DOI 10.

1515/polyeng-2013-0330J Polym Eng 2014; 34(6): 543554

Fazliye Karabork*, Erol Pehlivan and Ahmet Akdemir

Characterization of styrene butadiene rubber

and microwave devulcanized ground tire rubber
composites
Abstract: Ground tire rubber (GTR) was devulcanized by
microwaves at the same heating rate (constant power) and
different times of exposure. The devulcanized rubber (DVR) and untreated GTR were characterized physically and
thermally. Composite materials were prepared from different proportions of the GTR, which was used as a filler, and
the DV-R, which was used as part of the styrene butadiene
rubber (SBR) matrix, and by varying the exposure time of
the microwave power. These composites were compared
with a control sample that was prepared from virgin SBR.
The sol content (soluble part) and Fourier transform infrared spectroscopy (FTIR) analyses of the devulcanized
samples were examined to define the efficiency of devulcanization. The cure characteristics and tensile properties
of the SBR composites were researched. In this study, it
was found that using DV-R as part of the rubber matrix
produced much better properties than using GTR as a
filler, thereby showing the significant benefits of microwave devulcanization. At the DV-R content of 50 phr,
the elongation at break of the DV-R 5 min/SBR composites increased to 445.06% from 217.25% for the GTR/SBR
composites, i.e., the elongation at break was enhanced by
105% by the devulcanization of GTR. Scanning electron
microscopy (SEM) photographs displayed a better interface coherence between the DV-R 5 min and SBR matrix
than the GTR/SBR composites.
Keywords: cure properties; ground tire rubber; mechanical properties; microwave devulcanization; SBR.
*Corresponding author: Fazliye Karabork, Department of
Mechanical Engineering, Aksaray University, 68100, Aksaray,
Turkey, e-mail: fazliyekarabork@hotmail.com
Erol Pehlivan: Department of Chemical Engineering, Selcuk
University, 42003, Konya, Turkey
Ahmet Akdemir: Department of Mechanical Engineering, Selcuk
University, 42003, Konya, Turkey

1 Introduction
In the last few decades, the rubber industry has faced a
major problem in finding a suitable way for dealing with
the huge amount of rubber products, especially tires, at
the end of their life. Millions of tons of used tires and
similar products at the end of their limited service life
are dumped in natural environments. The environmental problems created by waste rubber and discarded tires
have become a serious issue. Many attempts have been
made to recycle waste rubber for both environmental and
economic reasons [1, 2]. Every year, approximately 3.3
million tons of used tires (at the end of their useful life)
are generated in Europe (etrma.org) and approximately
180,000 tons in Turkey (lasder.org.tr). The recycling
of discarded tires has some very important outcomes
including environmental protection, energy savings and
provision of raw materials. Therefore, the development
of an efficient way to utilize rubber waste is an emergent
economic and environmental task faced by the rubber
industry worldwide [2, 3].
Rubber recycling is a difficult task because of the vulcanization reaction, which takes place in three-dimensional structures. After undergoing reactions, vulcanized
rubber turns into an infusible and insoluble form and
cannot be converted into other forms [4, 5]. The crosslinks
in the main skeleton of the polymer, which form during
the vulcanization process, turn the thermoplastic structures into thermosets that are impossible to reshape by
heating. Therefore, physical and chemical treatments for
waste tires are necessary to destroy the three-dimensional
structure [6, 7].
A lot of study has revealed that ground tire rubber
(GTR) recycling should target the production of thermoplastic elastomers, and its reuse in the rubber industry
[8]. Rubber recycling currently is receiving special attention, because other disposal methods, such as burning
for energy generation, are dangerous for the environment [3]. Some new physical and chemical devulcanization techniques for recycling are being developed to
recycle used tires. However, all of these devulcanization

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544F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites
methods are unable to produce a product that is similar
to virgin rubber. Rubber recycling technologies such as
mechanical [9, 10], mechanochemical [1115], ultrasonic
[16], chemical [1719], microwave [3, 2022] and biological methods [23] have been developed with the targets
of higher product quality and percent yield. Devulcanization provided the advantage of rendering the rubber
suitable for reformulating and recycling into usable
products [24].
The microwave devulcanization technique is based
on the application of a controlled amount of microwave
energy to the material at a certain energy level that is
sufficient to cleave carbon-sulfur (302 kJ/mol) and sulfur-sulfur bonds (273 kJ/mol), but insufficient to cleave
carbon-carbon bonds, which have a higher bond energy
(349 kJ/mol). In this method, tire waste can be reclaimed
without depolymerization as a material that is capable of
being recompounded and revulcanized and has physical properties essentially equivalent to the original vulcanizate [6, 25]. The use of microwaves for heating has
the advantage of volumetric heating, which is faster and
supports a more homogeneous heating than other conventional methods based on different heat transfer mechanisms, such as convection and conduction. However, one
critical requirement of the microwave process is the presence of polar groups or components in the polymer. The
presence of carbon black in nonpolar rubbers makes the
rubbers receptive to microwave energy. This fact makes
it possible to use the microwave heating to devulcanize
waste tire rubber [7, 26].
The goals of this research were to obtain devulcanized
rubber (DV-R) from waste tires and then to combine it with
a styrene butadiene rubber (SBR) matrix to produce a new
composite material. The curing characteristics, mechanical properties and morphology of these materials were
investigated and compared with the characteristics of
untreated GTR/SBR composites.

2 Materials and methods

2.1 Materials and characterization
The GTR used in this study was supplied by Un-sal Rubber
Co. Ltd (Adana, Turkey). The GTR, which was prepared by
grinding under ambient conditions, was an unclassified
ground rubber from the treads and sidewalls of car, truck
and bus tires. The original rubber, SBR 1502, was obtained
from Petkim (Izmir, Turkey). Toluene was purchased
from Merck (Germany). Sulfur, cyclohexyl benzothiazyl

sulfenamide (CBS), stearic acid and zinc oxide (ZnO) for

vulcanization studies were procured from local sources.
The particle size distribution of the GTR was characterized using 35, 60, 120 and 230 mesh sieves. The thermal
characterization was performed by thermogravimetric
analysis (TGA) to determine the composition and thermal
degradation properties of the samples. The analysis was
performed with a Perkin Elmer thermogravimetric analyzer under nitrogen from ambient temperature to 800C
with a heating step of 10C/min.

2.2 Microwave treatment of GTR and

characterization of DV-R
The GTR was treated in an adapted microwave apparatus
consisting of a domestic-type microwave oven (Samsung
MW71E) and a stirring apparatus. The power of the magnetron was set to 800 W, and 100 g of the GTR was put in
a 1000ml beaker and stirred at a speed of 6 rpm. The processing variable was the exposure time, which was varied
from 1 to 5 min. The samples were identified as DV-R followed by a number corresponding to the exposure time in
min. The temperature of the samples was measured after
each treatment.
The sol content of the GTR and DV-R material was
measured with a Soxhlet apparatus using toluene as
solvent. The extraction was completed in 24 h, and it was
made with 2 g of both GTR and DV-R. After the extraction,
the sample was dried for 24h at 70C, and its weight was
recorded. The percent sol content was calculated from the
following equation [27]:
Solcontent % = [(Wi -W)/Wi ] 100%
where Wi is the weight of the sample before extraction and
W is the weight of the dry rubber sample after extraction.
The chemical groups of GTR, before and after
the sample was devulcanized, were analyzed with a
Perkin Elmer Spektrum 400 [Fourier transform infrared
spectroscopy (FTIR)] from 4000 to 450cm-1 with a 4cm-1
resolution and then the efficiency of devulcanization was
determined.

2.3 Preparation of DVR and SBR composites

Virgin SBR, other additives and various proportions of
the DV-R samples were mixed for 15min on an open tworoll mixing mill at room temperature. The formulations
of the composites are presented in Table 1. Formulation

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F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites545

Table 1Formulations of the devulcanized rubber (DV-R)/styrene
butadiene rubber (SBR) composites.
Ingredients (phra)

SBR 1502

Devulcanized rubber
Carbon black (N330)
Process oil

ZnO

Stearic acid

CBS

Sulfur

100
0
67.75
35.5
3
1
1.8
1.75

90.9
10
66.85
35.5
3
1
1.8
1.75

72.7
30
65.05
35.5
3
1
1.8
1.75

54.5
50
63.25
35.5
3
1
1.8
1.75

Parts per hundred rubber.

CBS, cyclohexyl benzothiazyl sulfenamide.
a

1 does not contain DV-R and is a control sample. Formulations 2, 3 and 4 were prepared at 10, 30 and 50 phr
DV-R. For comparison, untreated GTR was mixed with
SBR in the same series. In the formulation of GTR/SBR
composites, GTR was used as a filler. As DV-R was considered to be an elastomeric component, it was used
as a component of raw rubber and not a filler. Because
DV-R contains rubber and carbon black, the amounts of
SBR and carbon black were adjusted in the formulations
of the composites. The amounts of the other additives
(ZnO, stearic acid and sulfur) in the formulations were
based on 100 g of rubber without taking the DV-R into
account, because it was assumed that the additives in
the DV-R originated from the parent compound and were
inactive [28].
The maximum sol content and suitable temperature
(Table 2) were obtained in the samples that were exposed
for 4 and 5 min but not the samples that were exposed
for 1, 2 and 3 min. Therefore, DV-R/SBR composites were
prepared by exposing the samples in the microwave for 4
and 5 min.

Table 2Sample temperatures after microwave treatment and sol

contents.
Sample

Max temperature (C)

Sol content (%)

N0
DV-R1
DV-R2
DV-R3
DV-R4
DV-R5

9010
16010
22010
30010
37010

2.3
10.7
13.1
18.5
25.4
34.8

Untreated ground tire rubber (GTR).

DV-R, devulcanized rubber.
a

2.4 Characterization of DV-R/SBR

composites
2.4.1 Cure characteristics
The cure characteristics of the rubber composites were
investigated by using a rheometer, Beijing RADE MR-C3,
at 170C. From the rheographs, the minimum torque (ML),
scorch time (ts2), maximum torque (MH) and optimum
curing time (t90) were obtained. The ML is a measure of
the rubbers resistance to flow during processing, and the
MH relates to the compounds final stiffness. The number
of min to reach 90% of the MH or t90 briefly expresses the
cure time required to almost complete the vulcanization
process. These samples were identified as R followed by
two numbers corresponding to the exposure time in min
and the DV-R content (1/10).

2.4.2 Measurement of mechanical properties

The mechanical properties of the DV-R/SBR and GTR/SBR
composites were measured with a Shimadzu AG-IC tensile
testing machine according to ASTM D 412 under laboratory
conditions (232C). The testing speed was 500 mm/min.
Dumbbell-shaped specimens were punched from the compression-molded sheets, and the hardness (Shore A) of the
new composites was measured with a Bareiss Shore meter
according to ASTM D 2240. At least three samples for each
composition were tested, and the average value is reported.

2.4.3 Determination of crosslink density

The chemical characteristics of the DV-R/SBR and GTR/
SBR composites were investigated by determining their
crosslink densities. The test specimens, which weighed
approximately 0.2 g each, were immersed in a solvent containing 100ml of toluene at room temperature (23C) for
72 h. The excess solvent on the surfaces of the specimens
was removed by drying with filter paper. The weights
of the swollen specimens were measured, and then the
specimens were dried to a constant weight. The crosslink
densities of the composites were determined by the FloryRehner equation with the Kraus correction [28, 29]:
c = -

1 ln( 1-vr ) + vr + X ( vr )
2Vs
vr1/3 -vr /2

where c is the crosslink density of composite (mol/m3),

Vs is the molar volume of the solvent (1.06910-4 m3/mol),

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546F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites
vr is the volume fractions of filled rubber in the swollen
specimen and X is the rubber-solvent interaction para
meter (0.3795 in this study [30]).

2.5 Morphology
The morphology of the GTR surface and the fracture surfaces of the DV-R/SBR and GTR/SBR composites were
evaluated with a ZEISS EVO LS 10 scanning electron
microscope (SEM). The sample surfaces were sputtercoated with gold powder using a Sputter Coater Auto 108.
Figure 2Scanning electron microscopy (SEM) photograph of
ground tire rubber (GTR).

3 Results and discussion

3.1 P
 hysical and thermal characterization
ofGTR
Figure 1 shows the particle size distribution of the GTR
used in these experiments. Particle size analysis showed
that the majority of the ground rubber particles were in
the 35120 mesh (0.50.125 mm) range. The particles in the
size range higher than 120 mesh (smaller than 0.125mm)
were found in small quantities. It is well known that particles of GTR that are suitable for utilization in new formulations and for devulcanization processes should be smaller
than 0.6mm and have high surface areas [3134].
An SEM photograph of representative GTR is shown in
Figure 2. It was observed that the GTR particles had irregular shapes and their surfaces were rough.
The partial composition of the GTR was determined by
TGA and results are given in Figure 3. The thermogram in
Figure 3 shows that the first weight loss (13%) below 350C
corresponded to a loss of water and highly volatile materials, such as low molecular weight plasticizers, oils, waxes

and antioxidants that were used for tire manufacture.

The second weight loss, at 350500C, was a large weight
change (52%), and it was assigned to the degradation of
the polymers and moderately volatile materials related to
the elastomers and curing agent. Finally, the last degradation phase, above 500C when approximately 35% of the
original weight of the GTR remained, corresponded to the
decomposition of carbon black.

3.2 Characterization of DV-R

The temperatures of the samples after microwave exposure are shown in Table 2. The Soxhlet extraction results,
including sol contents of the samples, are given in the
same table. It can be observed that, as expected, the
sample temperatures increased immediately after the

106.5

DTG

100

0.3213
0

70
Weight (%)

60
50
Weight (%)

-2

80

-3
425C

70

-4

60

-5

30

50

-6

20

40

40

10
0

28.85
50 100

<0.063

0.0630.125

0.1250.25

0.250.5

Sieve size (mm)

Figure 1Particle size distribution of ground tire rubber (GTR).

Derivative weight (% min)

-1
90

-7
TGA
376C
200

300

400

500

600

700

-8
-8.341
800

Temperature (C)

Figure 3Thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG) curves for ground tire rubber (GTR).

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F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites547

Table 3Comparison of the sol content of the devulcanized ground tire rubber (GTR) from this study and other devulcanization methods.
Devulcanization
method

Literature

Material

Sol content (%)

Mechanochemical

De etal., 2006 [14]

27.0

Thermochemical

Grigoryeva etal., 2004 [35]

Ground tire rubber and

devulcanization agent (TMTD)

Ground tire rubber and

devulcanization agent
(Phthalic anhydride)

Ground tire rubber

Ground tire rubber

Mechanical
Microwave

Li etal., 2005 [1]

This study

microwave exposure and were almost linear with the time

of exposure.
Soxhlet extraction evaluates only the fraction of
soluble matter present in the sample, which is a good
parameter to use to evaluate the efficiency of the devulcanization process [3, 7]. The initial sol content of the
GTR was 2.30% and it rose to 25.36% and 34.77% after
microwave devulcanization for 4 and 5 min, respectively.
The higher sol content showed that the devulcanization process was more efficient. It can be observed that
the time of treatment in the microwave has a significant
influence on the sol content. This was expected because

2125.60

3296.89

2338.16

2950.08

1528.89

3302.02

871.26 712.08

2315.61

818.85
961.30
1036.06
1372.92
1427.77

2913.82
2846.89

3790.51

2019.76
2315.77
2141.70

3297.49

2901.77 2845.90

4000 3600 3200

2800

1427.84 1369.70

787.65
810.16
1046.16

C
2400

2000 1800

1600

1400

1200

1000

34.0
34.8

when the starting material was treated for longer periods

of time, it reached higher temperatures and generated
materials with higher sol contents. The sol content of the
devulcanized GTR in this study was compared with the sol
content obtained with different devulcanization methods
in other references in Table 3.
To obtain information about the structure and functional groups after microwave devulcanization, FTIR
spectra are presented in Figure 4, where the FTIR spectra of
the DV-R (after microwave exposure times of 4 and 5 min)
and GTR were compared. During the microwave devulcanization of GTR, the amount of energy released is utilized for

1633.40
820.87
1538.70
1423.06 1372.92 1028.00 959.69

2915.73
2847.65

27.6

800

600 450

Wave number (cm-1)

Figure 4Fourier transform infrared spectroscopy (FTIR) spectra of: (A) ground tire rubber (GTR); (B) DV-R4; and (C) DV-R5.

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548F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites
exposure time, but it increased with the addition of
untreated GTR. The MH increased remarkably with the
addition of 30 phr of GTR, and further additions of GTR
resulted in a decrease in the torque. This relationship
indicated that the elastic modulus was lower in the composites containing DV-R. The decrease in the value of the
MH may be due to the presence of short rubber chains and
crosslink precursors in the DV-R [14].
Figure 6A and B show the ts2 and optimum cure time
(t90) as functions of DV-R content. The ts2 of the composites decreased slightly with an increase in both the GTR
and DV-R concentrations. Furthermore, the ts2 of the
DV-R/SBR composites are lower than those of the GTR/
SBR composites. It is clear that there are more unsaturated rubber bonds in the DV-R than in the GTR. The
shorter ts2 for the composites indicate that the crosslinking reactions start earlier in the vulcanization process.
Ishiaku etal. [37] showed that a reaction between the SBR
matrix and the DV-R can catalyze crosslinking. Diffusion
of the accelerator from the DV-R into the virgin rubber
can reduce the ts2 [27, 38]. De etal. [14] reported that the
revulcanized rubber has active crosslinking sites, which
lower the ts2.
The t90 is the vulcanization time required to obtain
a product with optimum physical characteristics. The t90
of the composite decreased with an increase in the concentration of both the GTR and DV-R in the composite
skeleton. Both ts2 and t90 decreased considerably with the
addition of DV-R5 to the matrix, which demonstrates the
presence of active functional sites in these composites.

breaking S-S bonds instead of C-C bonds, because the S-S

bond energy is lower than the energies of various organic
bonds. However, a few C-C and C-S bonds may break along
with the S-S bonds at higher temperatures and after longer
durations of heating. The devulcanization was carried out
for a maximum of 5min at 37010C (maximum temperature) and the rubber crosslinks can break easily without
main chain scission. The peaks of the C-H stretching vibration (30002800 cm-1) and the -CH2 deformation (1447cm-1
and 1372 cm-1) did not show significant differences between
GTR and DV-R [23, 36]. The peak at 1538cm-1 was assigned
to the C-S bond, which represents untreated GTR. After
the devulcanization process, the peak value of the C-S
bond decreased (especially for the DV-R5 sample), which
showed the devulcanization of the GTR during the microwave devulcanization.

3.3 C
 haracterization of DV-R/SBR
composites
3.3.1 Cure characteristics
The cure characteristics of the DV-R/SBR and GTR/SBR
composites are given in Table 4. The DV-R content and
microwave exposure time affected the curing behavior.
The effects of the DV-R content on the ML and the MH
are shown in Figure 5A and B. The ML increased slightly
with the addition of DV-R in all cases (4 and 5 min), but
it increased remarkably with the addition of untreated
GTR. This indicates firstly that there was some interaction
between the DV-R and the virgin rubber and secondly that
the processing of composites containing GTR was more
difficult than for composites containing DV-R. The reason
for the increase in the ML could be the agglomeration of
waste rubber particles in the SBR matrix [1].
The MH, a measure of crosslink density, decreased
slightly with the addition of DV-R and the microwave

3.3.2 Mechanical properties of composites

The DV-R content and the exposure time were found to
have a strong, distinct effect on the mechanical properties
of the DV-R/SBR and GTR/SBR composites. The mechanical properties of the SBR composites with different

Table 4Cure characteristics of the devulcanized rubber (DV-R)/styrene butadiene rubber (SBR) and ground tire rubber (GTR)/SBR
composites.
Sample

RKa

DV-R (phr)

Control

ML (dNm)
MH (dNm)
ts2 (min)
t90 (min)

0
10.80
19.48
1.88
3.32

R41

R43

10

30

11.89
20.92
1.47
2.90

12.02
18.09
1.20
2.95

R45

4 min

50

13.22
19.91
0.97
2.20

R51

R53

10

30

11.88
20.39
1.52
3.01

12.92
22.15
0.87
1.97

a
Control sample.
MH, maximum torque; ML, minimum torque; t90, optimum curing time; ts2, scorch time.

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R55

5 min

50

11.95
18.26
0.93
1.82

R01

R03

R05

Untreated GTR
10

13.46
23.39
1.57
2.98

30

18.64
31.01
1.00
1.88

50

16.71
22.81
1.18
2.37

F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites549

Control

20

DV-R4

DV-R5

GTR

16

Max Torque, MH (dNm)

Min Torque, ML (dNm)

18
14
12
10
8
6
4
2
0

35

Control

DV-R4

DV-R5

GTR

30
25
20
15
10
5
0

Control

10

30

50

Control

Devulcanized rubber content (phr)

10

30

50

Devulcanized rubber content (phr)

Figure 5Effects of devulcanized rubber content on: (A) minimum torque (ML); and (B) maximum torque (MH).

The effects of the GTR and DV-R contents on the

tensile strength and the elongation at break are shown in
Figure 7A and B. With the addition of 10 phr of DV-R and
GTR to the composite, the values of the tensile strength
and elongation at break increased. These increases may
be because the smaller DV-R and GTR particles act as

1.8

Control

DV-R4

DV-R5

GTR

Skorch time, ts2 (min)

1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
Control

10

30

50

3.5

Optimum cure time, t90 (min)

concentrations of GTR and DV-R are shown in Table 5.

These composites tend to become weak and brittle with
increasing concentrations of GTR and DV-R. The results in
Table 5 show that the mechanical properties of the DV-R/
SBR were far superior to the properties of SBR filled with
GTR at the same loading.

3.0

Control

DV-R4

DV-R5

GTR

30

50

2.5
2.0
1.5
1.0
0.5
0

Control

Devulcanized rubber content (phr)

10

Devulcanized rubber content (phr)

Figure 6Effects of devulcanized rubber content on: (A) scorch time (ts2); and (B) optimum cure time (t90).

Table 5Mechanical properties of devulcanized rubber (DV-R)/styrene butadiene rubber (SBR) and ground tire rubber (GTR)/SBR
composites.
Properties
Sample
RK
R41
R43
R45
R51
R53
R55
R01
R03
R05

Elongation
at break (%)

Tensile strength
(N/mm2)

100% Modulus
(N/mm2)

200% Modulus
(N/mm2)

300% Modulus
(N/mm2)

Hardness
(Shore-A)

Crosslink
density (mol/m3)

525
595
341
366
614
449
445
618
279
217

7.49
7.17
5.35
4.74
7.82
6.50
4.91
9.20
4.29
6.39

1.96
1.48
2.56
2.13
1.80
2.18
1.98
1.78
2.14
3.67

3.09
2.76
3.99
3.22
2.81
3.38
2.79
2.86
3.38
6.09

4.42
3.95
4.95
4.08
4.01
4.72
3.78
4.33

57
58
64
66
56
67
67
57
64
64

54.91
69.19
79.18
94.79
74.04
93.35
106.03
77.63
87.99
119.87

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550F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites
Control

10

DV-R4

DV-R5

GTR

Elongation at break (%)

Tensile strenght (N/mm2)

8
7
6
5
4
3
2
1
0

Control

10

30

DV-R4

DV-R5

GTR

10

30

50

600
500
400
300
200
100
0

50

Control

700

Control

Devulcanized rubber content (phr)

Devulcanized rubber content (phr)

Figure 7Effects of devulcanized rubber content on: (A) tensile strength; and (B) elongation at break.

reinforcing agents in the materials. This result was supported by prior work by Rooj etal. [5]. However, the values
of the tensile strength and elongation at break decreased
for 30 and 50 phr loadings of both DVR and GTR. The
deterioration of the mechanical properties of the GTR/
SBR composites is related to the weak adhesion between
the GTR particles and the SBR matrix. Because the GTR
particles are not well-dispersed in the matrix of SBR, they
are weak sites for stress-transmission and result in lower
mechanical properties for the composite. The values of

4.5

Control

DV-R4

DV-R5

GTR

4.0

200% modulus (N/mm2)

100% modulus (N/mm2)

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0

Control

10

30

7.0

Control

300% modulus (N/mm2)

6.0

Control

DV-R5

10

30

GTR

5.0
4.0
3.0
2.0
1.0
Control

50

Devulcanized rubber content (phr)

Devulcanized rubber content (phr)

DV-R4

6.0

50

the properties for composites that contained DV-R were

much better than for the composites with GTR. Because
DV-R takes part in the crosslinking reaction, there is strong
interfacial bonding between the SBR matrix and DV-R that
leads to good tensile properties.
The tensile strength and elongation at break increased
with the time of exposure to microwave power. The higher
tensile strength and elongation at break may be due to the
decrease in the number of crosslinked sites in the DV-R5/
SBR and the strong interfacial bonds between the SBR

DV-R4

DV-R5

GTR

10

30

50

5.0
4.0
3.0
2.0
1.0
0

Control

Devulcanized rubber content (phr)

Figure 8Effects of devulcanized rubber content on: (A) 100% modulus; (B) 200% modulus; and (C) 300% modulus.

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Hardness (shoe-A)

70

Control

DV-R4

DV-R5

GTR

68
66
64
62
60
58
56
54
52
50

Control

10

30

140

Crosslink density (mol/m3)

F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites551

120

DV-R4

DV-R5

GTR

100
80
60
40
20
0

50

Control

Control

Devulcanized rubber content (phr)

10

30

50

Devulcanized rubber content (phr)

Figure 9Effects of devulcanized rubber content on: (A) hardness; and (B) crosslink density.

matrix and DV-R, which transmit stress very well in the

composite structure.
The effects of the GTR and DV-R content on the modulus
at 100%, 200% and 300% elongations are presented in
Figure 8AC. The values of the modulus increased with
increases in the GTR content, especially at 50 phr, indicating that the GTR loading in the rubber matrix enhanced
the rigidity of the composite. The important increase in
the modulus is attributed to the higher modulus of the

GTR than the composite matrix; therefore, GTR acts like

a rigid particulate filler that cannot be deformed easily.
The addition of GTR to a soft composite matrix leads to the
development of a local stretching in the composite matrix
that exceeds the overall strain of the composite. The 300%
modulus was not obtained for the GTR/SBR composites
with 30 and 50 phr loadings. Hence, DV-R is comprised of
a gel fraction, which has a higher modulus, and a sol fraction, which could be co-crosslinked with the SBR matrix,

Table 6Comparison of the changes of the mechanical properties of the virgin rubber and devulcanized ground tire rubber (GTR) for the
different devulcanization methods according to control samples reported in the literature
Devulcanization
method
Mechanical

Literature

Mechanochemical

Mechanochemical
Thermochemical

Mechanochemical

Microwave

Li etal., 2005 [1]

Rubber blends

Maridas and Gupta, 2003 [39]

De and De, 2011 [28]

Grigoryeva etal., 2004 [35]

Zhang etal., 2009 [15]

This study

Dev. rubber
(phr or w%)

NR and devulcanized GTR

NR and devulcanized GTR

SBR and devulcanized GTR

SBR and devulcanized GTR

NR and devulcanized GTR

SBR and devulcanized GTR

10 phr
30 phr
50 phr
10%
20%
30%
40%
20 phr
20%
40%
60%
10%
30%
50%
10 phr
30 phr
50 phr

Variation of 200% modulus.

Variation of 100% modulus.
+ increase in the variation.
- decrease in the variation.
NR, natural rubber; SBR, styrene butadiene rubber.

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Variation Variation of
of tensile
elongation
strength (%) at break (%)
+13.36
-12.07
-0.78
-5.85
-20.47
-25.73
-28.07
+4.68
+40
+50
+80
+6.97
-16.28
-34.88
+4.36
-13.29
-34.52

-0.42
-10.67
-19.08
-6.53
-11.26
-19.98
-23.49
-5.21
+35.29
-41.17
-67.06
-0.80
-27.42
-43.55
+16.99
-14.42
-15.17

Variation
of 300%
modulus (%)

+14.29
+21.43
+21.43
+28.57
+18a

+9.37b
+71.87b
+137.50b
-9.22
+6.70
-14.56

552F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites

Figure 10Scanning electron microscopy (SEM) photographs of tensile fracture surfaces: (A) ground tire rubber (GTR)/styrene butadiene
rubber (SBR) composites; (B) DV-R4/SBR composites; and (C) DV-R5/SBR composites.

and the values of the modulus of the GTR/SBR composites

were lower than the values that were obtained by loading
GTR with DV-R5.
The hardness of the composites showed an increase
with longer microwave exposure time and higher DV-R
loading (Figure 9A). The increase in the hardness of
the composites is most likely due to the increase in the
crosslink density of the composites.
Figure 9B shows the variations of the crosslink densities of the composites as functions of DV-R content.
Because the crosslink density of the DV-R was reduced
by devulcanization, the crosslink density of the DV-R/

SBR composites was a little lower than that of the GTRfilled SBR composites. The moderate increase in crosslink
density of the composites with the addition of DV-R was
due to the presence of active crosslinking sites in the
DV-R, which may take part in crosslinking during the vulcanization process. It is proven that the crosslink density
of the DV-R/SBR composites is lower than that of the GTR/
SBR composites, which further confirmed that the devulcanization was accomplished by the microwave treatment
(Figure 9B).
The changes in the mechanical properties of the
virgin rubber and devulcanized GTR for the different

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F. Karabork etal.: Characterization of SBR and microwave devulcanized GTR composites553

devulcanization methods are compared in Table 6. In this

table, we bring attention to the references that are related
to the devulcanization of waste tire rubber.

3.4 Morphology
SEM micrographs of tensile fractured surfaces of GTR/SBR
and DV-R/SBR composites with 30 phr and various exposure times are shown in Figure 10AC. The surfaces of SBR
composites filled with the GTR exhibited a morphology of
brittle fracture, which is evidence of inferior properties,
especially elongation at break. There were some cracks,
pores and many cavities on the fracture surfaces of the
composites (Figure 10A). This morphology showed that
the adhesion of GTR to the SBR matrix was poor. The weak
adhesion results in damage or alteration of the mechanical properties, which is in agreement with the other conclusions from our experimental results. The exposure time
also affected the fracture surface morphology. The fracture
surface of the DV-R4/SBR composite was similar to the
GTR filler/SBR composite (Figure 10B) because the adhesion was poor between the DV-R4/SBR composites. The
tensile fractured surface of composites with 30 phr DV-R5
is shown in Figure 10C. Desirable adhesion exists between
the DV-R filler and the SBR matrix and a crosslinking reaction occurs between the DV-R and the SBR matrix.

4 Conclusions
DV-R was produced by a microwave technique and then
DV-R and untreated GTR were blended with virgin SBR in

different proportions. A considerable increase in the sol

fraction occurred during the devulcanization process.
An FTIR study confirmed the microwave devulcanization
of GTR. The sol content of the untreated GTR was 2.3%,
and the sol content reached its maximum of 34.77% for
DV-R5. The curing characteristics and mechanical properties of the DV-R/SBR composites were compared with the
properties of the GTR/SBR composites. The ML increased
and the MH decreased to a small extent with an increase
in the DV-R, but both characteristics showed a remarkable
increase with the addition of untreated GTR. It was a fact
that the processability of the composites did not change
meaningfully with the DV-R loadings. At 10 phr DV-R and
GTR loadings of SBR composites, the tensile strength and
elongation at break were improved in comparison to the
virgin SBR. At higher concentrations of DV-R and GTR,
these properties deteriorated. As a result of microwave
devulcanization, the DV-R/SBR composites had better
mechanical properties than the GTR-filled SBR composites
at the same loadings. However, the elongation at break of
the DV-R5/SBR composites decreased only 15.17% versus
the control sample at 50 phr loading, while the elongation
at break was 30.18% and 58.59% for DV-R4/SBR and GTR/
SBR composites, respectively. This research has shown
that the microwave treatment can be used as a convenient
technique for rubber recycling studies.
Acknowledgments: The authors acknowledge the support
of the Coordination Committee of Scientific Research Projects of Selcuk University, Turkey (Project no: 10201043).
Received December 30, 2013; accepted April 1, 2014; previously published online May 1, 2014

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