case of silica-30(control) composite due The temperature dependence curve of loss factor (Tanδ) (Fig. 7c)
to strong filler-filler interaction filler particles form small clusters and shows that the position of the maximum value of loss tangent (Tanδmax )
subsequently these small clusters may be dispersed freely without is not considerably influenced by the silica loading. All the SBR/SiO2-
contact between them. But in case of high filler loading these small DeVulcSBR composites show the glass transition (Tg ) in the narrow
clusters begin to attach themselves as a result a strong filler-filler net- temperature range from – 24 °C to – 28 °C but the highest Tanδ at Tg
work is formed (Vilgis et al., 2009). This network in case of silica- decreases with silica loading in SBR/SiO2-DeVulcSBR composite as
30(control) composite and the strong rubber-filler network in silica- evident from Table 7. The interaction between rubber and filler and the
30(control-TESPT) composite may impede the evaporation of decom- phase continuity determines the Tanδ at low temperature. The main
position products to reduce the rate of initiation of polymer chain characteristic of reinforced elastomer is that most of the polymer chains
scission to produce volatile small products. Therefore, it could inhibit are in contact with the filler surfaces.
the occurrence of SBR chain scission and improve the thermal stability Incorporation of filler into the polymer matrix induces a gradient of
(Yin et al., 2014). Tg in the polymer chains which are in the vicinity of the fillers due to
strong dynamical heterogeneities (Long and Lequeux, 2001; Ediger,
2000). But the highest Tanδ at Tg decreases with silica loading with
3.5. Dynamic mechanical analysis simultaneous broadening of the peak of SBR/SiO2-DeVulcSBR compo-
site. The interaction between rubber and filler and the phase continuity
The change in the microstructure of the composite by the SiO2 determines the Tanδ at low temperature. Increase in the proportion of
loading, greatly affect the dynamic viscoelastic properties of the com- silica loading decreases the chain mobility and increases the extent of
posite material. The temperature dependence of storage modulus, loss restriction due to rubber-filler interaction in the composite which ul-
modulus and Tanδ of the composites is shown in Fig. 7a, b and c re- timately decreases the Tanδ value. The effect of filler loading on the
spectively. The highest room temperature (25 °C) storage modulus is damping behavior of the composite may be due to the decreasing free
achieved for silica-40 composite. The hydrodynamic reinforcement and volume with increasing silica content, which restricts the mobility of
the interaction between filler-filler and filler-rubber are responsible for the polymer chains and as a result damping value decreases. Moreover,
the increase in the storage modulus of the composite. When rigid the internal frictions between filler and polymer segments and among
spherical particles are dispersed into a fluid, an increase in viscosity the filler particles over the transition range increases with temperature
takes place in case of liquid or a modulus enhancement in case of and consequently enhance the mobility of the polymer segments which
polymer at low filler volume fraction due to hydrodynamic reinforce- ultimately increase the damping behavior (Trakulsujaritchok and
ment (Heinrich et al., 2002; Fukahori, 2007; Leblanc, 2010; Berriot Hourston, 2006).
et al., 2002). The hydrodynamic effect accounts for the increase in The plot of storage modulus (E′) vs loss modulus (E′ ′) i.e. Cole – Cole
modulus under condition of low strain and low volume fraction of filler plot of SBR/SiO2-DeVulcSBRs and silica-30(control-TESPT) composites

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 7. (a) Storage modulus; (b) loss modulus; (c) Tan ∂ and (d) storage modulus vs loss modulus of different SBR/SiO2-DeVulcSBRs, SBR/SiO2(30) and SBR/
SiO2(30)-TESPT vulcanizates.

Table 7 surface. The micrographs also indicate that SBR/SiO2-DeVulcSBR

Values of E′, Tanδmax and Tg of the composites. composites exhibit superior silica dispersion even at high filler content
Sample Code E′ (MPa) at 25 °C Tanδmax Tg at peak temperature
40 phr than that of SBR/SiO2 composites. The SEM micrograph of silica-
30(control-TESPT) composite (Fig. 8f) is almost comparable with that
Silica-10 4.88 0.97 −26.5 of the SBR/SiO2-DeVulcSBR composites which indicates the effective-
Silica-20 7.65 0.97 −24.3 ness of DeVulcSBR as interfacial modifier of silica particles in the
Silica-30 12.33 0.85 −24.6
composites. However, slica-30(control) composite shows huge ag-
Silica-40 17.95 0.75 −24.6
Silica-30(control) 10.25 1.18 −27.8 glomerates of silica particles shown in Fig. 8e.
Silica-30(control-TESPT) 7.59 1.21 −27.8

4. Conclusion
is shown in Fig. 7d. The relaxation dynamics of the composites can be
explained on the basis of Cole – Cole plot. Irrespective of the con- Devulcanization of waste SBR vulcanizate was carried out using bis
centration of silica loading all composite shows depressed semicircle (3-triethoxysilyl propyl) tetrasulfide in an open-roll mixing mill. The
which clearly signifies the reinforcement in the composite but the ra- extent of devulcanization such as cross-link density decreases from
dius of the arc changes which indicates the relaxation dynamics and 1.106 × 10−3 mol/cm3 (DeVulcSBR) to 0.968 × 10−3 mol/cm3 (GSBR)
considerable alteration of chain conformation (Lipinska and Imiela, whereas sol content increases from 4 % (GSBR) to 24.5 % (DeVulcSBR)
2019). All the plot shows smooth arcs indicating homogeneous dis- which indicates the superior quality of DeVulcSBR in product applica-
persion of silica into the composite. tions. The characteristic peaks of Si-C-H bending (1242 cm−1), Si-O
cage like stretching (1065 cm−1) and Si-O stretching of Si-alkoxy
compound (1078 and 965 cm−1) of DeVulcSBR through FTIR study
3.6. Morphology of SBR composites indicates the attachment of fragmented TESPT with DeVulcSBR.
Moreover, the disappearance of peak of −OH stretching and appear-
Fig. 8 represents the SEM images of the tensile fractured surface of ance of characteristic peak of Si-O-Si stretching (1070 cm−1) in SBR/
the SBR/SiO2-DeVulcSBR composites at different silica loading, silica- DeVulcSBR/SiO2 vulcanizate firmly indicates the chemical interaction
30(control-TESPT) and silica-30(control) composites. It is evident from between silica and DeVulcSBR. Thus DeVulcSBR prepared in this pro-
the Fig. 8(a)-(d) that the presence of DeVulcSBR facilitates silica dis- cess is not only used as a replacement of fresh SBR but also as an in-
persion due to chemical interaction between the pendent ethoxy group terfacial modifier in SBR/SiO2-DeVulcSBR vulcanizate without any
(- OEt) of DeVulcSBR and the silanol groups (−OH) on the silica coupling agent. The cure rate constant (K) of silica-30 vulcanizate (81.5

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J. Ghosh, et al. Resources, Conservation & Recycling 154 (2020) 104629

Fig. 8. SEM micrograph of (a) Silica-10; (b) Silica-20; (c) Silica-30; (d) Silica-40; (e) Silica-30 (control) and (f) Silica-30 (Control-TESPT) at 2000X magnification.

min−1) is almost comparable with that of the silica-30(control-TESPT) Declaration of Competing Interest
vulcanizate (81.9 min−1) whereas the respective value of silica-
30(control) vulcanizate (63.25 min−1) is much lower indicating cure None.
deactivation. The tensile strength and elongation at break of silica-30
vulcanizate are 10.34 MPa and 451 % respectively, whereas the re- Acknowledgements
spective values of silica-30(control) vulcanizate are 4.34 MPa and 336
% respectively. Dynamic mechanical analysis reveals that room tem- The authors thankfully acknowledge the partial financial support by
perature storage modulus increases and highest tanδ at Tg decreases the Department of Science and Technology (DST), Science and
with silica loading in silica-30 vulcanizate due to strong rubber-filler Engineering Research Board (SERB), New Delhi, India, (Project No. SB/
interaction. The results indicate that in SBR/DeVulcSBR compound the S3/ME/40/2013 Dated April 09, 2014) for carrying out the present
optimum dose of silica loading is 30 phr. The SEM analysis of silica-30 research work.
vulcanizate shows uniform dispersion of silica in submicron length
scale whereas in silica-30(control) vulcanizate bigger agglomerates are References
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DeVulcSBR as interfacial modifier in silica-30 composite was compared Adhikari, B., De, D., Maiti, S., 2000. Reclamation and recycling of waste rubber. Prog.
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Alan, N.G., 2001. Engineering With Rubber – How to Design Rubber Components, 2nd
ventional silica coupling agent TESPT. The properties of both the edition. Hanser Publishers, Munich.
composites are almost comparable and much higher than that of the Andrew, C., 1999. An Introduction to Rubber Technology, 1st edition. Rapra Technology
silica-30(control) composite. Thus, the developed devulcanized SBR has Ltd., Germany.
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tremendous potential in green tire application as well as other high vulcanization. Resour. Conserv. Recycl. 133, 250–262.
performance rubber/silica nanocomposites. Berriot, J., Montes, H., Lequeux, F., Long, D., Sotta, P., 2002. Evidence of the shift of the
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