Polymer Degradation and Stability 128 (2016) 115e125

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Reclaiming waste tire rubber by an irradiation technique

Mahdieh Molanorouzi, Saeed Ostad Mohaved*
Polymer Group, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Tire rubber recycling reduces production costs, saves resources, and decreases the environmental issues.
Received 14 January 2016 Waste tire rubber were devulcanized by a laboratory microwave oven with the aid of the devulcanizing
Received in revised form agent and the oil. The effect of several devulcanizing agents, hexadecylamine (HDA), Diphenyl disulfide
8 March 2016
(DPDS), N-cyclohexyl-2-benzothiozyl sulfenamide (CBS) 2-mercaptobenzothiazole disulfide (MBTS) and
Accepted 9 March 2016
two types of the oils, aromatic and paraffinic with various contents in different irradiation temperatures
Available online 12 March 2016
was studied. For homogeneous devulcanization, the waste rubber was ground to a median particle size of
319 mm before further treatment and subsequent irradiation process. The results showed that used waste
Keywords:
Tire rubber
rubber powder was devulcanized effectively. Among of the devulcanizing agents and based on Horikx
Devulcanization analysis, formulated compound with DPDS with the sol fraction, crosslink density (CLD) and devulca-
Microwave nization percent of 16.5%, 85 mol/m3 and 48%, respectively, was the most suitable compound for
Reclamation devulcanization when compared with formulated compounds with other devulcanizing agents. Among
Devulcanization agent of compounds with different DPDS content, compound with 30 phr aromatic oil and 6 phr DPDS in
formulation with devulcanization temperature of 240
C, had the best devulcanizing parameters.
Paraffinic oil had an adverse effect on devulcanization of the DPDS formulated compounds. For selected
studied compounds, during microwave irradiation, a part or total amount of the polysulphides crosslinks
were broken and the structure of the remained sulphur crosslinks were mostly mono sulphide. In the
morphology study of the most devulcanized compounds, a coarse morphology of the non-devulcanized
rubber covered by the devulcanized rubber were observed. The effect of the oil content was also obvious.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction rubber composition of tire consists of natural rubber (NR, specially

for heavy vehicles tires), styrene-butadiene rubber (SBR) and
Tire rubber recycling or reclaiming is the process of recycling butadiene rubber (BR) [5]. Various attempts have been reported for
vehicles' tires that are no longer suitable for use on vehicles due to reclaiming tire rubbers [4,6e16]. They used several strategies for
wear or irreparable damages, i.e., punctures [1]. The demand for reclaiming (devulcanization) tire rubbers. They were included
tire will grow by 4.3% yearly and will reach to 2.9 billion in 2017 [2]. mechanical shear by two roll mill and a chemical agent [10e12],
As an estimation, over 17 and 3.3 million tons used tires are mechanical shear by an internal mixer and a devulcanization aid
generated each year worldwide and in the EU, respectively [3]. [7,9,14,16] mechanical shear by a single or twin screw extruder
Hence, end-of-life tires are a serious environmental concern and it's [4,13] and miscellaneous techniques using supercritical carbon di-
recycling is a must. Rubber reclaiming is one of the recycling oxide and a chemical agent [6]. However, the produced devulca-
methods applied to the waste rubber [4]. It uses thermal, me- nizates had low degree of devulcanization, resulting in poor
chanical and irradiation energies, with or without aid of mechanical and dynamical properties when they revulcanized.
devulcanizing chemicals (agents) to breakdown SeS bonds in vul- The three dimensional rubber network can also broken down by
canized rubber networks. The product in most cases is a partially irradiation (microwave) [17e19]. Garcia et al. [17] studied on the
devulcanized rubber which can replace partially virgin rubber and physical and chemical changes that occur in the ground tire rubber
can be revulcanized for manufacturing rubbery articles. A typical after different microwave exposure periods. For this purpose
chemical, thermal, rheological and morphological analyses were
performed on the tire rubber, which contained natural rubber (NR)
and styrene-butadiene rubber (SBR) as polymeric material. The
* Corresponding author. results showed that the microwave treatment promoted the
E-mail address: [email protected] (S.O. Mohaved).

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116 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125

breaking of sulphur cross-links and consequently increased the 280
C, respectively, as processing aids (Mehran Tyre 290 and
rubber fluidity. However, long periods of exposure led to degra- Fariman), 2-propanethiol, hexylamine, cyclohexanethiol (Sigma
dation and modification of some properties. De Sousa et al. [18] Aldrich), diphenyl disulfide (DPDS, Sigma-Aldrich), N-cyclohexyl-2-
investigated on devulcanization of natural rubber (NR) by micro- benzothiozyl sulfenamide (Perkacit CBS, Flexsys), hexadecylamine
waves, as well as the influence of the amount of carbon black on (HDA, Cayman Chemical Co.),2-mercaptobenzothiazole disulfide
this process through devulcanization of the NR with controlled (Perkacit MBTS, Flexsys), N-Cyclohexyl-2-benzothiazole sulfena-
composition on it. The results highlighted that the increase of the mide (SANTACURE e CBS, Flexsys), zinc oxide (activator; Harcros
temperature is responsible for the occurrence of devulcanization, Durham Chemicals, UK), stearic acid (activator; Anchor Chemicals
which is dependent on both the amount of carbon black present in Ltd., UK) and elemental sulphur (curing agent; Solvay Barium
the rubber and the time of exposure to microwaves. Zhang et al. Strontium, Hannover, Germany), N-tert-butyl benzothiazole-2-
[19] presented a paper in TMS annual meeting. They discussed sulfenamide (SANTACURE e TBBS, Flexsys).
about microwave absorption properties of the waste tire at various
temperatures. They characterized the conditions favorable for the
microwave heating of the waste tires. Karabork et al. [20] investi- 2.2. Devulcanization of the waste powder and preparation of the
gated on devulcanization of ground tire rubber by microwaves at rubber compounds
the same heating rate (constant power) and different times of
exposure. The devulcanized rubber (DV-R) and untreated GTR were First, waste powder samples were extracted by acetone to
characterized physically and thermally. The sol content and Fourier remove low molecular substances, i.e. oils, residue of curing
transform infrared spectroscopy (FTIR) analyses of the devulcan- chemicals and un crosslinked rubbers, using a Soxhlet apparatus
ized samples were examined to define the efficiency of devulca- and 300 mL of acetone and 100 g of the rubber for 24 h at 70
C, as
nization. In another attempt, Poyraz and co-workers [21] studied described in ASTM D297-93. After extraction, the samples were
on devulcanization of scrap ground rubber by short-term micro- dried in an oven with circulating air for 12 h. This material was used
wave irradiation and successive carbon nanotube growth. for devulcanization. Appropriate amount of CBS, DPDS, TMTD and
Based on our knowledge, in most published reports, microwave HDA which were used as devulcanizing agents, were mixed with
irradiation has been used lonely for devulacanization of the waste 30 g oil and then added to 100 g of above mentioned waste powder
rubber without using chemical agent. In addition, there is not any in a 500 mL glass beaker. The waste powder was soaked in the oil
report that compares the effect of the various chemical agents on for 12 h at 80
C in an oven to allow it to penetrate into the rubber
microwave devulcanization of the waste rubber. Authors [22,23] fully. This produced four compounds (compounds AeD; Table 2).
already studied the effect of various operative parameters There was also a reference compound (RC), which was mixed with
including several devulcanizing agents on microwave devulcani- the aromatic oil and no chemical (Table 2).
zation of ethylene-propylene-diene monomer (EPDM) and butyl Relatively, high level of the oil was incorporated in the formu-
rubber. In this study, the same parameters along with some more lation of the compounds. The oil dissolves the devulcanizing agent
complementary aspects on tire rubbers will be considered and and simultaneously, helps the rubber to swell more effectively. The
discussed. beaker was placed in a laboratory microwave oven (GMO-530,
Gosonic) with an output power of 900 Watts, frequency of
2000 MHz, and internal capacity of 30 L for various final temper-
2. Experimental atures. The devulcanized rubber compounds were bulky in size
after they were recovered from the microwave oven. They were
2.1. Materials: waste rubber, filler, and rubber chemicals subsequently processed on a laboratory two roll mills with cylin-
ders 14 cm in diameter and 32 cm long with 4 mm nip width at
Passenger car waste tire rubber was obtained from local city ambient temperature for 2 min to produce sheets which were
sites and subsequently subsequently ground to particles with a easier to work with.
median size of 319 mm (Fig. 1). Thermogravimetric analysis (TGA; To investigate the effect of various amounts of the devulcanizing
STA 1500, Scinco Co., Ltd.) was subsequently used to determine the agent (DPDS) and aromatic and paraffinic oils on the devulcanization
composition of the waste powder. TGA was performed in a nitrogen of the waste tire powder, seven more compounds were prepared
atmosphere below 550
C and in air above 550
C, respectively. The (compounds E,F,G and H; Table 3 and I,J and K; Table 4). Compounds
TGA curves and corresponding composition of the waste rubber in Table 4 had 2 phr DPDS as devulcanizing agent and all compounds
powder are shown in Fig. 2 and Table 1. The other ingredients were in Tables 3 and 4 were devulcanized at 240
C in the microwave oven
aromatic and paraffinic oils with initial boiling points, 270 and as explained earlier. The radiation time was about 3 min.

Fig. 1. Waste tire rubber particle size distribution.

 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125 117

Fig. 2. Thermogravimetric analysis test results for waste tire rubber powder.

Table 1
Physical properties and composition of tire rubber waste powder.

Property Amount

Sol content (%) 7.5

Density (g/cm3) 1.05
Crosslink Density (CLD)a (mol/m3) 165
TGA Unburned mineral and metal (%) 1.3
Carbon black (%) 34.5
Rubber (%) 62.4
Oil (%) 1.8
a
CLD was calculated using the Flory-Rehner equation [21].

Table 2
Devulcanizing formulations for the waste tire rubber powder. Effect of the devulcanizing agent, devulcanization temperature, 200
C.

Compound Waste rubber (phr) HDAa DPDSa CBSa MBTSa Aromatic oil (phr)

A 100 5 30
B 100 5 30
C 100 5 30
D 100 5 30
Reference (RC) 100 30
a
Devulcanizing agent (phr).

Table 3 oils and non-crosslinked rubber residues of the samples were

Devulcanizing formulations for the waste tire rubber powder: Effect of the extracted by toluene for 48 h at 110
C using a Soxhlet apparatus.
devulcanizing agent amount, devulcanization temperature, 240
C.
The extraction was performed using 300 mL of acetone and/or
Compound Waste rubber (phr) DPDSa Aromatic oil (phr) toluene and 100 g of the rubber. After extractions, the samples
E 100 2 30 were dried in an oven with circulating air for 12 h. The sol
F 100 4 30 fraction was defined as the sum of the soluble fractions in
G 100 6 30 acetone and toluene minus added oils to samples before
H 100 8 30
devulcanization.
a
Devulcanizing agent (phr). The solvent used for the crosslink density (CLD) determinations
was toluene. For the determination, 5 g of extracted rubber was
placed in 300 mL of the solvent in labelled bottles and allowed to
2.3. Measurement of the crosslink density, sol content, mono, di and swell for 16 h at 21
C. The weight of the samples was measured
polysulfidic crosslinks and devulcanization percent of the rubber every day until it reached equilibrium. The solvent was then
compounds removed. The samples were dried in air for 9 h and then in an oven
at 85
C for 24 h, and allowed to stand for an extra 24 h at 23
C
In the first stage, the low molecular polar substances, i.e. polar before reweighing. The CLD was then calculated using the Flor-
oils, residues of accelerators and curing chemicals was extracted yeRehner equation [24]:
by acetone and subsequently non polar components, non polar
118 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125

Table 4
Devulcanizing formulations for the waste tire rubber powder. Effect of oil content, devulcanization temperature, 240
C.

Compound Waste rubber (phr) DPDSa Aromatic oil (phr) Paraffinic oil (phr)

I 100 2 15 e
E 100 2 30 e
J 100 2 45 e
K 100 2 e 30
a
Devulcanizing agent (phr).

content, and CLDs of the devulcanized waste rubbers were sum-


2
1 ln 1  y0r þ y0r þ x y0r marized in Table 5.
V ¼
1=3  (1) For analysing the relationship between sol content and
Vs y0r  y0r 2
decreasing CLD after degradation of a network as a result of
devulcanization, Horikx analysis [27] was used. When only main
where V is the CLD (mol/m3), Vs is the molar volume of toluene
chain scission takes place during devulcanization, the relative
(1.069  104 m3/mol at 25
C), y0r is the volume fraction of rubber
decrease in CLD is given by Ref. [28]:
(polymer) in the swollen gel, and c is the interaction parameter
(c ¼ 0.405 [25]), which was calculated using the following equation 2 2 3
[26]: 1  s 0:5
wf 6 f 7
1 ¼ 1  4 2 5 (4)
1 wi
yοr ¼ ! (2) 1  si0:5

1 þ ddr 1
1ffil
ws
w0 1
s and when pure crosslink scission takes place during devulcaniza-
tion, the relative decrease in CLD is given by:
where dr (1.05 g/cm3) and ds (0.867 g/cm3) are the densities of the
2  2 3
rubber and solvent, respectively; ffil is the initial weight fraction of 0:5
wf 6g f 1  s f 7
filler in the sample after double extractions by acetone and toluene; 1 ¼14  2 5 (5)
ws is the weight of the swollen gel; and w0 is the weight of the dried wi
g i 1  si
0:5
sample.
The sol content and devulcanization % were calculated as
where si, wi and sf, wf are sol fractions and CLD's before and after
follows:
devulcanization, respectively. In these experiments, si and wi are
wi  w0 0.075 and 165 mol/m3 (Table 1), respectively. gi and gf are the
Sol contenet ¼ Sol fraction  100 ¼  100 (3) average number of crosslinks per chain in the remaining insoluble
wi
network before and after devulcanization, respectively. The rela-
tionship between g and s is as follow [28]:
Devulcanization ð%Þ ¼ 100  ðinitial waste rubber CLD
h
0:5 i
 final rubber CLDÞ
ð2 þ gÞ  g2 þ 4g
 =initial waste rubber CLD S¼ (6)
2g
where wi is the initial weight of the sample before double extrac- The value of gi was calculated by replacing s in Equation (6) by
tions; the initial waste rubber CLD was calculated to be 165 mol/m3 the value of 0.075 (initial sol content- Table 1).
(Table 1). Note that the Krause correction was not made because the By fixing the values of gi and si in Equations (4) and (5) and with
results were used primarily to compare the CLD of the compounds cooperation of Equation (6), Horikx curves can be drawn
tested. The devulcanization temperature, devulcanization %, sol (Figs. 3e6). Mono, di and polysulfidic crosslinks in rubber

Table 5
Devulcanization temperature, sol content, crosslink density, and devulcanization % of the rubbers.

Compound Devulcanization chemical Final temperature (
C) Sol content (%) CLD (mol/m3) Devulcanization (%)

RC e 200 7.5 165 00.0

A HDA 200 12.0 71 57
B DPDS 200 16.5 85 48
C CBS 200 12.0 96 42
D MBTS 200 10.0 93 43
B-1 DPDS 180 10.0 44 73
B-2 DPDS 220 14.0 71 57
B-3 DPDS 240 15.0 81 51
B-4 DPDS 260 12.0 78 53
B-5 DPDS 280 18.0 79 52
E DPDS 240 12.0 107 35
F DPDS 240 23.0 87 47
G DPDS 240 14.0 89 46
H DPDS 240 18.0 114 31
I DPDS 240 11.0 107 35
J DPDS 240 10.0 99 40
K DPDS 240 12.0 160 3
 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125 119

w
Fig. 3. The sol fraction versus relative reduction in CLD (1  wfi ) for compounds A to D and reference compound (final devulcanization temperature, 200
C).

w
Fig. 4. The sol fraction versus relative reduction in CLD (1  wfi ) for compounds B and B-1 to B-6 at various final temperatures.

compounds were measured using 2-propanethiol, hexylamine and pieces. The tests were performed at 21
C and a cross-head speed of
cyclohexanethiol as described in literature (Scheme 1) [29]. Note, in 500 mm/min. The hardness was measured using cylindrical sam-
this study and to increase the efficiency of SeS di bonds breakage, ples, 12.5 mm thick and 29.0 mm in diameter in a Shore A
hexanethiol replaced with cyclohexanethiol. Mechanism of sulphur durometer hardness tester.
crosslinks breakage by 2-propanethiol þ n-hexylamine and
cyclohexanethiol þ n-hexylamine are depicted in Scheme 2-a and
2-b, respectively [23]. Mono, di and polysulphide % in sulphur
bridges for selected rubber compounds were presented in Table 6. 2.5. Examination of the devulcanized rubber surfaces by scanning
electron microscopy
2.4. Measurement of the mechanical properties of the revulcanized
compound The surfaces of the devulcanized rubber compounds were
examined by a LEO 1530 VP field emission gun scanning electron
The tensile strengths, elongations at the break, tear strength and microscope (SEM). Small pieces of the rubber samples approxi-
modulus at different elongations of the rubber vulcanizates were mately 5 mm by 5 mm in dimensions were coated with gold and
determined in uniaxial tension in a SANTAM STM-20 mechanical then examined and photographed in the SEM. The rubber surfaces
testing machine, using standard dumbbell and rectangular test were then studied from the SEM micrographs shown in Figs. 7e9.
120 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125

w
Fig. 5. The sol fraction versus relative reduction in CLD (1  wfi ) for compounds E, F, G and H (final devulcanization temperature, 240
C).

w
Fig. 6. The sol fraction versus relative reduction in CLD (1  wfi ) for compounds I, E and J (final devulcanization temperature, 240
C).

3. Results and discussion rubber, a transition in the range 516e573
C was observed. This was
attributed to the combustion of carbon black (after changing the
3.1. Devulcanization of the waste powder atmosphere to air). The unburned residue was attributed to the
minerals and metals in the sample.
The particle size of the waste powder is an important factor for The proposed radical and ionic devulcanization mechanism of
controlling devulcanization temperature as it was found by authors tire rubber is shown in Schemes 3 and 4, respectively. For the case
earlier [22,23]. For large particles, i.e. 0.5e1 cm in diameter, hot of DPDS, CBS and MBTS (radical mechanism), first, the polymer
spots appeared in the sample during microwaves irradiation and chains divide into two radicals through sulphur bridges by micro-
when a part of the sample degrades, the other part may still remain wave radiation. Subsequently, formed radicals combine with the
cold. Fig. 1 shows used waste rubber powder with a median particle radicals of the reagents (these radicals simultaneously produce by
size of 319 mm. It also shows that 10, 50 and 90% of the waste rubber microwave radiation) and make stable molecules. The devulcani-
particles have diameters less than 133, 367 and 614 mm, respec- zation mechanism for HDA is ionic. Here, the polymer chains with
tively. Subsequent results in Table 5 show efficient devulcanization the aid of HDA and microwave radiation divide in to two ions
of the used waste rubber powder. through their sulphur crosslinks [23].
w
Table 1 and Fig. 2 show the TGA results for the used waste The sol fraction versus relative reduction in CLD (1  wfi ) for
rubber powder. The TGA curve show that rubber degradation began irradiated compounds prepared with different devulcanizing
at 231
C and finished at 516
C. Mass loss was also observed in the agents, HDA, DPDS, CBS, MBTS and reference compound (com-
range 33e231
C, because of the 1.8% oil presence in the initial pounds A,B,C,D and RC, without devulcanizing agent, Table 2) at
rubber waste. In addition to the mass loss related to the oil and 200
C are depicted in Fig. 3 (CLD of RC was the same of the initial
 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125 121

Scheme 1. Experimental procedure for the measurement of types and densities of sulphur crosslinks [29]. Note, in this study and to increase the efficiency of SeS di bonds
breakage, hexanethiol replaced with cyclohexanethiol.

waste rubber and consequently, it was not indicated in figure). As during devulcanization. The closer data points to the dotted curve
observed, compound with DPDS content with the sol fraction and show more sulphur crosslinks breakage when compared with main
CLD of 16.5% and 85 /m3, respectively, had a devulcanization chain scission and it is more desired. The sol fraction and CLD
percent of 48% (Table 5, Compound B). The data of this compound values for RC, HDA, CBS and MBTS (compounds RC,A,C and D,
were completely close to the sulphur crosslink scission curve Table 5) were 7.5% and 165 mol/m3, 12% and 71 mol/m3, 12% and
(Equation (5), the dotted curve in Fig. 3). If only sulphur crosslinks 96.1 mol/m3 and 10% and 93 mol/m3, respectively. Interestingly, for
break during devulcanization, data points should lie on the dotted Compound RC the CLD was exactly the same of the initial waste
curve and in case of complete main chain scission, they should lie rubber powder before devulcanization (165 mol/m3, Table 1). It
on the solid curve. Note, dotted and solid curves were constructed means microwave irradiation without using devulcanizing agent
by using Equations (5) and (4) as described in reference 25, had not any effect on sulphur crosslink breakage. The data for
respectively. Lying data between these two curves mean a combi- compounds A and D are not desired as they lie under the sulphur
nation of sulphur crosslink and main chain scission occurrence crosslink scission curve (Fig. 3). Although, the devulcanization
122 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125

Scheme 2. Mechanism of sulphur crosslinks breakage by (a) 2-propanethiol þ n-hexylamine (b) cyclohexanethiol þ n-hexylamine [23].

Table 6
Mono, di and polysulphides fractions in sulphur bridges for selected rubber compounds.

Compound no. Total CLD (mol/m3) Mono sulphide % Disulphide % Polysulphide %

Initial waste rubber powder 165 60 18 22

I 107 80 18 2
B-1 44 88 12 e

Fig. 7. SEM micrograph showing the interior of the reference compound (RC) after Fig. 8. SEM micrograph showing the interior of Compound I after freeze-fracture.
freeze-fracture.

sensitively unchanged in range of 51e53%. The data for three

percent of Compound A was greater when compared with the compounds, B-1, B-2 and B-4 (180, 220 and 260
C) were
values for compounds B,C and D but due to aforementioned reason, completely under the sulphur crosslink breakage curve and
DPDS was chosen as suitable devulcanizing agent. Fig. 4 shows sol consequently, they are not desired. However, at 200, 240 and 280
C
fraction versus relative reduction in CLD for DPDS devulcanized (compounds B, B-3 and B-5), the points lie down on the sulphur
compounds (compound's B and B-1 to B-5, Table 5) at various final crosslink breakage curve and/or between two curves which in-
microwave temperatures, 180, 220, 240, 260 and 280
C. Generally, dicates a pure sulphur breakage and/or a combination of the main
devulcanization percents of the compounds decreased with chain scission and sulphur crosslink breakage during irradiation
increasing temperature. The reason may refers to a group of new process. Among of above mentioned compounds, the point for
main chain reactions named “main chain un saturation volatile Compound B-3 lie down very close to the sulphur crosslink
formation crosslinking” [30] and or the formation of new mono and breakage curve and consequently, 240
C can be selected as opti-
polysulphide sulphur bridges as it is shown in Table 6. Scheme 5 mum end devulcanization temperature. Table 7 compares the
[23] clearly describes the formed radicals after microwave radia- selected mechanical properties of the revulcanized Compound, B-3
tion and subsequent chain and sulphur crosslinks growth. Our and reference compound, RC (curing recipe for revulcanization of
founds are in conformity with the other's report [31]. the Compound B-3, accelerator TBBS, 4 phr, ZnO, 2.5 phr and stearic
The highest and lowest values belonged to compounds B-1 and acid, 2 phr as it was routine for passenger car tires). As it observes,
B at 180 and 200
C with the values of 73 and 48%, respectively. For the most of the mechanical properties of the revulcanized rubber
temperatures above 240
C, devulcanization percents remained were inferior when compared with those of the reference rubber.
 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125 123

4 phr DPDS, the most devulcanization percents, 31 and 47%,

respectively. However, their corresponding data points in Fig. 5
stand just on or above chain scission curve. The data points of
Compounds E and G with 2 and 6 phr DPDS, respectively, stand
exactly on the sulphur crosslink breakage curve but due to higher
devulcanization percent for Compound G (46%), it can be concluded
that 6 phr DPDS is enough for effective devulcanization at 240
C.
Fig. 6 investigates the effect of aromatic oil content on devulcani-
zation process. The values of aromatic oil content were 15, 30 and
45 phr for compounds I, E and J, respectively (Table 4). For prepa-
ration of Compound K, 30 phr paraffinic oil was used. All com-
pounds had 2 phr DPDS in their formulations. Increasing aromatic
oil from 15 to 30 phr had not any effect on devulcanization percent
(cf. Compound I with E in Tables 4 and 5) but it has beneficial effect
on devulcanization process through lying the data points on
sulphur crosslink breakage curve for Compound E (Fig. 6).
Increasing aromatic oil to 45 phr had detrimental effect on devul-
canization process through lying down data point under sulphur
Fig. 9. SEM micrograph showing the interior of Compound B-1 after freeze-fracture. crosslink breakage curve (Fig. 6), although, devulcanization percent

Scheme 3. Proposed radical devulcanization mechanism of tire rubber.

Scheme 4. Proposed ionic devulcanization mechanism of tire rubber by HDA.

As an illustration, the tensile strength, elongation at the break and increased from 35 to 40%. Comparison between devulcanization
tear strength were reduced from 19 to 10 MPa, 540 to 226% and 24 percents of two compounds E with 30 phr aromatic oil and K with
to 18 N/mm for RC and revulcanized B-3, respectively. Fig. 5 com- the same amount paraffinic oil reveals adverse effect of paraffinic
pares sol fraction versus relative reduction in CLD for compounds E, oil on devulnization process (Table 5). The reason may refer to
F, G and H with different DPDS contents of 2, 4, 6 and 8 phr, lower solubility of DPDS in paraffinic oil when compared with ar-
respectively. These compounds had 30 phr aromatic oil in their omatic oil. In this case, formed DPDS radicals can't reach to broken
formulations and devulcanized at 240
C (Table 3). Interestingly, macromolecules easily.
increasing DPDS had not beneficial on devulcanization process.
Compound H with 8 phr DPDS had the least and Compound F with
124 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125

Scheme 5. Polymer sulphur crosslink and chain growth mechanism [23].

Table 7
Selected mechanical properties of the revulcanized Compound B-3.

Compound no. Hardness (ShoreA) Tensile strength (MPa) Elongation at the break (%) Tear strength (N/mm) Modulus at 50% (MPa) Modulus at 100% (MPa)

B-3 62 10 226 18 3 5
RC 68 19 540 24 2.5 4

3.2. Mono, di and polysulphides fractions in sulphur bridges for

selected rubber compounds

Table 6 depicts mono, di and polysulphide percents in sulphur

bridges for selected rubber compounds I, B-1 and waste rubber
powder. As it observes, the sulphur bridges in initial waste rubber
have 22% poly, 60% mono and 18% disulphides. It can be concluded
that the waste rubber was cured by an efficient or semi-efficient
cure system with relatively low concentration of the elemental
sulphur. A quick look in Table 6 reveals that for the Compounds I
and B-1 after microwave irradiation, a part or total amount of the
polysulphides were broken resulting in lower CLD's while the
mono sulphide crosslinks remained unchange. The CLD of the
waste rubber was 165 mol/m3 which reduced to the values of 107
and 44 mol/m3 for Compounds I, and B-1, respectively. As a result,
the structure of the remained sulphur crosslinks were mostly mono
sulphide.

Fig. 10. SEM micrograph showing the interior of the revulcanized Compound B-3 after
3.3. The morphology of the devulcanized waste rubber powder freeze-fracture.

The mechanical properties of the blends were affected by the

devulcanized rubber. Fig. 9 belongs to Compound B-1 with 73%
resulting polymer morphology [22,23]. Figs. 7e10, show the in-
devulcanization (Table 5). The predominant microstructure matrix
ternal structure of the initial waste rubber, compounds I and B-1
is devulcanized rubber and fine morphology of the non-
and the revulcanized Compound B-3 (Tables 4 and 5) after freeze-
devulcanized rubber in a smooth matrix of devulcanized rubber
fracture, respectively. Fig. 7 shows the surface of the vulcanized
also seen in the image. The border of matrix with vulcanized rubber
rubber. It is completely heterogeneous and coarse. Fig. 8 clearly
in this compound is smooth. This may attributed to the high level of
shows internal structure of Compound I with relatively low
the oil in formulation of this compound (30 phr). Fig. 10 shows the
devulcanization percent (35%, Table 5). It does show a coarse
surface of the revulcanized Compound B-3. Here, the predominant
morphology of the non-devulcanized rubber covered by the
 M. Molanorouzi, S.O. Mohaved / Polymer Degradation and Stability 128 (2016) 115e125 125

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