See

discussions, stats, and author profiles for this publication at:

https://www.researchgate.net/publication/266144913

Reclaiming of ground rubber tire by

safe multifunctional rubber additives:
I. Tetra benzylthiuram disulfide

Article in Rubber Chemistry and Technology December 2012

DOI: 10.5254/rct.12.88949

CITATIONS READS

5 217

3 authors:

Swapan Kumar Mandal Md. Najib Alam

University of Kalyani Chulalongkorn University
20 PUBLICATIONS 107 CITATIONS 17 PUBLICATIONS 54 CITATIONS

SEE PROFILE SEE PROFILE

Subhas Chandra Debnath

University of Kalyani
56 PUBLICATIONS 504 CITATIONS

SEE PROFILE

All content following this page was uploaded by Md. Najib Alam on 28 September 2014.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original docum
and are linked to publications on ResearchGate, letting you access and read them immediately.
RECLAIMING OF GROUND RUBBER TIRE BY SAFE MULTIFUNCTIONAL
RUBBER ADDITIVES: I. TETRA BENZYL THIURAM DISULFIDE

SWAPAN KUMAR MANDAL, NAJIB ALAM, SUBHAS CHANDRA DEBNATH*

DEPARTMENT OF CHEMISTRY, UNIVERSITY OF KALYANI, KALYANI, NADIA 741235(W.B), INDIA

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

ABSTRACT
The present paper describes the mechanical reclaiming of ground rubber tire (GRT) by safe tetra benzyl thiuram
disulfide (TBzTD), a multifunctional rubber additive. The versatility of the proposed agent is that it acts as a reclaiming agent
during reclaiming and as a curing agent during revulcanization of the reclaimed materials. In this regard, we want to introduce
a safe reclaiming agent in reclamation of GRT for improving its physical and mechanical performance. Reclaiming GRT has
been carried out in an open roll mixing mill at various time intervals and different concentrations of the reclaiming agent
(TBzTD) in the presence of spindle oil. The degree of reclaiming has been evaluated by the measurement of sol content, gel
content, Mooney viscosity, inherent viscosity of sol rubber, and degree of cross-link of the reclaimed materials as a function
of milling time. Also, the influence of gel content on cross-link density at various time intervals on the open two roll mixing
mill has been determined. A unique correlation between gel fraction and cross-link density obtained at various time intervals
and concentrations of reclaiming agent indicate that an optimization of the concentration of safe TBzTD and milling time has
a positive influence on improving the efficiency of reclamation. The reclaiming conditions have been optimized in view of the
mechanical properties of the revulcanized GRT and the aging resistance properties of the revulcanized reclaim. The
influences of the concentration on the mechanical properties in the revulcanized reclaim have also been studied. Scanning
electron microscopy (SEM) studies further indicate the coherency and homogeneity in the revulcanized reclaimed rubber
when reclamation is carried out by optimum concentration of safe TBzTD after maximum time of reclaiming. [doi:10.5254/
rct.12.88949]

INTRODUCTION
The disposal of discarded rubber products like tires, tubes, hoses, conveyor belts, etc. is a
major environmental problem of 21st century. These materials seems to be nonbiodegradable or
degrade very slowly by environmental plants or animals. Hence these materials are not
ecologically friendly. To save the environment from the problem of waste rubber products,
reclaiming or recycling is desirable. Reclaiming not only protects our environment, but also
saves the limited petroleum resources from which the raw material originates. Numerous
techniques1 have been proposed for reclaiming waste rubber products, including mechanical,24
thermo mechanical,5 cryo mechanical,6 microwave,7 ultrasound,8,9 and microbial desulfurization
techniques.1012 In a review paper, Adhikari et al.13 have discussed various reclamation
methods. Currently, the majority of the rubber industry uses a chemical reclaiming process with
various types of organic disulfide and mercaptans as reclaiming agents at elevated temperatures.
Based on these chemicals, many processes have been developed and subsequently patented.
Knorr14 has shown the action of diaryl disulfide on synthetic and natural rubber scraps of
technical goods at 150180 8C. Schnecko15 has reviewed elastomer recycling and reported the
development of some chemical probes for devulcanization of cross-linked rubber. These
chemical probes selectively break carbonsulfur and sulfursulfur bonds, but they do not cleave
carboncarbon bonds. Rubber vulcanizates can also be reclaimed by transition metal alloys and
derivatives.16 In these techniques, the vulcanized rubbers are swollen into organic solvent and
then treated with suitable reducing agent, for example, Mn powder. Two-mercaptobenzothia-
zol17 was also found to be an effective reagent for reclamation of waste powder rubber.
Anderson18 patented the reclamation of sulfur-vulcanized rubber in the presence of oil, water

*Corresponding author. Ph: 91-33-2582-8750(O) [ext. 305]; email: debnathsubhas@yahoo.com

629
630 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

vapor, and aryl disulfide at elevated temperature ranges from 175 to 195 8C and a pressure in the
range of about 230260 psi for about 34 h. Here, aryl disulfide is the mixture of disulfides,
namely, diphenyl disulfide, dicresyl disulfide, and dixylyl disulfide. Kohler19 reported a new
technique for the devulcanization of sulfur cured scrap rubber using the material termed De-vulc
developed by Sekhar.20 De and coworkers21,22 have developed a simple technique for reclaiming
of waste rubbers with an ecologically friendly renewable resource material. The major
constituent of the resource material is diallyl disulfide. Other constituents of the renewable
resource material are different disulfides, monosufides, polysulfides, and thiol compounds. The
experiments of mechanical reclaiming supported by the renewable resource material have been
conducted on various types of rubbers, which were NR,23 SBR,24 and a NR/PBR25 blend
system. De and his coworkers26 use a multifunctional reclaiming chemical, for example, tetra
methyl thiuram disulfide, for reclamation of ground rubber tire (GRT). They showed that a
minimum concentration of reclaiming agent and 3540 min of milling were sufficient to obtain
the desired properties of devulcanized rubber from ground rubber tire. The thiuram disulfides
used as reclaiming agents are merely produced form secondary amine. Most of the secondary
amine has been shown to produce nitrosamines, which are believed to be carcinogens.27 A
significant amount of rubber chemicals are produced from these secondary amines. In fact, in a
survey it was shown that these rubber additives and the vulcanizates obtained from these
chemicals contain varying proportions of nitrosamines.28 In a recent survey, de Vocht et al.29
have shown that exposure to N-nitrosamines, namely, N-nitrosodimethylamine (NDMA) and N-
nitrosomorpholine (NMor), decreased on average 2 to 5-fold in the German rubber industry with
comparable concentration levels in other European countries. Although average levels are well
below the current limits, exposure has not been eliminated, and incidental high exposures do still
occur.29
In the present paper, we are trying to describe the mechanical reclamation of GRT of undefined
particle size by safe tetra benzyl thiuram disulfide (TBzTD) derived from safe amine as the main
reclaiming agent in order to introduce this safe reclaiming agent to the devulcanization of GRT in
the presence of spindle oil. Oil plays several roles apart from raising the plasticity of reclaimed
rubber, such as an accelerating activity on the process of oxidation of the rubber30 and a gel
preventing activity by acting as a radical acceptor. It also facilitates the dispersion of the reclaiming
agent into the rubber matrix. Hence reclaiming oil with a high compatibility should be used.30 The
reclaiming oils often have active double bonds or methylene groups in the molecules, through
which they are more easily oxidized than the rubber molecule.30 It is assumed that these activated
molecules, which formed by the auto-oxidation reaction, accelerate the oxidation of the rubber.
Yamashita31 published a review on the different reactions that might occur during reclaiming. The
auto-oxidation accelerated degradation reactions are described, and these reactions occur
particularly in the reclaiming process that involves shearing actions. Without the addition of
reclaiming agents, auto-oxidation reactions will progress through hydroperoxides formed by the
attack of oxygen, which is always present in the rubber. Use of reclaiming agents speeds up and
introduces new pathways for the reclamation reactions.31 Starting from the main chain session and
cross-link session of polymer, the reclaiming agent and reclaiming oil should be used with a
compatibility ratio for the devulcanization of ground rubber tire. The extent of reclaiming has been
evaluated by the measurement of sol content, inherent viscosity of sol rubber, gel content, Mooney
viscosity, cross-link density, and molecular weight between two cross-links of gel rubber of the
reclaimed rubber as a function of milling time and concentration of the reclaiming agent. Curing
behavior, mechanical properties, and aging characteristics of revulcanized rubbers have been
studied. A possible mechanism of mechanical devulcanization is also presented.
 RECLAIMING OF GROUND RUBBER TIRE (GRT) 631

EXPERIMENTAL
MATERIALS

GRT purchased from local market was used. The GRT was an unclassified ground rubber from
the tread and side walls of passenger and truck tires. TBzTD (ICI Ltd. India), zinc oxide (Merck),
stearic acid (Loba Chemie, India), sulfur (Loba Chemie, India), spindle oil (MCI, India), and
toluene (Merck) were used as received.

PREPARATION OF RECLAIMED RUBBER

One hundred grams of ground rubber tire were mixed with TBzTD in various proportions
along with 10 ml spindle oil and allowed to stand for 24 h. The mixture was then transferred to an
open two roll mixing mill, and milling was carried out for various time intervals. It was found that
with progress of milling the materials became sticky and band formation occurred on the roll. The
reclaiming was carried out around ambient temperature.

REVULCANIZATION

Prior to vulcanization the reclaimed materials were compounded with 5 phr zinc oxide, 2 phr
stearic acid, and 0.5 phr sulfur on a laboratory size two roll mixing mill of roll size 203 3 102 mm
(Berstorff GmbH, Hannover, Germany), with a friction ratio 1.2 per ASTM D 1554 T (1954). The
mixing time of the curative using a two roll mill was 10 min. After reclaiming, the samples changed
to sticky and soft materials, which were easily milled to form a smooth, continuous sheet.

MOLDING OF RUBBER STOCKS

About 40 g of the compounded rubber stock after 24 h of storage was placed in a mold and
pressed between the heated platens of a hydraulic press. The samples were cured at 140 8C and a
pressure of 6 tons was applied for the respective optimum cure times (t t90) obtained from the
rheographs. After curing, the sheet was taken out of the mold and immediately cooled under water
to restrict further vulcanization.

AGING CHARACTERISTICS

Revulcanized GRT vulcanizates were aged in a hot air aging oven at 70 2 8C. After aging for
72 h, modulus, tensile properties, elongation at break and hardness were measured.

CHARACTERIZATION OF RECLAIMED RUBBER

After reclaiming by the above milling procedure at different milling times with various
concentrations of reclaiming agent, small pieces (approximately 0.2 g) of samples were broken off
and placed in 20 ml toluene for 5 days at room temperature for sol-gel determination. Gel was then
filtered, washed with toluene, and dried in a hot air oven at 100 8C for 24 to 48 h for constant weight.
The inherent viscosity (ginh) of the sol fraction was measured by an Ubbelohde type suspended
level capillary viscometer (Technico; nominal constant 0.05 cS/s; ASTM D.445) at room
temperature. The inherent viscosity was determined by the following equation:
ginh ln gr =C
where gr is the relative viscosity of sol rubber and C is the concentration of sol rubber (g/dL).
The swelling ratio was determined with about 0.2 g of reclaim (accurately weighed). The
sample was immersed in 20 ml of pure toluene at room temperature for 5 days to allow the swelling
632 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

to reach diffusion equilibrium. At the end of this period, the test piece was taken out, and the adhered
liquid was rapidly removed by blotting paper and immediately weighed. The sample was dried in
vacuum to constant weight and the dried weight was taken. The swelling ratio was defined as
R W1  W0 =W0
where W0 is the weight of the test piece before swelling and W1 is the weight of the sample after
swelling at t time of immersion. The swelling ratio was a direct measurement of the degree of cross-
linking. Since the evaporation time of the solvent from the small sized particle is critical, because the
evaporation is directly dependent on the shape and size of the particle, it was assumed that the
ground particles had the same cross-link density as in the sheet form and they were measured as a
function of solvent evaporation time in air. The cross-link densities were determined by the Flory
Rehner equation32
  h 1=3
i
VC 1=MC  ln1  V2 V2 vV22 = VS dr V2  V2 =2

where V2 is the volume fraction of the polymer in the swollen specimen, VS is the molar volume of
the solvent, dr is the density of the polymer, MC is the molecular weight of the polymer between
cross-links, and v is the interaction parameter.
The volume fraction of a rubber network in the swollen phase is calculated from equilibrium
swelling data as
V2 W2 =d2 =W1 =d1 W2 =d2 
where W1 is the weight fraction of the solvent, d1 is the density of the solvent, W2 is the weight
fraction of the polymer in the swollen specimen, and d2 is the density of the polymer. For the GRT-
toluene system, v 0.3795, the molar volume of toluene VS is 106.2 cm3/mol, and the density of
toluene is 0.8662 g/cm3. The density of the polymer was determined at various concentrations of
reclaiming agent.

CHARACTERIZATION OF REVULCANIZED VULCANIZATES

Cure characteristics of rubber compounds have been investigated with the help of a Monsanto
Oscillating Disc Rheometer, R-100, at 140 8C. From the rheographs, optimum cure time, scorch
time, extent of cure, and cure rate index are obtained.
The cure rate index (CRI), which is a measure of the rate of the cure reaction, is estimated by the
method reported by Yehia and Stoll33 by the equation CRI 100/ (t90  t2).
The dumbbell shaped test specimens are punched out from the vulcanized sheet after 24 h of
storage by a tensile specimen cutter as per ASTM D 1554 T (1954). Modulus, tensile strength, and
percentage of elongation at break were measured following ASTM D 41251 T in an Amsler
(Sweden) tensile tester. Stressstrain was measured by the HioksHouse field Universal Testing
Machine (Test Equipment Ltd. Surrey, U.K.) according to the ASTM D 412-98a test method using
dumbbell shaped species at a cross-head speed of 50 mm/min at room temperature (25 2 8C).
Shore A hardness of the vulcanizates are determined by the Zorn Stendal, 1463 (GDR) hardness
tester as per ASTM D 141556 T. The mechanical properties are also measured after accelerated
aging conditions as per ASTM D 573-53.

SCANNING ELECTRON MICROSCOPY

To study the coherency and homogeneity in the GRT vulcanizates, scanning electron
microscopic (SEM) studies have been done on a JEOL, JSM 5800.
 RECLAIMING OF GROUND RUBBER TIRE (GRT) 633

FIG. 1. Effect of reclaiming time on sol content of reclaimed rubber.

RESULTS AND DISCUSSION

Mechanical reclaiming of GRT was carried out in an open two roll mixing mill at the various
concentrations of reclaiming agent, TBzTD (2, 3, 4, and 5 g) at various milling times. The extent of
reclaiming was monitored by the measurement of % of sol content, % of gel content, Mooney
viscosity, inherent viscosity of sol rubber, swelling ratio, and cross-link density of reclaimed rubber.

SOL FRACTION AND INHERENT VISCOSITY OF SOL RUBBER

Figure 1 shows the sol content of reclaimed rubber versus milling time at various concentrations
of reclaiming agent. It was found that the highest sol content was obtained at 50 min milling but the
maximum increase was observed up to 20 min milling, then the increasing trend slowed down,
showing a major dependence of the sol fraction on milling time. During milling, a vulcanized rubber

FIG. 2. Effect of reclaiming time on inherent viscosity of sol rubber.

634 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

FIG. 3. Effect of reclaiming time on cross-link density of reclaimed rubber.

sample undergoes tremendous mechanical shearing, resulting in random polymer chain breakdown.
In that time TBzTD also breaks into radicals as the temperature rises due to mechanical shearing.34
These radicals are combined with the broken polymer chain radicals and thereby prevent the
recombination of the polymer chain, which explains the increase of sol content with increasing
milling time. It is also clear from Figure 1 that the highest sol content is obtained at 50 min milling,
when 5 g TBzTD is used. It has been also noted that at 40 min milling, sol content is comparable for
every concentration of the reclaiming agent. It was also found that sol content is very low in the case
without TBzTD in the presence of spindle oil. Therefore the presence of TBzTD as a reclaiming agent
definitely improves the sol content of reclaimed rubber. It is evident from Figure 2 that the inherent
viscosity increases with increasing milling time. Here we see that inherent viscosity is highest when 4
g TBzTD is used at 50 min milling. Since inherent viscosity is directly related to the molecular weight,
so the molecular weight of the sol fraction increases with increasing milling time. De et al.22 explain
the reason for such an increase in molecular weight in the presence of disulfide reclaiming agent. For a
good quality reclaim the sol fraction and inherent viscosity of the sol fraction should be as high as
possible. It is also very important to note that when 2 g TBzTD is used the inherent viscosity is
comparable with 4 g TBzTD at 50 min milling. Hence we can get moderate inherent viscosity by using
minimum concentrations of reclaiming agent with increasing milling time.

GEL FRACTION AND CROSS-LINK DENSITY

Figure 3 represents the cross-link density of reclaimed rubber at various concentrations of

reclaiming agent, TBzTD, as a function of milling time. The gel fraction (% gel 100% sol) and
cross-link density of the sample decreased with increase in milling time. This is due to breakdown of

SCHEME 1. Breaking of TBzTD to thiocarbamate radicals.

 RECLAIMING OF GROUND RUBBER TIRE (GRT) 635

SCHEME 2. Combination of thiocarbamate radicals with broken polymer radical.

cross-links and polymer chains. It has been found that gel fraction and cross-link density decrease to
an optimum value at 40 min milling and then decrease slowly. We conclude that gel content and
cross-link density are mostly dependent on milling time. It is also clear from Figure 3 that cross-link
density is lowest for 2 phr TBzTD at 50 min milling. In the absence of TBzTD cross-link density is
maximum, that is, the extent of devulcanization is minimum.
Molecular weight between cross-links of reclaimed rubber is determined according to the
FloryRehner equation32 as describe above at different concentrations of TBzTD as a function of
milling time. Molecular weight between cross-link bonds increases with milling time and reaches
an optimum value at 40 min milling for every concentration of reclaiming agent. The reason for the
increase of the molecular weight with milling time may be explained with the help of the mechanism
636 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

SCHEME 3. Chain extension during final part of milling.

involved during the course of reclaiming when the reclaiming of GRT is carried out in the presence
of TBzTD on an open two roll mill: the tremendous mechanical shearing forces break both polymer
chains and cross-links bonds simultaneously while breaking TBzTD to form thio carbamate
radicals (shown in Scheme 1). Simple aliphatic disulfides have bond strengths of the order of70 k
cal/mol in the central SS bond as well as in the CS bond, which is too high for appreciable thermal
dissociation in the radicals at moderate temperatures. In thiuram disulfide, potential resonance
stabilization of the radicals should appreciably weaken the central bond and facilitate the formation
of the thio carbamate radical.34 Initially this thio carbamate radical may combine with a broken
polymer radical (shown in Scheme 2), and the molecular weight decreases. But with progress of
milling no more thio carbamate radicals are available to combine with broken polymer radicals. As
a result, end capping of the shear generated low molecular weight radicals by the thio carbamate
radicals gradually decrease with milling time. Therefore, such fragmented uncapped polymer
radicals may couple themselves, leading to chain extension (molecular weight increases) during the
final part of milling (shown in Scheme 3).

SWELLING RATIO OF RECLAIMED RUBBER

The swelling ratio is the direct measurement of the degree of cross-linking. Figure 4 represents
the swelling ratio of reclaimed rubber as a function of milling time at varied concentrations of the
reclaiming agent. The figure shows that the swelling ratio continuously increases with increasing

FIG. 4. Effect of reclaiming time on swelling ratio of reclaimed rubber.

 RECLAIMING OF GROUND RUBBER TIRE (GRT) 637

FIG. 5. Effect of reclaiming time on Mooney viscosity of reclaimed rubber.

milling time and that the maximum value of the swelling ratio arises at 50 min milling when 2 g
TBzTD is used. It is also clear that the swelling ratio is the same at 40 min milling time for both 2 g
and 3 g TBzTD.
Figure 5 shows the Mooney viscosity of reclaimed rubber as a function of milling time at
various concentration of TBzTD. With increasing milling time Mooney viscosity decreases. The
lowest Mooney viscosity is obtained for 2 phr TBzTD at 50 min milling.

CURE BEHAVIOR

Figures 6 and 7 show the cure behavior of reclaimed GRT obtained at various milling times and
different concentrations of reclaiming agent at a cure temperature of 140 8C. The torque attains a
maximum at less than 25 min and reaches a constant level. Figure 8 represents the maximum
rheometric torque (R) of compounded reclaim as a function of milling time. As the reclaiming time
increases the maximum torque increases up to 40 min milling. The maximum torque reaches the
highest level at 40 min milling with 5 g TBzTD and then decreases with increasing milling time.
This may be due to the presence of short rubber chains. The cure rate index increases with increasing
milling time up to 40 min milling and then decreases with increasing milling time as shown in
Figure 9. This can be a result of the presence of active functional groups in the reclaimed sample,
which is the characteristic of reclaimed rubber.35 During milling both main chain scission and
cross-link scission occurs, so there is some probability of loss in mechanical properties with
increased milling time. For this reason at 50 min milling time sol content, inherent viscosity, and
swelling ratio are maximum (comparable with 40 min milled), although gel content, Mooney
viscosity, and cross-link density are minimum for a particular concentration of reclaiming agent.
There is a loss in mechanical properties of the reclaim vulcanizate at 50 min milling. So we have
optimized the concentration of reclaiming agent at 2 phr TBzTD and 40 min milling time
(comparing the data of Table I) to obtain sufficient values of mechanical properties.

MECHANICAL PROPERTIES

The processing parameters during reclamation are found to have a pronounced effect on the
mechanical properties of revulcanized rubbers. Figures 10 and 11 present the stressstrain
638 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

FIG. 6. Cure behavior of reclaimed GRT after 20 min milling: (1) TBzTD (2 g phr); (5) TBzTD (3 g phr);
(9) TBzTD (4 g phr); (13) TBzTD (5 g phr).

dependencies for 20 and 40 min milled reclaimed rubber vulcanizates at different concentrations of
reclaiming agent. It is clear from the stressstrain graphs that stressstrain is maximum for 2 phr
TBzTD at 40 min milling time. The mechanical properties of the revulcanized rubber are shown in
Table I. From Table I we see that at higher concentrations of TBzTD, modulus and hardness
increases. Modulus at 50% and 100% elongation increases with increasing the concentration of the
reclaiming agent. The modulus may be higher at 50% and 100% elongation because of higher cross-
link density of the rubber vulcanizates, arising out of the gel present in reclaimed rubber. As cross-
link density increases in the rubber matrix, chain mobility decreases and a higher load is required for
50% and 100% elongation. Tensile strength increases with an increase in the cross-link density of
reclaimed rubber. The tensile strength may be higher because of a higher extent of reclaiming with
increased milling time. As milling time increases, gel content and cross-link density of reclaimed

FIG. 7. Cure behavior of reclaimed GRT after 50 min milling: (4) TBzTD (2 g phr); (8) TBzTD (3 g phr);
(12) TBzTD (4 g phr); (16) TBzTD (5 g phr).
 RECLAIMING OF GROUND RUBBER TIRE (GRT) 639

FIG. 8. Effect of reclaiming time on maximum rheometric torque (R) of reclaimed GRT.

rubber decreases, but molecular weight between cross-link bonds and inherent viscosity of sol-
rubber increases. But the gel part in the reclaimed rubber remains as such without dispersing as a
continuous matrix, and this gel remains present as weak sites for stress transmission to its
surroundings, resulting in a lower tensile strength. Because 20 min milled reclaimed rubber
contains a higher amount of cross-linked gel than that of 40 min milled reclaimed rubber, the tensile
strength value is less for 20 min milled reclaimed rubber and higher for 40 min milled reclaimed
rubber. For the same reason, elongation at break also increases with increasing milling time.
Hardness also increases with milling time. Above all the tensile strength and elongation at break are
highest at 2 phr TBzTD.

FIG. 9. Effect of reclaiming time on cure rate index (min1) of reclaimed GRT.
 640

TABLE I
MECHANICAL PROPERTIES OF REVULCANIZED RECLAIM

Maximum Scorch Optimum Concentration 50% 100% Tensile Elongation Milling

Mix torque time cure time Cure rate of TBzTD, Modulus, Modulus, strength, at time,
no. Ra, dN m t2, min t90, min index 100/(t90  t2) phr MPa MPa MPa break Hardness min
1 44.5 2.75 20 5.797 2 1.43 2.94 6.17 180 69 20
2 44 2.75 19.5 5.970 1.43 2.87 6.26 190 69 30
3 47 2.75 15 8.163 1.29 2.58 6.36 197 68.5 40
4 45.5 2.50 20 5.714 1.59 2.97 5.80 175 70 50
5 49 2.50 19 6.060 3 1.56 3.34 5.35 155 70 20
6 49 2.50 21.5 5.263 1.65 3.50 5.29 145 70.5 30
7 53 2.25 15 7.843 1.6 3.14 4.84 140 70 40
8 51.5 2.50 18 6.451 1.62 3.39 5.47 150 72 50
9 52.5 2.75 17 7.017 4 1.86 3.79 5.59 140 74 20
10 54.5 2.25 16.5 7.017 1.93 3.73 5.39 140 73 30
11 55 2.75 15 8.163 1.61 3.68 5.28 140 72 40
12 55 2.25 16.5 7.017 1.74 3.69 5.49 140 71.5 50
13 55.5 2.50 17.5 6.666 5 1.86 4.24 5.25 125 73.5 20
14 58.5 2.50 16 7.407 1.84 4.16 5.05 125 75 30
15 58.5 2.75 15 8.163 1.77 4.02 5.12 120 74 40
16 57.5 2.50 16.5 7.142 2.03 4.35 4.83 115 74.5 50
RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)
 RECLAIMING OF GROUND RUBBER TIRE (GRT) 641

FIG. 10. Stress vs (%) strain curves for 20 min milled revulcanized reclaim at various concentration of
reclaiming agent.

AGING CHARACTERISTICS

Tensile properties and hardness of revulcanized reclaim were measured after 72 h of aging at 70
2 8C in an air-aging oven. The aging characteristics are given Table II. Modulus at 50% and 100%
elongation increases with a particular concentration of TBzTD. During aging, residual curing
occurs, and consequently cross-link density increases. It is also clear that tensile strength and
elongation at break decreases with a particular concentration of TBzTD. The percentage retention
of tensile strength and elongation at break increases with increase in milling time. However, the

FIG. 11. Stress vs (%) strain curves for 40 min milled revulcanized reclaim at various concentration of
reclaiming agent.
642 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

TABLE II
MECHANICAL PROPERTIES OF 72 H AGED REVULCANIZED RECLAIM

Concentration 50% 100% Tensile Milling

Mix of TBzTD, Modulus, Modulus, strength, Elongation time,
no. phr MPa MPa MPa at break Hardness min
1 2 1.82 (127) 3.57 (121) 5.70 (90) 150 (79) 73 (104) 20
2 1.86 (130) 3.79 (132) 5.73 (93) 150 (83) 74 (105) 30
3 1.87 (145) 3.41 (132) 6.02 (96) 155 (79) 73 (107) 40
4 1.77 (111) 3.56 (120) 5.35 (92) 150 (86) 74.5 (106) 50
5 3 2.04 (131) 4.0 (120) 5.47 (98) 135 (87) 75.5 (108) 20
6 2.23 (135) 4.23 (121) 5.12 (97) 125 (86) 75 (106) 30
7 1.86 (116) 3.72 (118) 4.62 (95) 130 (93) 75 (107) 40
8 2.89 (178) 4.05 (119) 5.21 (95) 120 (80) 75.5 (105) 50
9 4 2.17 (117) 4.57 (121) 4.93 (88) 115 (82) 77.5 (105) 20
10 2.33 (121) 4.52 (121) 5.18 (96) 115 (82) 77.5 (106) 30
11 2.20 (137) 4.54 (123) 5.11 (97) 110 (79) 76 (106) 40
12 2.27 (130) 4.61 (125) 5.04 (92) 110 (79) 77 (107) 50
13 5 2.39 (128) 4.94 (117) 4.94 (94) 95 (76) 78 (106) 20
14 2.75 (149) 5.08 (122) 4.97 (98) 100 (80) 79 (105) 30
15 2.43 (137) 5.10 (127) 4.85 (95) 105 (87) 78.5 (106) 40
16 2.56 (126) 4.89 (112) 4.71 (98) 95 (83) 76.5 (103) 50

percentage retention of tensile strength and elongation at break value of revulcanized reclaimed
rubber is higher compared with that of the control NR compound.23 This phenomenon shows some
antiaging characteristics of reclaimed rubber. If reclaimed rubbers are used in product formulation,
the use of antioxidant may be reduced or even altogether excluded. From Table I we show that at 2
phr TBzTD the highest value of tensile strength is 6.36 M Pa (comparable with 5.783 M Pa for
TMTD)26 and maximum elongation break of 197. This mechanical property is also supported by the
stressstrain data of TBzTD at 40 min milling at 2 phr TBzTD concentration. Figure 11 shows that
at 40 min milling for 2 phr TBzTD concentration stressstrain is maximum. Table I proves that
hardness is minimum for 2 phr TBzTD concentration only. Therefore optimum concentration and
conditions for reclaiming GRT by TBzTD is 2 g and 40 min milling time, respectively.

SCANNING ELECTRON MICROSCOPY

The scanning electron micrographs (SEM) of tensile fractured surface of GRT vulcanizates
with various concentration of reclaiming agent are shown in Figure 12. The micrographs show that
when the reclaiming is carried out with 2 g TBzTD, the state of homogeneity is maximum as a result
of the optimum extent of reclaiming, the amount of cross-linked precursor in the vulcanizates is
minimum, and fewer vacuoles appear.

CONCLUSION
The ground rubber tire (GRT) is reclaimed mechanically with safe TBzTD in the presence of
spindle oil as a reclaiming oil. The devulcanized ground rubber tire is revulcanized without the extra
addition of TBzTD. The curing behavior and mechanical properties of the vulcanizates are
measured before and after aging. The results state that there is a definite influence of concentration
 RECLAIMING OF GROUND RUBBER TIRE (GRT) 643

FIG. 12. Scanning electron micrographs (SEM) of tensile fractured surface of RR vulcanizates with various concentration
of reclaiming agent: (a) 2 g phr TBzTD at 40 min milling time; (b) 3 g phr TBzTD at 40 min milling time;
(c) 4 g phr TBzTD at 40 min; (d) 5 g phr TBzTD at 40 min milling time.

of TBzTD and milling time within the results. Lower gel fraction and higher inherent viscosity of
sol after reclaiming will increase the quality of GRT. With increasing milling time sol content,
inherent viscosity, and swelling ratios increase and simultaneously gel content and cross-link
density decrease. Therefore, ground rubber tire (GRT) has been devulcanized extensively.
Revulcanized GRT shows the maximum tensile strength and stressstrain value by applying
minimum concentration of safe accelerator. Hence the optimized concentration of TBzTD is 2 phr
to obtain sufficient mechanical properties.

ACKNOWLEDGEMENTS
The author thanks IIT Kharagpur for measuring Mooney viscosity and stressstrain data.
Thanks also to Jadovpur University for SEM studies.

REFERENCES
1
W. C. Warner, RUBBER CHEM. TECHNOL. 67, 559 (1994).
2
A. A. Phadke, A. K. Bhattacharya, S. K. Chakraborty, and S. K. De, RUBBER CHEM. TECHNOL. 56, 726 (1983).
3
N. R. Braton, Waste Age 3, 61 (1972).
644 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 85, No. 4, pp. 629644 (2012)

4
N. R. Barton and J. A. Koutsky, Chem. Eng. News 52, 21 (1974).
5
A. A. Harshaft, Environ. Sci. Technol. 6, 412 (1972).
6
A. A. Phadke and S. K. De, Conserv. Recyl. 9, 271 (1986).
7
S. R. Fix, Elastomeric 112, 38 (1980).
8
A. Tukachinsky, D. Schworm, and A. I. Isayev, RUBBER CHEM. TECHNOL. 69, 104 (1996).
9
V. U. Levin, S. H. Kim, A. I. Isayev, J. Massey, and E. V. Meerwall, RUBBER CHEM. TECHNOL. 69, 104 (1996).
10
M. Loffler, G. Straube, and E. Straube, Biohydrometall. Technol. Proc. Int. Biohydrometall. Symp. 2, 673 (1993).
11
A. Tsuchii and K. Takeda, Appl. Environ. Microbial. 56, 269 (1990).
12
A. Tsuchii, K. Takeda, and Y. Tokiwa, Biodegradation 7, 405 (1997).
13
B. Adhikari, D. De, and S. Maiti, Prog. Polym. Sci. 25, 909 (2000).
14
K. Knorr, Kautsch. Gummi Kunsts. 47, 54 (1994).
15
H. Schnecko, Kautsch. Gummi Kunsts. 47, 885 (1994).
16
L. Oliveira and L. Carlos, Chem. Abstr. 106, P34401d (1987).
17
H. Okamoto, S. Inagaki, Y. Onauchi, and J. Furukawa, Nippon Gomu Kyokaishi 52, 774 (1979).
18
E. Anderson, Jr., U.S. Patent 4,554,675, 1985.
19
R. Kohler and J. ONeill, Rubber World 216, 32 (1977).
20
B. C. Sekhar, European Patent Application EP 0690091 AL, 1995.
21
D. De, B. Adhikari, and S. Maiti, J. Polym. Mater. 14, 333 (1997).
22
D. De, S. Maiti, and B. Adhikari, J. Appl. Polym. Sci. 73, 2951 (1999).
23
D. De, S. Maiti, and B. Adhikari, J. Appl. Polym. Sci. 75, 1493 (2000).
24
D. De, S. Maiti, and B. Adhikari, Kautsch. Gummi Kunsts. 53, 346 (2000).
25
D. De, A. K. Ghosh, S. Maiti, and B. Adhikari, Polym. Recycl. 4, 151 (1999).
26
D. De, A. Das, D. De, B. Dey, S. C. Debnath, and B. C. Roy, Eur. Polym. J. 42, 917927 (2006).
27
R. Preussman and G. Eisenbrand, Chemical Carcinogens, ACS Monograph 182, Vol. 1, C. E. Searle, Ed., American
Chemical Society, Washington, D.C., 1984.
28
B. Spiegelhalder and R. Preussmann, Carcinogenesis 4, 1147 (1983).
29
F. de Vocht, I. Burstyn, K. Straif, R. Vermeulen, K. Jakobsson, L. Nichols, B. Peplonska, D. Taeger, and H. Kromhout, J.
Environ. Monit. 9, 253259 (2007).
30
Kawasaki et al., Ordinary Overall Research Publication Meeting of the Japanese Rubber Society, Lecture Reprints 36, 37
(1979).
31
S. Yamashita, Int. Polym. Sci. Technol. 8, T/77 (1981).
32
P. J. Flory, Jr. and J. Renher, J. Chem. Phys. 11, 521 (1943).
33
A. A. Yehia and B. Stoll, Kautsch. Gummi Kunsts. 40, 950 (1987).
34
E. M. Bevilacqua, RUBBER CHEM. TECHNOL. 32, 721 (1959).
35
V. M. Makarov and V. F. Drozdovski, Reprocessing of Tires and Rubber Wastes, Ellis Howard, New York, 1991, Ch. 2.

[Received August 2011, Revised February 2012]

View publication stats