eXPRESS Polymer Letters Vol.9, No.

12 (2015) 1076–1086
Available online at www.expresspolymlett.com
DOI: 10.3144/expresspolymlett.2015.97

Devulcanization of styrene butadiene rubber by microwave

energy: Effect of the presence of ionic liquid
S. Seghar1,4, N. Aït Hocine2*, V. Mittal3, S. Azem4, F. Al-Zohbi5, B. Schmaltz5, N. Poirot6
1
LMR, CERMEL, Université François-Rabelais de Tours, 37300 Joué-Lès-Tours, France
2
LMR, INSA Centre Val de Loire, 3 rue de la Chocolaterie, BP 3410, 41034 Blois, France
3
Department of Chemical Engineering, The Petroleum Institute, Abu Dhabi, UAE
4
LEC2M, Université Mouloud Mammeri, BP 17, Tizi-Ouzou 15000, Algérie
5
PCM2E (E.A. 6299), Université François-Rabelais de Tours, Bâtiment J-Parc de Grandmont, 37200 Tours, France
6
GREMAN, IUT de Blois, 15 rue de la Chocolaterie, 41000 Blois, France

Received 25 April 2015; accepted in revised form 15 July 2015

Abstract. In this study, styrene butadiene rubber (SBR) was devulcanized using microwave irradiation. In particular, effect
of ionic liquid (IL), pyrrolidinium hydrogen sulfate [Pyrr][HSO4], on the devulcanization performance was studied. It was
observed that the evolution of the temperature reached by rubber powder exposed to microwave irradiation for different
energy values was favored by the presence of ionic liquid [Pyrr][HSO4] significantly over the whole range of the
microwave energy values. Beyond the threshold point of 220 Wh/kg, the soluble fraction after devulcanization sharply
increased with increasing devulcanization microwave energy. For the powder mixed with [Pyrr][HSO4], the increase was
more significant. Furthermore, the crosslink density was observed to decrease slowly with the microwave energy up to
220 Wh/kg, beyond which the crosslink density decreased significantly for the rubber impregnated with IL. For the rubber
with IL, significant and continuous increase in Tg with microwave energy values was observed in comparison with the SBR
where no change in transition temperature was observed. Mechanical shearing of rubber gums in the two-roll mill favored
the devulcanization process, which indicated that the combination of mechanical loading with microwave energy and IL is
an efficient procedure allowing an optimal devulcanization of rubbers.

Keywords: rubber, recycling, devulcanization, microwaves, ionic liquid

1. Introduction process which leads to recycling the waste tires as

Increase in the demand of rubber in recent years, polymeric materials, thus, also decreasing the extent
particularly in tire industry, has resulted in not only of environmental risks.
increased prices of raw materials, but also accumu- Passenger car tire material is a blend of different poly-
lation of harmful wastes. Garbage dumps of used mers with the main component being styrene-buta-
tires represent flammable sites and generate prolif- diene rubber (SBR). Each polymer contributing to the
eration of various insects and rodents carrying dis- tire formulation has its own specific degradation and
eases. Moreover, slow degradation of rubber residues devulcanization characteristics. As a result, a num-
results in severe environmental pollution. Recy- ber of physical and chemical methods have been
cling such waste safely is therefore a big challenge developed to break the crosslink bonds or induce
for industrialists and academic researchers. Devul- active groups on the surface of ground rubber. These
canization of waste rubber products is one of such methods are based on mechanical energy [1], ultra-

*
Corresponding author, e-mail: [email protected]
© BME-PT

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sound [2, 3], microwave irradiation [4, 5], chemical ing to the highest devulcanization proportion. Simi-
desulfurization reagents [6, 7] or biotechnological larly, Scagliusi et al. [13] devulcanized chloroprene
methods [8]. Depending on their efficacy, they lead rubber, followed by re-vulcanization. The authors
to the devulcanization or the reclaiming process. observed that properties of the recycled material
Devulcanization targets the sulfuric crosslinks in changed with microwave irradiation time, as com-
the vulcanized rubber and thus carbon-sulfur (C–S) pared to the original material. Hardness and frac-
and sulfur-sulfur (S–S) bonds are selectively cleaved, ture resistance were observed to decrease, whereas
while reclaiming is usually accompanied with con- rupture strain increased. Vega et al. [5] also com-
siderable scission along the polymeric chains result- bined microwave irradiation with the effect of
ing in lower molecular mass fractions [9]. diphenyl sulfide (DPDS), chemical agent supposed to
Microwave devulcanization process was proposed improve devulcanization process. The authors high-
by Goodyear in 1978 and successfully implemented lighted the beneficial effects of DPDS on the effi-
by Novotny et al. [4]. It consists of exposing the ciency of microwave devulcanization process. In
waste rubber, for a short time, to controlled micro- another study, Hong et al. [14] also compared devul-
wave irradiation. However, only sulfur-vulcanized canization performance of microwave and ultra-
rubber containing polar groups or components can sonic procedures and concluded that microwave
be heated and thus be devulcanized with this tech- technique is better than ultrasonic method.
nique. To improve devulcanization efficiency and reduce
Microwave heating is based on the interaction of treatment energy, promising new approach consists
the oscillating electrical field of microwaves with of impregnation of the waste rubber with solvent
the molecular dipoles and/or charged ions present and then heat treating the impregnated material
in the sample. Microwave irradiation triggers heat- with microwave radiation. In fact, impregnation of
ing by three main mechanisms: dipolar polariza- the waste rubber could promote the heat rise when
tion, ionic conduction and interfacial polarization. exposed to microwave radiation.
While the dipolar polarization mechanism (dielec- Ionic liquids (ILs), considered as an alternative to
tric heating) explains the heating phenomena of conventional organic solvents, are of interest in a
dipoles, the ionic conduction mechanism explains the variety of technological processes. For instance,
heating in samples with free ions or ionic species. they were recently used to improve the degree of
The interfacial polarization (also called the Maxwell- dispersion of a nanosized ZnO and Silica in NBR
Wagner effect) mechanism describes the heating in matrix [15]. The desire for green solvents for indus-
non-homogeneous systems created by the suspen- trial processes is partially responsible of this keen
sion of conducting particles in a non-conducting interest. ILs are (molten) salts composed of large
medium. Fix [10] extensively studied the efficiency variety of organic cations and organic/inorganic
of the microwave devulcanization process and such anions [16]. They present several interesting prop-
operation was concluded to be feasible. erties: excellent solvent for various organic/inor-
Other studies by Goodyear society on the devulcan- ganic materials, negligible vapor pressure, high
ization of EPDM rubber by microwaves showed thermal and chemical stability, non-flammability,
that properties of the treated material were not con- high ionic conductivity, low viscosity and large elec-
siderably altered [4, 10]. EPDM being a non-polar trochemical capacitance [16, 17]. The ionic conduc-
rubber, microwave energy was transferred in the tion mechanism is the most important effect in the
whole volume of the material via carbon black filler heating of ILs by microwave; it increases their
initially introduced as reinforcing particles. dielectric loss factor.
Bani et al. [11] also performed similar studies and In this study, styrene butadiene rubber (SBR) was
observed that the microwave devulcanization devulcanized using microwave irradiation and the
process was effective only beyond the heating tem- performance of the devulcanization treatment was
perature of 300°C. analyzed in term of crosslink scission. Effect of
Landini et al. [12] used a microwave technique to [Pyrr][HSO4], on the devulcanization performance
devulcanize bromobutyle (BIIR), and optimal power was studied, which represents one of the originali-
and time of treatment were identified as factors lead- ties of this study.

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2. Experimental gium). Before the devulcanization treatment, the

2.1. Materials rubber was grounded, at ambient temperature, with
The analyzed material in this study was a styrene- a disc mill PQ500 (Phenix Machinery, Sancheville
butadiene rubber (SBR) obtained by mixing virgin 28800, France) containing a 4 mm screen. The
SBR and additive components in an open two roll obtained ground SBR was passed in a succession of
mill, at room temperature. Parts per hundred rubber different mesh sieve, which allowed evaluating the
[phr] of the whole formulation are reported in particle size distribution of the ground rubber. It
Table 1. appeared that ~96% of the SBR powder has a size
The material studied in this work is a mixture of ranging from 1 to 4 mm and ~4% has a size lower
two grades of SBR: 50 phr of SBR1500 with a than 1 mm. The SBR powder of size ranging from 1
styrene content of 23.5% and 50 phr of SBR1900 to 4 mm has used in this study.
with a styrene content of 75%. We deliberately chose
such a mixture in order to limit the amount of buta- 2.2. Microwave devulcanization procedure
diene, which reduces the number of carbon-carbon A commercial microwave oven (Galanz, Foshan,
double bonds (C=C) leading to a loosely cross- China) was adapted to be used for devulcanization
linked network. Reduction of C=C bonds also lim- treatment of SBR ground rubber in laboratory. Stir-
its the influence of the external environment (oxy- ring system and infrared temperature sensor (Spark-
gen, ozone …) on the rubber structure during pro- Fun IR Thermometer Evaluation Board-MLX90614,
cessing and storage. A loosely cross-linked network Lextronic, France) were additionally installed in the
facilitates the penetration of solvent through the oven and the process was controlled by a computer.
rubber and therefore improves the sensitivity of A mass M of ~50 g of ground SBR placed in a
methods which allow evaluation of cross-link den- 250 mL beaker was exposed to microwave irradia-
sity and soluble fraction. tions under magnetron power P of 656 watts, at dif-
Differential scanning calorimetry (DSC) tests were ferent time values t. The stirring speed was 40 rpm.
conducted in a nitrogen environment on un-vulcan- The corresponding microwave specific energy E
ized and vulcanized SBR, using Netzsch equipment was evaluated from Equation (1):
(Netzsch maia 200F, Selb, Germany). Samples
Pt
weighing about 10 mg were heated from –100°C up E5 ~ (1)
M
to 280°C at a rate of 10°C/min.
After mixing operation, the rubber was vulcanized In order to improve the efficiency of the rubber
at 170°C for 7 min, under compression in a hydraulic microwave processing, the same procedure was
molding press (Agila, Kortrijk-Bissegem, Bel- repeated, but by mixing priory the SBR powder in
10 wt% of ionic liquid pyrrolidinium hydrogen sul-
Table 1. Components used for the rubber formulation fate [Pyrr][HSO4], in a crystallizer during 10 min-
Components
Quantity utes. The mixture was left to stand for 1 hour at least,
[phr]
prior to microwave treatment. No specific other treat-
Styrene butadiene rubber (SBR 1502) 50
Styrene butadiene rubber (SS260) 50
ment was applied for IL and SBR powder before
Carbon black (HAF N330) 60 microwave treatment. Properties of this IL are sum-
Naphtenic oil 25 marized in [18]. It was used because it is a good heat
Paraffinic oil 1.2 vector and it readily absorbs microwave energy,
Rubber antioxidant: N-Isopropyl-N!-phenyl-p-
which could quickly increase the temperature of the
phenylene-diamine (IPPD) 1.25
Rubber antioxidant: N-(1,3-Dimethylbutyl)-N!- mixture during the devulcanization treatment. More-
phenyl-p-phenylenediamine (6PPD) 1.25 over, it does not evaporate and does not degrade
Rubber antioxidant: 2,2,4-trimethyl-1,2-dihydro-
below 200°C. Furthermore, this IL is a green solvent
quinoline (TMQ) 1
Antiozonant agents (Paraffinic wax) 2 with low vapor pressure, high chemical and thermal
Activator: zinc oxide (ZnO) 5 stability and it is a non-flammable liquid. Thus, the
Dispersing agent and accelerator activator: Stearic goal of using such IL was to favor the transfer of the
acid 2
microwave energy until the core of the material
Vulcanization agent: sulfur (S) 1.5
Accelerator: N-cyclohexyl-2-benzothiazole granulates and to obtain uniform distribution of the
sulphenamide (CBS) 1.5 temperature through the volume of these particles.

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Table 2. Coding and devulcanization conditions devulcanization process. The soluble fraction S of
SBR without
SBR with Magnetron Treatment
Energy
the material was evaluated using Equation (2):
10 wt% power time
[Pyrr][HSO4] [Wh/kg] M i 2 Mf
[Pyrr][HSO4] [W] [s]
S 3,4 5 ~100 (2)
SBR SBR-P 0 0 0 Mi
SBR-110 SBR-P-110 656 30 110
SBR-220 SBR-P-220 656 60 220 where Mi and Mf are the SBR rubber weight before
SBR-330 SBR-P-330 656 90 330 and after extraction operation respectively.
SBR-440 SBR-P-440 656 120 440 After swelling in cyclohexane (Sigma-Aldrich, Stein-
heim, Germany) at room temperature for 72 h, the
It was observed that the ground rubber ignited when soluble fraction was weighed and then dried in a
it was exposed for microwave energy inducing tem- vacuum oven at 50°C for 24 h. The apparent
perature higher than 210°C. This is probably due to crosslink density !c was determined according to
the inflammation of the naphtenic oil (CIRCOSOL Equation (3) [19]:
4240) and paraffinic process oil (FLEXON 876) 2
nr 1 xnr 1 ln11 2 nr 2
used as plasticizers in the rubber mixture. In fact, nc 5 1>3
(3)
the flash points of these oils are 221 and 246°C, ns 10.5nr 2 nr 2
respectively. Thus, the magnetron power value of with:
656 watts and the maximal time of treatment of 120 s mr
were selected such as the induced maximal temper- nr 5 (4)
rr
ature was lower than ~210°C. The treatment condi- mr 1 ms a b
rs
tions are summarized in Table 2. The SBR soaked
in [Pyrr][HSO4] is denoted SBR-P in this paper. In Equations (3) and (4), !r is the volume fraction of
The heat capacity Cp of the [Pyrr][HSO4] was deter- the polymer in the swollen specimen, !s is the molar
mined by the DSC approach. It was achieved by volume of the solvent, " is the Flory-Huggins poly-
heating a small quantity of IL from ambient temper- mer solvent interaction parameter (equal to 0.489
ature to 200°C and the heat flow was recorded dur- for SBR-Cyclohexane (ASTM-D6814-02)), mr is
ing the test. Thermo-gravimetric analyses (TGA) the mass of the dry rubber, ms is the mass of the sol-
were also performed on [Pyrr][HSO4] using a Perkin- vent absorbed by the rubber, #r and #s are the densi-
Elmer Diamond TG/DTA (Waltham, Massachu- ties of the dry rubber and solvent respectively.
setts, U.S.A). A small quantity of the liquid was The percent devulcanization was calculated accord-
heated from room temperature up to 550°C, at a rate ing to the standard ASTM test method D6814-02,
of 10°C/min and under a nitrogen atmosphere. The using Equation (5):
mass variation of the liquid was measured as a nf
function of temperature. Devulcanization 3 , 4 5 a 1 2 b 100 (5)
ni ~
2.3. Evaluation of the devulcanization where !i and !f are the crosslink densities of the
Right after devulcanization treatment, the SBR was samples before and after devulcanization, respec-
washed with distilled water then dried in a vacuum tively.
oven (Heraeus Vacuum oven VT6025, Hanau, Ger- The devulcanization process theoretically results in
many) at 30°C for 24 h. Soluble fraction of ground crosslink scission. However, actual route also causes
SBR and devulcanized ground SBR were then deter- breaking of principal polymer chains. When this
mined by extraction in a Soxhlet extractor for 24 h phenomenon is considerable, it induces the loss of
in acetone (Sigma-Aldrich, Steinheim, Germany) to the recyclate properties. To further understand the
remove low-molecular weight polar substances like devulcanization mechanism, theoretical relation-
remains of accelerators and curatives. This opera- ship developed by Horikx [20] was used, which cor-
tion was immediately followed by an extraction for relates the rubber soluble fraction of the devulcan-
72 h in toluene (Sigma-Aldrich, Steinheim, Ger- izates and the relative decrease in crosslink density.
many) to remove the non-polar components such as When only main-chain scission takes place, the rel-
oil and non-crosslinked polymer residues or soluble ative decrease in the apparent crosslink density is
polymer chains released from the network by the given by Equation (6):

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2
nf 11 2 !Sf 2
12 512 c 2
d (6)
ni 11 2 !Si 2

where Si and Sf are the soluble fraction of the

untreated vulcanizate and reclaimed vulcanizate
respectively, !i is the crosslink density of the
untreated vulcanizate and !f is the crosslink density
of the reclaimed vulcanizate.
For pure crosslink scission, the soluble fraction is
related to the relative decrease in crosslink density
by Equation (7):
2
nf gf 11 2 !Sf 2 Figure 1. DSC curves of the SBR before and after vulcan-
12 512 c 2
d (7) ization
ni gi 11 2 !Si 2
where $i and $f are the average numbers of cross- thermic peak beginning at ~160°C and reaching its
linked units per chain before and after treatment maximum at ~210°C, was observed. This peak cor-
respectively. These parameters were determined responds to the temperature of the SBR vulcaniza-
from the relation between soluble fraction S and the tion reaction. Such a transition was not present in the
number of crosslinked units per chain $, given by vulcanized rubber thermogram, thus, further prov-
Charlesby [21, 22] under the following form Equa- ing that the vulcanization of the material was entirely
tion (8): accomplished.
The heat capacity Cpe of [Pyrr][HSO4] is reported in
1
S5 (8) Figure 2 as a function of temperature. This heat
11 1 g 2 gs 2
capacity is evaluated from Equation (9):
After applying microwave devulcanization process mr we 2 w0
on SBR soaked in [Pyrr][HSO4] and no-soaked Cpe 5 C (9)
me ~ wr 2 w0 ~ pr
SBR, glass transition temperature Tg of these mate-
rials was determined following the same experi- where mr and me are masses of aluminum oxide and
mental protocol described above. Tg could be a per- ionic liquid [Pyrr][HSO4] respectively ; %0, %r and
tinent indicator of microstructure change which %e are heat flows measured for empty crucible, alu-
may be caused by, among others, the vulcanization minum oxide and IL respectively; Cpr represent
or devulcanization process. mass calorific capacities of aluminum oxide. The
Finally, the Mooney viscosity ML (1+4)·100°C was heat capacity of distilled water was also measured
measured using a Mooney viscometer from Gibitre and showed in Figure 2. It can be seen that Cp of
Instruments (Bergamo, Italy). [Pyrr][HSO4] was constant up to 120°C and was
All specimens were continuously stored under con-
trolled temperature of 4°C.

3. Results and discussion

Figure 1 shows the heat flow recorded during heat-
ing, as a function of temperature, for un-vulcanized
and vulcanized SBR. It exhibited an endothermic
transition characteristic of glass transition tempera-
ture, Tg, estimated at –48°C for the raw SBR and at
-43°C for the vulcanized SBR. The increase of Tg
from –48 to –43°C confirmed the successful vul-
canization of the studied material. In fact, the vul-
canization treatment led to the formation of 3D net-
work, thereby reducing macromolecular mobility Figure 2. Heat capacity of [Pyrr][HSO4] and water as a
resulting in augmentation of Tg. Moreover, an exo- function of temperature

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Figure 3. Temperatures of water and [Pyrr][HSO4] as a Figure 5. Temperature of ground rubber with and without
function of microwave irradiation time ionic liquid as a function of microwave energy

three times smaller than that of distilled water, thus, was found to be ~289°C, as shown in Figure 4. To
proving a good heat transfer capacity of this IL. avoid the degradation of [Pyrr][HSO4] during the
Figure 3 presents temperature evolutions of devulcanization treatment, this temperature value
[Pyrr][HSO4] and distilled water as a function of should not be exceeded when the SBR rubber com-
the time, recorded under microwave irradiation at bined with [Pyrr][HSO4] is treated by microwave
magnetron power of 656 W. It was evident that the irradiation as described above.
temperature of the IL increased more quickly than Figure 5 shows the evolution of the temperature
water to become two times greater after 100 s of reached by rubber powder exposed to microwave
exposition. Moreover, contrary to the temperature irradiation, for different energy values. The presence
of the water that stabilized at 100°C beyond 80 s, of ionic liquid [Pyrr][HSO4] significantly favored
the temperature of the IL increased continuously over the material heating over the whole range of the con-
the range of analysis time. These results further sidered microwave energy values. In fact, the temper-
confirmed the relative high ability of [Pyrr][HSO4] ature reached by the SBR soaked in [Pyrr][HSO4]
to convert microwave energy in heat, compared to was 1.70 times greater than the dry SBR. This result
water. suggested that [Pyrr][HSO4] could play energy vec-
Figure 4 shows the weight loss of [Pyrr][HSO4] as a tor role during the microwave devulcanization
function of temperature, obtained by TGA measure- process.
ments. The curve exhibited a first plateau followed Figure 6 shows evolutions of the soluble fractions
by a sudden decrease corresponding to its thermal (Equation (2)) of treated rubber as a function of
degradation. The onset degradation temperature, microwave energy. The soluble fraction indicates
Tonset, was evaluated by the method of tangent and the extent to which the rubber network is broken.
From the Figure 6, it was evident that microwave
treatment of sulfur-cured SBR exhibited a soluble
fraction similar up to 220 Wh/kg, irrespective of IL
soaking. This indicated that up to this treatment
energy value, rubber network was still intact. Beyond
this threshold point, the soluble fraction sharply
increased with increasing devulcanization micro-
wave energy i.e. by increasing the treatment tem-
perature. The increase was more significant for the
powder mixed with [Pyrr][HSO4], further proving
the positive role played by the IL in the microwave
devulcanization process of rubbers.
Figure 7 depicts crosslink densities (Equation (3))
Figure 4. TGA curve of [Pyrr][HSO4]
of SBR and SBR-P samples, as a function of micro-

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Figure 6. Soluble fraction of ground rubber with and with- Figure 8. Devulcanization of ground rubber with and with-
out ionic liquid as a function of microwave energy out ionic liquid as a function of microwave energy

wave energy. The crosslink density decreased slightly value, average temperature reached by SBR-P was
and slowly with the microwave energy up to much higher than the one reached by dry SBR.
220 Wh/kg, critical value beyond which the crosslink Also, the devulcanization process seemed to be effi-
density decreased significantly for the SBR-P rub- cient above a temperature threshold of ~200°C, in
ber. These results agreed well with the findings agreement with the results found by Saiwari et al.
shown in Figure 6 and confirmed that the liquid [23] in the devulcanization of SBR in an internal
ionic [Pyrr][HSO4] favored the microwave devul- mixer with addition of treated distillate aromatic
canization process. Figure 8 also shows the devul- extract (TDAE) oil and diphenyldisulfide (DPDS).
canization proportions (Equation (5)) of the SBR and To further analyze the devulcanization of rubbers
SBR-P, as a function of microwave energy. Curves by microwave process, the distribution of the treat-
showed the same trends as soluble fractions (Fig- ment temperature was recorded with an infrared
ure 6), confirming existence of a relationship between camera FLIR JADE-MWIR, in both SBR and SBR-P,
the two quantities (Equations (2) and (5)). Devul- after subjecting them to microwave energy. The
canization fractions are also represented in Figure 9 obtained micrographs are shown in Figure 10, as an
as a function of average temperature generated in example for treatment energy of 40 Wh/kg. The
rubber powder, measured with infrared sensor dur- temperature was observed to be more homogeneous
ing microwave irradiation. It should be noticed that and better diffused in the SBR-P powder than in the
rubber powder was mixed with an agitator during dry SBR powder. This result proved that microwave
the devulcanization treatment. The experimental data irradiation produced efficient internal heating by
of both SBR and SBR-P were fitted by power laws. direct coupling of microwave energy with the IL,
It was evident that for a given microwave energy resulting in higher average temperature and homo-

Figure 7. Crosslink density of ground rubber with and with- Figure 9. Devulcanization of ground rubber with and with-
out ionic liquid as a function of microwave energy out ionic liquid as a function of temperature
reached during microwave treatment

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Figure 10. Temperature of the ground rubber (a) without ionic liquid and (b) with ionic liquid, measured with a thermal
camera

geneous heating throughout the treated material, ground rubber mixed with IL. For instance, for the
which can partially explain the lower crosslinking same microwave energy of 440 Wh/kg, apparent
density of the SBR-P shown in Figure 7. devulcanization in SBR-P reached ~50%, which
Figure 11a and 11b show the experimentally deter- was four times greater than dry SBR.
mined soluble fractions of SBR and SBR-P respec- Figure 12 shows the evolution of Tg for the SBR
tively, as a function of devulcanization fractions eval- and SBR-P, as a function of microwave energy. The
uated using Equation (5), for different microwave Tg of the SBR remained almost constant in the
energy values. Theoretical curves of Horikx given whole range of the applied microwave energy val-
by Equations (6) and (7) are also plotted in Fig- ues, suggesting that there was no significant change
ure 11. The experimental data fitted well with the in the material microstructure in this range. How-
Horikx’s curve corresponding to the crosslink scis- ever, a significant and continuous increase in Tg with
sion (Equation (7)), suggesting that devulcanization microwave energy values was observed for SBR-P,
process occurred in all microwave treated materials indicating that the structure changed as the micro-
by rather selective breakage of crosslinks. wave energy was enhanced. The increase of the Tg
However, magnitude of this devulcanization was has also been reported by others authors for devulcan-
higher as the microwave energy was increased and ization of sulfur vulcanized rubber by ultrasound
when the SBR was imbibed in IL. An increase in [24]. This change in Tg was attributed to the forma-
the microwave energy resulted in a shift of the data tion of cyclic sulfur structures in the polymer chains.
point to the right hand region of the graph which Such a structure limits the mobility of the chains,
indicated decrease of crosslink density. The shift increasing the Tg of the elastomer. For microwave
phenomenon was even more pronounced for the devulcanization of ground tire rubber [25], this dif-

Figure 11. Horikx diagram for ground rubber (a) without ionic liquid and (b) with ionic liquid

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Figure 12. Glass transition temperatures of ground rubber Figure 14. Mooney viscosity ML (1+4) 100°C for unvul-
with and without ionic liquid as a function of canized raw rubber and different recycled rub-
microwave energy bers (MU is Mooney unit of viscosity: 1 MU =
0.083 N·m)
ference in the Tg values was also attributed to the
higher carbon black content of the devulcanized sponding to the main-chain scission (Equation (7)).
samples. On the other hand, the volatilization at high These points moved from 13 to 38% and from 50 to
temperature (above 200°C) of the extender oil which 65% for SBR and SBR-P respectively. This result
works as a plasticizer for the rubber molecules also indicated that the mechanical shearing of rubber,
tends to diminish the molecular mobility of the rub- involved herein into the two-roll mill, favored the
ber, increasing its Tg. devulcanization process, suggesting that combining
Gums were generated from the devulcanized SBR mechanical loading with microwave energy and IL
and SBR-P materials, treated with microwave energy could be a most profitable procedure allowing an
of 440 Wh/kg. To do this, a laboratory two-roll mill optimal devulcanization of rubbers.
was used with the friction ratio of 1.3, at tempera- Figure 14 shows the Mooney viscosity and Mooney
ture of 50°C and mixing time of 10 min for each relaxation of virgin unvulcanized rubber and
blend. reclaimed rubber obtained after ground rubber mix-
The soluble fractions and the devulcanization propor- ing. The Mooney viscosity of the rubber gives an
tions of the obtained mixtures are reported in Horikx indication of the relative devulcanization degree.
diagram in Figure 13. Data of microwave treated Indeed, more is the degree of devulcanization, lower
SBR powder are also plotted in this figure. It can be is the Mooney viscosity [26]. Thus, curves in Fig-
observed that experimental points of mixtures shifted ure 14 confirmed the earlier results. The specimen
significantly to the right region of the Figure 13, generated from the ground rubber previously treated
while remaining well fitted by theoretical curve corre- by microwave in the presence of IL exhibited
Mooney viscosity close to that of the virgin rubber,
proving high devulcanization of this specimen.

4. Conclusions
Devulcanization styrene butadiene rubber (SBR) by
microwave irradiations has been studied. The effect
of IL (pyrrolidinium hydrogen sulfate [Pyrr][HSO4])
on this devulcanization was particularly analyzed.
High ability of this IL to convert microwave energy
in heat has been proved. The increase in the soluble
fraction with increasing microwave energy was also
more significant for the powder mixed with
[Pyrr][HSO4], further confirming the positive role
Figure 13. Horikx diagram for SBR powder and SBR mix- of the IL in the microwave devulcanization process
ture of rubbers. The measured crosslink density decreased

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with the microwave energy, more significantly for [5] Vega B., Montero L., Lincoln S., Agulló N., Borrós S.:
the SBR-P, testifying that the IL favored the micro- Control of vulcanizing/devulcanizing behavior of
diphenyl disulfide with microwaves as the heating
wave devulcanization mechanism. Results high-
source. Journal of Applied Polymer Science, 108, 1969–
lighted a relationship between the soluble fraction 1975 (2008).
and the devulcanization quantities. In fact, the devul- DOI: 10.1002/app.27578
canization evaluated from Equation (5) was also [6] De D., De D., Singharoy G. M.: Reclaiming of ground
higher as the microwave energy was increased and rubber tire by a novel reclaiming agent. I. Virgin natu-
when the SBR was impregnated in IL, confirming ral rubber/reclaimed GRT vulcanizates. Polymer Engi-
neering and Science, 47, 1091–1100 (2007).
again the positive role of this IL in the devulcaniza-
DOI: 10.1002/pen.20790
tion treatment. Analysis of the temperature distribu- [7] Rajan V. V., Dierkes W. K., Joseph R., Noordermeer J.
tion through the ground rubber proved that micro- W. M.: Recycling of NR based cured latex material
wave irradiation produced efficient heating when reclaimed with 2,2!-dibenzamidodiphenyldisulphide
microwave energy was coupled with the IL. This in a truck tire tread compound. Journal of Applied
could explain the better devulcanization of the rub- Polymer Science, 102, 4194–4206 (2006).
DOI: 10.1002/app.24563
ber in presence of the IL. Finally, the experimental
[8] Tsuchii A., Takeda K.: Rubber-degrading enzyme from
data fitted well with the Horikx’s curve correspon- a bacterial culture. Applied and Environmental Micro-
ding to the crosslink scission, suggesting that devul- biology, 56, 269–274 (1990)
canization process occurred in all microwave treated [9] Karger-Kocsis J., Mészáros L., Bárány T.: Ground tyre
materials by rather selective breakage of crosslinks. rubber (GTR) in thermoplastics, thermosets, and rub-
The magnitude of this devulcanization was higher as bers. Journal of Materials Science, 48, 1–38 (2013).
DOI: 10.1007/s10853-012-6564-2
the microwave energy was increased and when the
[10] Fix S. R.: Microwave devulcanization of rubber. Elas-
rubber was imbibed in IL. tomerics, 112, 38–40 (1980).
As a main conclusion, the use of IL exhibits strong [11] Bani A., Polacco G., Gallone G.: Microwave-induced
potential towards successful and efficient devulcan- devulcanization for poly(ethylene–propylene–diene)
ization of rubbers and reduce the energy required recycling. Journal of Applied Polymer Science, 120,
for devulcanization treatment. 2904–2911 (2011).
DOI: 10.1002/app.33359
[12] Landini L., de Araújo S. G., Lugão A. B., Wiebeck H.:
Acknowledgements Preliminary analysis to BIIR recovery using the micro-
The authors thank the society Phenix Industries from wave process. European Polymer Journal, 43, 2725–
Sancheville (28800), France, for its technical help. 2731 (2007).
DOI: 10.1016/j.eurpolymj.2007.03.017
[13] Scagliusi S. R., Araújo S. G., Landini L., Lugão A. B.:
References Study of properties of chloroprene rubber devulcan-
[1] Fukumori K., Matsushita M., Mouri M., Okamoto H., izate by radiation in microwave. in ‘International
Sato N., Takeuchi K., Suzuki Y.: Dynamic devulcan- Nuclear Atlantic Conference 2009. Rio de Janeiro,
ization and dynamic vulcanization for recycling of Brazil – INAC’ p.8 (2009).
crosslinked rubber. Kautschuk Gummi Kunststoffe, [14] Hong Y. J., Jeong K. M., Saha P., Suh J., Kim J. K.:
59, 405–411 (2006). Processing and characterization of microwave and
[2] Sun X., Isayev A. I.: Ultrasound devulcanization: Com- ultrasonically treated waste-EPDM/LDPE polymer
parison of synthetic isoprene and natural rubbers. Jour- composites. Polymer Engineering and Science, 55,
nal of Materials Science, 42, 7520–7529 (2007). 533–540 (2014).
DOI: 10.1007/s10853-007-1623-9 DOI: 10.1002/pen.23916
[3] Sun X., Isayev A. I.: Continuous ultrasonic devulcan- [15] Maciejewska M., Zaborski M.: Effect of ionic liquids on
ization: Comparison of carbon black filled synthetic the dispersion of zinc oxide and silica nanoparticles,
isoprene and natural rubbers. Rubber Chemistry and vulcanisation behaviour and properties of NBR com-
Technology, 81, 19–46 (2008). posites. Express Polymer Letters, 8, 932–940 (2014).
DOI: 10.5254/1.3548195 DOI: 10.3144/expresspolymlett.2014.94
[4] Novotny D. S., Marsh R. L., Masters F. C., Tally D. N.: [16] Armand M., Endres F., MacFarlane D. R., Ohno H.,
Microwave devulcanization of rubber. U.S. Patent Scrosati B.: Ionic-liquid materials for the electrochem-
4104205 A, USA (1978). ical challenges of the future. Nature Materials, 8, 621–
629 (2009).
DOI: 10.1038/nmat2448

1085
 Seghar et al. – eXPRESS Polymer Letters Vol.9, No.12 (2015) 1076–1086

[17] Silvester D. S., Rogers E. L., Compton R. C., Mcken- [22] Charlesby A.: Gel formation and molecular weight
zie K. J., Ryder K. S., Endres F., Macfarlane D., distribution in long-chain polymers. Proceedings of
Abbott A. P.: Technical aspects. in ‘Electrodeposition the Royal Society of London A, 222, 542–557 (1954).
from ionic liquids’ (eds.: Enders F., MacFarlane D. R., DOI: 10.1098/rspa.1954.0094
Abbot A. P.) Wiley-VCH, Weinheim, 287–351 (2008). [23] Saiwari S., Dierkes W. K., Noordermeer J. W. M.: Com-
[18] Anouti M., Jacquemin J., Porion P.: Transport proper- parative investigation of the devulcanization parame-
ties investigation of aqueous protic ionic liquid solu- ters of tire rubbers. Rubber Chemistry and Technol-
tions through conductivity, viscosity, and NMR self- ogy, 87, 31–42 (2013).
diffusion measurements. Journal of Physical Chem- DOI: 10.5254/rct.13.87933
istry B, 116, 4228–4238 (2012). [24] Levin V. Y., Kim S. H., Isayev A. I.: Effect of crosslink
DOI: 10.1021/jp3010844 type on the ultrasound devulcanization of SBR vulcan-
[19] Flory P. J.: Molecular size distribution in three dimen- izates. Rubber Chemistry and Technology, 70, 641–649
sional polymers. III. Tetrafunctional branching units. (1997).
Journal of the American Chemical Society, 63, 3096– DOI: 10.5254/1.3538450
3100 (1941). [25] Scuracchio C. H., Waki D. A., da Silva M. L. C. P.: Ther-
DOI: 10.1021/ja01856a063 mal analysis of ground tire rubber devulcanized by
[20] Horikx M. M.: Chain scissions in a polymer network. microwaves. Journal of Thermal Analysis and Calorime-
Journal of Polymer Science, 19, 445–454 (1956). try, 87, 893–897 (2007).
DOI: 10.1002/pol.1956.120199305 DOI: 10.1007/s10973-005-7419-8
[21] Charlesby A.: Solubility and molecular size distribu- [26] Sutanto P.: Development of a continuous process for
tion of crosslinked polystyrene. Journal of Polymer EPDM devulcanization in an extruder. PhD Thesis,
Science, 11, 513–520 (1953). University Library Groningen, Netherlands (2006).
DOI: 10.1002/pol.1953.120110601

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